PROCESSES TO SEPARATE OR REMOVE A PERMANGANATE REDUCING COMPOUND AND TO PRODUCE ACETIC ACID

专利摘要:
A process is provided to produce acetic acid by efficiently separating substances that reduce permanent acid (PRC's) and methyl iodide. A mixture (3A) containing PRC's and methyl iodide is distilled in a distillation step (5) to separate the mixture into a suspended flow (5A), a side flow (5B) and a bottom flow (5C), separating or thereby removing the PRC's from the mixture. In the distillation step (5), an extraction agent (water, etc.) capable of extracting the PRC's, preferably in methyl iodide, is added in the concentration region, where the PRC's and methyl iodide are concentrated in the distillation tower , and a descending extract from the concentration region is removed as the lateral flow (5B).
公开号:BR112017020974B1
申请号:R112017020974-8
申请日:2016-05-27
公开日:2020-11-24
发明作者:Masahiko Shimizu；Hiroyuki Miura；Yoshihisa Mizutani
申请人:Daicel Corporation；
IPC主号:

专利说明:

TECHNICAL FIELD
[001] The present invention relates to processes used to separate permanganate reducing compounds (PRC's), such as acetaldehyde and methyl iodide, from one another to remove PRC's, and also refers to processes to produce acetyl acid by methanol carbonylation using the previous separate processes. TECHNICAL FUNDAMENTALS
[002] Acetic acid is produced industrially by carbonylation of methanol in the presence of water, a radio catalyst, a metal iodide and methyl iodide. For the reaction of methanol carbonylation, the reaction mixture contains small amounts of by-products (impurities), for example, a carbonyl compound (for example, acetaldehyde, butyraldehyde, crotonaldehyde, 2-ethylcrotonaldefdo, and an aldol condensation product thereof) , an organic iodide (for example, a C2-12 alkyl iodide such as ethyl iodide, butyl iodide or hexyl iodide) and others. These impurities result in poor quality of acetic acid product. For example, a test with a permanganate reducing compound (permanganate time) detects extremely small amounts of impurities (permanganate reducing compounds; PRC’s), even if the extremely small amounts are difficult to determine quantitatively by current advanced instrumental analysis. Unfortunately, acetaldehyde and methyl iodide have boiling points close to each other, and thus it is difficult to efficiently separate acetaldehyde and methyl iodide from each other, only by means of common distillation. In addition, separation of impurities by combining distillation with water extraction has also been reported. According to this process, for the coexistence of methyl acetate with PRC's, as well as methyl iodide, methyl acetate is dissolved and distributed in an aqueous phase in the extraction of water, and thus methyl iodide can also be undesirably extracted in the aqueous phase. . This results in a loss of methyl iodide.
[003] Public domain publication of Japanese patent application 8-67650 (JP-8-67650A, Document associated with patent 1) describes a process for removing acetaldehyde, comprising the steps of: separating a methanol carbonylation reaction mixture into a volatile phase containing acetic acid, methyl acetate and methyl iodide and a less volatile phase containing a radio catalyst; distill the volatile phase to form a mixture of the product containing acetyl acid and a suspended part containing methyl acetate and methyl iodide; separate the suspended part into a lower phase (a methyl iodide phase) and an upper phase (an aqueous phase containing acetaldehyde); distill the lower phase and / or the upper phase in a distillation column (a column that removes acetaldehyde) to form an acetaldehyde concentrate from the top of the column; and subjecting the acetaldehyde concentrate to a water extraction.
[004] However, in the distillation of the upper phase (aqueous phase) containing acetaldehyde, it is necessary to provide a large amount of energy for distillation and separation of acetaldehyde due to the distillation of water with a great latent heat for evaporation, or it is necessary to reduce the amount of energy required for distillation by increasing the number of distillation stages (or plates). Whereas, in the distillation of the lower phase (methyl iodide phase), it is necessary to increase an amount of reflux or increase the number of distillation stages, due to a small difference in the boiling point between methyl iodide and acetaldehyde. Furthermore, the distillation of a homogeneous mixture or liquid from the upper and lower phases also involves an increase in the amount of steam (in the amount of thermal energy) in the distillation column, and / or an increase in the number of distillation stages . This results in economically low acetic acid production.
[005] Furthermore, the process described in the accompanying associated document 1 fails to increase efficiency in removing acetaldehyde in the distillation column, as acetaldehyde is not concentrated in the suspended part efficiently.
[006] WO 2014/031407 (Document associated with patent 2) describes a process to produce acetic acid, the process comprising the steps of: separating a composition of crude acetate in a column of lights (a separating column) in a suspense stream comprising methyl iodide, water, methyl acetate, and permanganate reducing compounds (PRC's), and a flow of acetate acid product; separating a portion of the suspense stream in a first distillation column to form an enriched stream in at least one PRC, wherein the enriched stream additionally comprises at least some of the methyl iodide; and extractively distilling the stream enriched with an extraction agent (for example, water) in a second distillation column to form a distillate comprising methyl iodide, and a residue comprising at least one PRC and optionally less than 1% by weight of methyl iodide. This document also describes a mass flow ratio of the enriched flow to the extraction agent of at least 0.01: 1.
[007] Unfortunately, according to this process, for distillation and separation in the first distillation column, as well as in the process described in the document associated with patent 1, it is necessary to supply a large amount of energy or it is necessary to increase the number of stages of distillation. In addition, the extractive distillation of the PRC's in the second distillation column requires a large amount of an extraction agent and a large number of the distillation stages and thus requires a large amount of separation energy. In addition, methyl acetate or acetate acid coexisting with the PRC's in the second stage of extractive distillation and dissolved in an aqueous phase in the extractive distillation with water and thus methyl iodide can be extracted undesirably in the aqueous phase. This results in a loss of methyl iodide. QUOTE LIST PATENT ASSOCIATED LITERATURE
[008] Document associated with patent 1: JP-8-67650A (claims, [007], [018], and examples) Document associated with patent 2: WO 2014/031407 (claims) SUMMARY OF THE INVENTION TECHNICAL PROBLEM
[009] Therefore, it is an objective of the present invention to provide a process for efficiently separating PRC's and methyl iodide from each other, and a process for producing acetic acid.
[0010] Another objective of the present invention is to provide a process for efficiently separating PRC's, which results in low quality of acetic acid, and methyl iodide from each other by a compact (or simple) device with a low energy, and a process to produce acetic acid.
[0011] And yet another objective of the present invention is to provide a process for efficiently separating PRC's and methyl iodide from each other, with a small number of distillation stages, and a process for producing acetic acid.
[0012] It is additionally an objective of the present invention to provide a process for efficiently separating PRC's and methyl iodide from one another by extractive distillation of PRC's, in the coexistence of methyl acetate and / or acetate acid, and a process for producing acetic acid. SOLUTION TO THE PROBLEM
[0013] The inventors of the present INVENTION carried out intensive studies to achieve the previous objectives and finally observed that (i) distillation of a mixed composition (or a mixture) containing methyl iodide and a low concentration of acetaldehyde forms a concentration zone (a high concentration zone, or a condensed zone or an enriched zone) of methyl iodide and acetaldehyde in a distillation column; (ii) extractive distillation with water, in which the water (which can preferably extract acetaldehyde) is added to the concentration zone of an upper part of the distillation column, takes the boiling point of the extract greater than the boiling point of acetaldehyde for easily increase the concentration of acetaldehyde in the extract, and efficiently separate the methyl iodide and acetaldehyde from each other to transfer acetaldehyde from the methyl iodide phase to the aqueous phase without concentrating acetaldehyde in the methyl iodide phase (extractive distillation allows for formation an extract containing a high concentration of acetaldehyde); and (iii) removing a liquefied fraction (or an extraction mixture) that falls into the concentration zone not as a bottom flow, but as a side flow, it reduces the amount of energy required for distillation and also reduces the number of distillation stages, and these findings establish a process that allows economically advantageous removal of acetaldehyde. The present invention was carried out based on the previous findings.
[0014] In the following, the present invention will be explained with reference to the reference numbers in the drawings. Referral numbers are used only to assist in understanding the present invention, and are not intended to limit the specific units or process flows indicated by the referral numbers. For example, although figure 1 shows a process comprising indirectly feeding a suspense flow or mixed composition (3A) from a first distillation column (3) to a second distillation column (5), any flow with a mixed composition composition ( 3A) can be fed to any one or a plurality of distillation columns, after the first distillation column (3); any one or a plurality of distillation columns is not limited to the second distillation column (5).
That is, an aspect of the present invention provides a process for separating or removing a permanganate reducing compound (in particular, at least acetaldehyde) from a mixed composition (or a mixture) (3A) containing at least one reducing compound permanganate (a PRC or PRC's including acetaldehyde) and methyl iodide, the process comprising distilling the mixed composition in a distillation step (5) to form a suspense flow (5A), a lateral flow (5B), and a lower flow ( 5C). In a distillation column of the distillation step (5), an extraction agent (or an extraction solvent) that can extract PRC's preferably from methyl iodide and is added to a concentration zone (a high concentration zone) of PRC's and methyl iodide; and an extraction mixture (a liquefied fraction, a falling liquid) which falls from the concentration zone and is withdrawn as the lateral flow (5B).
[0016] The mixed composition (3A) can contain methyl iodide in a concentration of not less than 1.5% by weight (for example, not less than 2% by weight), or it can be a mixed composition in which at least methyl iodide between permanganate-reducing compounds (PRC's) and methyl iodide are concentrated, compared to a mixed flow produced in a previous unit operation. In addition, the mixed composition (3A) can generally contain methyl iodide in a concentration of not less than 10% by weight (for example, not less than 20% by weight). Thus, according to the present invention, the mixed composition (3A) can be separated biphasically and can contain at least a portion of an organic phase, at least a portion of an aqueous phase, or a mixture of the organic phase and the aqueous phase .
[0017] According to a process like this, an upward flow containing concentrated PRC's and methyl iodide is naturally placed in countercurrent contact with a downward flow of the extraction agent, and an extract with a high concentration of PRC's can be formed with a small amount of the extraction agent without highly concentrating the PRC's by distillation, to separate methyl iodide and PRC's from each other. Thus, the process not only enables efficient separation of PRC's and methyl iodide from each other, but also takes the smaller distillation space to efficiently extract PRC's with a small amount of thermal energy, and a small number of distillation stages. .
Therefore, (i) the concentration of PRC (in particular, the concentration of acetaldehyde) in the extraction mixture or side flow (5B) may be greater than (or increased compared to) the concentration of PRC in each of mixed composition (3A) and lower flow (5C). For example, (ii) the concentration of each PRC's or the concentration of all PRC's in the extraction mixture or side flow (5B) (for example, an aqueous phase formed from the extraction mixture) can be about 0 , 1 to 45% by weight (for example, about 5 to 45% by weight). Furthermore, (iii) the ratio of PRC's (in particular, acetaldehyde) to methyl iodide in the extraction or side flow mixture (5B) may be greater than PRC's (in particular, acetaldehyde) relative to methyl iodide in each flow of the mixed composition (3A) and the lower flow (5C). In addition, the concentration of methyl iodide in the aqueous phase formed from the side flow (5B) can be reduced compared to a concentration of methyl iodide, in an aqueous phase formed by water extraction from a distillate (a suspended condensate) to from a conventional acetaldehyde removal column, and thus a loss of methyl iodide can be reduced.
[0019] The mixed composition (3A) may additionally contain methyl acetate. Furthermore, the mixed composition (3A) can contain at least one component selected from the group consisting of acetate, methanol, water, dimethyl ether and an acetaldehyde derivative (a substance derived from acetaldehyde).
[0020] The flow rate of the extraction agent can be relatively low and, for example, the weight ratio of the flow rate of the extraction agent with respect to the flow rate of the mixed composition (3A) [the first / the last] can be about 0 , 0001/100 to 100/100, preferably about 0.0001 / 100 to 20/100, and particularly about 0.001 / 100 to 10/100 in terms of liquid matter.
[0021] Specifically, the distillation column of the distillation step (5) can in general be provided with a receiver disposed in a position lower than an add-on port for the extraction agent. The height of the receiver can be the same as the height of a feed port for the mixed composition (3A), or it can be greater or less than a feed port for the mixed composition (3A).
[0022] In a case where the receiver is arranged in a position lower than the feed port for the mixed composition (3A), the receiver can be positioned higher than the bottom flow. A receiver like this can allow a vapor or evaporation fraction from the mixed composition to ascend to the concentration zone, and may be able to receive the extraction mixture (liquefied fraction, liquid that falls) that falls from the concentration zone. The extraction agent that is separable from methyl iodide to form an extract phase can be added to the concentration zone formed below (or above) the receptor. The extraction mixture can be removed as a side flow (5B) from a withdrawal port that communicates with the receiver. The extraction agent can be added or sprayed from an additive port positioned at a higher position in the distillation column than the feed port for the mixed composition. More specifically, the distillation column can be provided with at least one chimney tray. An aqueous extraction agent can be added or sprayed on the concentration zone which is formed below (or on top of) a higher flue pan, and containing a vapor or evaporation fraction from the mixed composition (3A); the extraction mixture from the concentration zone (or the liquid that falls from the concentration zone, the liquefied mixture) can be received in a section of the tray or area of the chimney tray; and the extraction mixture retained in the section or area of the tray can be removed as the lateral flow (5B).
[0023] The extraction agent may be an aqueous extraction agent, for example, at least one aqueous solvent selected from the group consisting of (i) water, (ii) an aqueous process flow produced in the process, and (iii) an aqueous solution (or an aqueous mixture) produced by water absorption treatment of a gas generated from the process. The aqueous solvent (or process flow) (ii) produced in the process can contain, for example, water and at least one component selected from the group consisting of PRC's, methyl iodide, acetate, methyl acetate, methanol, dimethyl ether , and all components (such as impurities) present in the aqueous process flow.
[0024] Feeding the extraction agent (for example, an aqueous solvent such as water) into the distillation column, from its upper position (for example, the top), probably allows the extraction mixture or the liquid to fall to form a liquid-liquid it remains easily separated. Thus, the extraction mixture (5B) can be liquid-liquid separable in an upper and a lower phase. In a case where the extraction mixture (5B) is separable into an aqueous phase and an organic phase, the aqueous phase can be separated, and the organic phase can be recycled in the distillation column or the like. For example, at least one portion (or the total amount) of the extraction mixture (5B) can be removed from the distillation column in the distillation step, (5) and separated biphasically into aqueous and organic phases, the aqueous phase containing at least acetaldehyde can be separated, and the organic phase containing at least methyl iodide can be recycled in the distillation column of the distillation step (5) directly or indirectly. The extraction mixture (5B) and the suspense flow (5A) can be separated biphasically independently or in combination (for example, at least the extraction mixture (5B) between the extraction mixture (5B) and the suspense flow ( 5A) can be separated biphasically) to form aqueous phase and organic phase, the aqueous phase containing at least acetaldehyde can be separated, and the organic phase containing at least methyl iodide can be recycled in the distillation column of the distillation step (5) . In the distillation column of the distillation step (5), the extraction mixture (the liquid that falls) can be kept in the tray to form an aqueous phase containing at least acetaldehyde and an organic phase containing at least methyl iodide, the aqueous phase it can be separated, and the organic phase can be recycled in the distillation column of the distillation step (5). The extraction mixture can be removed from the distillation column in the distillation step, and separated biphasically to form an aqueous phase containing at least acetaldehyde and an organic phase containing at least methyl iodide, and at least a portion of the aqueous phase and the phase organic can be recycled in the distillation column of the distillation step. The organic phase can be fed in a higher or lower position than the lateral flow (or to) withdrawal port (5B) to form a concentration zone in the distillation column of the distillation step (5).
[0025] According to the present invention, PRC's (for example, acetaldehyde) can be efficiently extracted with an aqueous extraction agent such as water, and the vapor pressure of PRC's (for example, acetaldehyde) in the extraction agent aqueous can be decreased (i.e., the boiling point of the extract can be increased or raised) to increase the concentration of PRC's in the extraction agent. Using a greater distribution factor of PRC's (for example, acetaldehyde) in the aqueous phase compared to the organic phase (or methyl iodide phase), the concentration of PRC's (for example, acetaldehyde) in the aqueous extraction agent phase (phase aqueous) may be greater compared to the organic phase (or methyl iodide phase). Thus, the reduced concentration of PRC's in the organic phase and the efficient dissolution of PRC's in the aqueous phase can separate PRC's and methyl iodide from each other. In addition, since the concentration of PRC's in the organic phase can be reduced, PRC's (for example, acetaldehyde) can be removed efficiently in the form of an aqueous solution, even in a small number of distillation stages (or plates) and energy low (energy saving).
[0026] The extraction mixture (the liquid that falls) removed can be separated biphasically in a decanter, for example, with the retention time of not less than 10 seconds. The residence time (or retention) can be the total residence time of the liquid that is in contact with the extraction agent in the receiver (or flue pan) of the distillation column and the residence time of the liquid in the decanter.
[0027] The mixed composition (3A) contains PRC’s (e.g., acetaldehyde) and methyl iodide. The mixed composition (3A) can be produced in a process to produce acetic acid. For example, the process of the present invention may comprise: (1) a reaction step to continuously carbonize methanol in the presence of a catalyst system containing a metal catalyst, metal halide and methyl iodide; (2) a rapid evaporation step to continuously separate the reaction mixture into a volatile phase (2A) containing the product of acetate and methyl iodide, and a less volatile phase (2B) containing the metal catalyst and the metal halide; (3) a first distillation step to continuously separate the volatile phase (2A) into a suspended part (3A) containing methyl iodide and acetaldehyde by-product, and a flow (3B) containing acetate acid; and (4) a step to condense a gas phase to form an organic phase and an aqueous phase, the gas phase being produced from at least one step selected from the group consisting of these steps and containing at least acetaldehyde and methyl iodide, wherein at least a portion of the organic phase (the organic phase rich in methyl iodide) and / or at least a portion of the aqueous phase can be subjected to the second distillation step (5), and water or at least a portion of the aqueous phase ( the aqueous phase rich in acetaldehyde) can be used as the extraction agent. For example, the suspended part (3A) can be placed in contact with water to form an organic phase rich in methyl iodide and an aqueous phase rich in acetaldehyde, and the organic phase can be subjected to the second stage of distillation (5), and the aqueous phase can be used as the extraction agent in the second distillation step (5).
[0028] The suspense flow (5A) and / or the lateral flow (extraction mixture) (5B) separated in the distillation step (5) can be additionally subjected to a third distillation step (7). For example, at least the extraction mixture (5B) between the suspense flow (5A) and the extraction mixture (5B) can be separated biphasically into an aqueous phase and an organic phase, and at least a portion of the aqueous phase can be separated. subjected to a subsequent distillation step (7) to form a suspended flow (a lower boiling point flow, an upper flow) (7A) containing acetaldehyde and methyl iodide, and a liquid flow (7B) (a flow of highest boiling point, bottom flow or lower flow) containing the extraction agent. The liquid flow (7B) containing the extraction agent can be reused as the extraction agent in the second distillation step (5). The suspended part (7A) can have a PRC concentration (representative, acetaldehyde) of about 1 to 99% by weight and a methyl iodide concentration of about 0.1 to 10% by weight, and the flow liquid (7B) may have a methyl iodide concentration of not more than 1% by weight (provided that each stream, including impurities, has a total amount of 100% by weight).
[0029] In the manner described above, at least the extraction mixture (5B) between the extraction mixture (5B) and the suspense flow (5A) can be separated biphasically into an aqueous phase and an organic phase (or a refined one) containing at least methyl iodide, at least a portion of the aqueous phase can be subjected to distillation in the subsequent distillation step (7) and / or the extractive distillation with water in a subsequent distillation step (8), the organic phase can be directly or indirectly recycled in the second distillation step (5) from a position lower than the withdrawal port for lateral flow (5B). Furthermore, a miscible solvent, which is miscible with the organic phase separated from the extraction mixture (5B), can be directly or indirectly fed in the second distillation step (5) from a position lower than the withdrawal port. for lateral flow (5B). The miscible solvent can be, for example, at least one component selected from the group consisting of water, acetate, methyl iodide and methanol.
[0030] The amount to be added of the miscible solvent can be not more than 30% by weight, with respect to the amount of the liquid that falls from the concentration zone in the distillation column of the distillation step (5). The total amount to be recycled from the aqueous phase separated from the extraction mixture (5B), and / or the amount to be added from the miscible solvent can be no more than 30% by weight with respect to the amount of liquid that falls from the concentration zone in the distillation step (5).
[0031] The process of the present invention may further comprise (8) a step to subject the following (a) and / or (b) extraction of water or extractive distillation with water: (a) at least a portion of the separated aqueous phase at least the extraction mixture (5B) between the extraction mixture (5B) and the suspended flow (5A), and (b) the suspense flow (7A) of the third distillation step (7). The water extraction step (8) can be a step to separate the suspended flow (7A) into a phase or flow (a refined) rich in methyl iodide and a phase or flow (an extract) rich in PRC's, or it can (8) a fourth distillation step to subject the suspended flow (7A) to extractive distillation with water to form a suspended flow (8A) and a liquid bottom flow (8B). In the distillation step (8), water extraction can be carried out under the condition that the ratio of methyl iodide to acetaldehyde in the suspended stream (8A) is greater than that in the liquid feed stream.
[0032] Another aspect of the present invention provides a process for producing acetic acid using the above separation process. The production process comprises distilling a mixed composition (or a mixture) (2A) containing at least one permanganate reducing compound (PRC), methyl iodide, methyl acetate and acetate to separate the mixed composition into a suspended part (3A ) containing at least acetaldehyde and methyl iodide, and an acetate acid stream (3B) containing acetate product; and subjecting at least a portion of the suspended part (3A) to the distillation step (5) to provide acetic acid. Specifically, acetic acid can be produced continuously by the process comprising: (1) a reaction step to continuously carbonize methanol in the presence of a catalyst system containing a metal catalyst, a metal halide and methyl iodide; (2) a rapid evaporation step to continuously separate the reaction mixture into a volatile phase (2A) containing acetate acid and methyl iodide product, and a less volatile phase (2B) containing the metal catalyst and the metal halide; (3) a distillation step to continuously separate the volatile phase (2A) into a suspended part (3A) containing methyl iodide and acetaldehyde by-product, and a flow (3B) containing acetate acid; and the distillation step (5) to distill at least a portion of the suspended part (3 A).
[0033] As used herein, acetaldehyde can be referred to simply as PRC’s. The extraction mixture in the distillation column of the distillation step (5) is removed as the side flow (5B), and thus the side flow (5B) taken from the distillation step (5) can be referred to simply as an extraction mixture (5B). The term "liquid that falls" is synonymous with "flow that falls". The term "extraction mixture" is synonymous with "extracted mixture" or "extraction mixture flow". ADVANTAGE EFFECTS OF THE INVENTION
[0034] According to the present invention, since PRC's are preferably extracted with an extraction agent from a concentration zone of PRC's and methyl iodide, and the extraction mixture is withdrawn as a side flow, PRC's and iodide from methyl are efficiently separated from each other. Thus, PRC’s and methyl iodide are efficiently separated from each other with significantly less extraction agent and low energy. Additionally, PRC’s and methyl iodide are further separated from each other by a compact (or simple) device with a distillation column with a small number of stages (or plates). Furthermore, PRC’s and methyl iodide are efficiently separated from each other even in coexistence with methyl acetate or acetate. BRIEF DESCRIPTION OF THE DRAWINGS
[0035] Figure 1 is a flow chart (or a flow diagram) to explain a production process (or production apparatus) for acetate acid according to an embodiment of the present invention.
[0036] Figure 2 is a flow chart (or a flow diagram) for explaining a production process (or production apparatus) for acetic acid according to another embodiment of the present invention.
[0037] Figure 3 is a flow chart (or a flow diagram) to explain a process according to a modality of examples.
[0038] Figure 4 is a flow chart (or flow diagram) to explain a conventional acetic acid production process (or production apparatus). Figure 5 is a graph showing a relationship between an acetaldehyde (AD) concentration. and a methyl iodide / acetaldehyde ratio (Mel / AD ratio) in the examples. DESCRIPTION OF THE MODALITIES
[0039] In the following, the present invention will be explained in detail with reference to the drawings, if necessary. In figures 1 to 4, each stage and an apparatus or main unit for the corresponding stage can be indicated by the same reference number. Unless otherwise specifically noted, an aqueous phase containing acetaldehyde obtained by liquid-liquid (or biphasic) separation is synonymous with a light phase or a higher phase, and an organic phase containing methyl iodide obtained by the liquid-liquid separation ( or biphasic) and synonymous with a heavy phase, a methyl iodide phase, or a lower phase. An aqueous phase obtained by extraction is synonymous with an extract, and an organic phase obtained by extraction means the same as a refined one.
[0040] Referring to a distillation column, the term "number of stages (or plates)" means both the theoretical number of stages (or plates) and the number of actual stages (or plates). For example, a theoretical stage (or plaque) corresponds to two real stages (or plaques) if the efficiency of the real stage (or plaque) is 50%. The type or type of the distillation column is not limited to a plate column (Oldershaw), and can be a fill column. The type or type of the distillation column is not particularly limited to a specific one. In the following, unless otherwise specifically noted, the term "number of stages (or plates)" simply means the number of actual stages (or plates) in a column of plates. The position in which a fluid flows in / out of a filling column (inlet / outlet position) means a position that corresponds to a plate height level of a plate column. For example, the 20th plate at the bottom of a column of plates with the number of actual stages (or plates) of 50 means a height level that corresponds to the 20th plate / 50 plates at the bottom of a filling column (the height "0.4" with respect to height "1" of a filling layer or bed of a filling column).
[0041] The embodiment of figure 1 shows a continuous process (or apparatus) for producing acetate acid from a reaction mixture (or a liquid reaction medium), produced by reaction of methanol carbonylation with carbon monoxide, in the presence of a catalyst system comprising a rhodium catalyst as a metal catalyst and a co-catalyst [lithium iodide as a metal halide and methyl iodide], as well as acetic acid, methyl acetate, and a finite (or limited) amount of Water.
The process (or production apparatus) comprises (1) a reaction step (a reaction system or a reactor) to carry out a methanol carbonylation reaction; (2) a rapid evaporation step (an evaporator) to separate a reaction mixture (or a reaction liquid) containing acetate acid product in a volatile phase (or lower boiling point fraction) (2A) and a lesser phase volatile (or higher boiling point fraction) (2B); (3) a first distillation step (a separator column or a distillation column) for separating the volatile phase (2A) into a first suspended part (3A), an acetate acid flow (3B) as a side flow, and a liquid bottom flow (higher boiling point fraction) (3C); (4) a first liquid-liquid separation step to condense the first suspended part (3A) to form two phases; (5) a second distillation step (a second distillation column) to separate an organic phase (a heavy phase rich in methyl iodide) formed in the liquid-liquid separation step (4) in a suspended flow (5A), one lateral flow (5B), and a lower flow (5C); (6) a second liquid-liquid separation step (a separation unit 6a, a holding tank 6b, and a decanter 6c) to separate the second suspense flow (5A) and the lateral flow (5B) into two phases; (7) a third distillation step (a third distillation column) to separate an aqueous phase (light phase) formed in the second liquid-liquid separation step (6) into a third suspended flow (7A) and a liquid flow (7B ); and (8) a fourth distillation step (a fourth distillation column) for subjecting a third suspended flow (7A) to extractive distillation with water to form a suspended flow (8A) and a liquid bottom flow (8B).
[0043] By the way, among these steps, the process of the present invention comprises at least the second distillation step (5). Other steps (for example, the first liquid-liquid separation step (4), the second liquid-liquid separation step (6), the third distillation step (7), and the fourth distillation step (8)) they are necessarily essential. The process of the present invention generally comprises the first stage of distillation (3), the stage of liquid-liquid separation (4), and the second stage of distillation (5), and may comprise the stage of liquid-liquid separation (6 ). The second distillation step (5) is not limited to a single distillation step and can contain a plurality of distillation steps using a plurality of distillation columns. For the production of acetic acid, the process of the present invention in general further comprises the reaction step (1) and the rapid evaporation step (evaporator) (2).
[0044] As the distillation column for each of the distillation steps (3), (5), (7), and (8) (including the separator column for the first distillation step (3)), a plate column, a filling column, or other columns.
[0045] Next, the process shown in figure 1 will be explained in more detail. (1) Reaction step (Reactor)
[0046] In the reaction step (reactor) (1), methanol and carbon monoxide are continuously fed into a reactor in the presence of a reaction medium containing a carbonylation and water catalyst system, and produce acetyl acid by methanol carbonylation.
The carbonylation catalyst system in general contains a metal catalyst (such as a cobalt catalyst, a rhodium catalyst, or an iridium catalyst), a catalyst stabilizer or reaction accelerator, and a co-catalyst. Metal catalysts can be used alone or in combination. The metal catalyst may preferably include a rhodium catalyst and an indium catalyst (in particular, a rhodium catalyst).
[0048] The metal catalyst can be used in the form of a simple metal, a metal oxide (including a complex metal oxide), a metal hydroxide, a metal iodide, a metal carboxylate (for example, an acetate), a metal salt of an inorganic acid (for example, a sulfate, a nitrate and a phosphate) or a metal complex. It is preferable to use the metal catalyst in a form (for example, a complex form) dissolved in a liquid phase (or a reaction liquid). The rhodium catalyst may preferably include, for example, a rhodium iodide complex (e.g., Rhl3, Rhl2 (CO) 4] ', and [Rh (CO) 2l2]} and a rhodium carbonyl complex. The metal catalyst has a concentration of, for example, about 100 to 5,000 ppm (on the basis of weight, the same applies below), preferably about 200 to 3,000 ppm, more preferably about 300 to 2,000 ppm, and particularly about 500 to 1,500 ppm in the complete liquid phase in the reactor.
The catalyst stabilizer or reaction accelerator may include a metal iodide capable of producing an iodide ion in the reaction medium, for example, an alkali metal iodide (for example, lithium iodide, sodium iodide and potassium iodide ). Among these stabilizers, lithium iodide is preferred. These co-catalysts or accelerators can be used alone or in combination.
The catalyst stabilizer or reaction accelerator in the complete liquid phase in the reactor has a concentration of, for example, about 1 to 25% by weight, preferably about 2 to 22% by weight, and more preferably about 3 to 20% by weight. The iodide ion in the reaction system can have a concentration of, for example, about 0.05 to 2.5 mol / L and preferably about 0.25 to 1.5 mol / L.
[0051] As the co-catalyst, methyl iodide can be used. The methyl iodide in the complete liquid phase in the reactor has a concentration of, for example, about 1 to 30% by weight, preferably about 5 to 25% by weight, and more preferably about 6 to 20% by weight (eg example, about 8 to 18% by weight).
A preferred carbonylation catalyst system may comprise a radio catalyst, a metal iodide as a catalyst stabilizer (e.g., lithium iodide), and methyl iodide as a co-catalyst. The reactor can be fed a mixture of catalyst (a liquid catalyst) containing the carbonylation and water catalyst system.
[0053] The reaction medium (or liquid phase) in general contains acetate acid product, methyl acetate formed by a reaction of acetate acid product and methanol raw material, and water. Acetic acid also works as a solvent. Furthermore, the reaction medium (or liquid phase) generally contains raw material of unreacted methanol. The proportion of methyl acetate in the complete reaction liquid can be about 0.1 to 30% by weight, preferably about 0.3 to 20% by weight, and more preferably about 0.5 to 10% by weight ( for example, about 0.5 to 6% by weight). The water in the reaction medium may have a low concentration. The water in the complete reaction liquid has a concentration of, for example, about 0.1 to 15% by weight, preferably about 0.5 to 10% by weight, and more preferably about 0.8 to 5% by weight. weight (for example, about 1 to 3% by weight) or can have a concentration of about 1 to 10% by weight (for example, about 2 to 5% by weight).
[0054] The partial pressure of carbon monoxide in the reactor can be a pressure of, for example, about 0.2 to 3 MPa and preferably about 0.4 to 1.5 MPa. A residual gas containing carbon monoxide produced in the subsequent step (s) can be recycled in the reaction system.
The carbonylation reaction produces hydrogen by a reaction of carbon monoxide with water. Hydrogen increases catalyst activity. Thus, hydrogen can be fed into the reactor, if necessary. Hydrogen can be fed into the reactor by recycling gaseous component (s) (including hydrogen, carbon monoxide, or other gases) depleted in the process, if necessary after purifying and / or separating the component (s) ) gaseous (s) in the subsequent step (s). The partial pressure of hydrogen in the reaction system can be a pressure of, for example, about 0.5 to 250 kPa (for example, about 1 to 200 kPa), preferably about 5 to 150 kPa, and more preferably about from 10 to 100 kPa (for example, about 10 to 50 kPa) in terms of absolute pressure.
The temperature of the carbonylation reaction can be, for example, about 150 to 250 ° C, preferably about 160 to 230 ° C, and more preferably about 170 to 220 ° C. The reaction pressure (total pressure of the reactor), including partial pressures of by-products, can be, for example, about 1.5 to 4 MPa.
[0057] In the reactor, the reaction of methanol carbonylation continues with the formation of a balance between a liquid phase reaction system and a gas phase system. The liquid phase reaction system contains the reagent (s) and the metal catalyst component, and the gas phase system comprises carbon monoxide, reaction products (hydrogen, methane and carbon dioxide), and components of lowest boiling point vaporized (for example, methyl iodide, acetic acid product, and methyl acetate). The vapor components (ventilation gas) can be removed from the top (or top) of the reactor (1), or they can be subjected to an absorption treatment to recover carbon monoxide and / or hydrogen which can then be recycled in the reactor .
[0058] The reaction mixture (the crude reaction liquid) contains acetate, components or impurities with a lower boiling point, each with a lower boiling point than that of acetate (for example, methyl iodide as a co-catalyst, methyl acetate as a reaction product of acetate and methanol, water, and acetaldehyde as a by-product) and components or impurities with a higher boiling point, each with a higher boiling point than that of acetyl acid [e.g., a metal catalyst component (e.g., a rhodium catalyst), lithium iodide as a catalyst stabilizer, and a C3-12 alkane carboxylic acid (e.g., propionic acid)]. In addition, acetaldehyde derivatives (acetaldehyde derivatives) are also produced. Acetaldehyde derivatives can include, for example, other aldehydes such as butyraldehyde, crotonaldehyde, 2-ethylcrotonaldehyde and 2-ethylbutyraldehyde; a ketone such as acetone or methyl ethyl ketone; an aldol condensation product thereof; and a C2-12 alkyl iodide, such as ethyl iodide, propyl iodide, butyl iodide, pentyl iodide or hexyl iodide. By-products can also include a 3-hydroxy channel (for example, 3-hydroxy butanal); formic acid or C3.12 alkane carboxylic acid (such as propionic acid, butanoic acid, hexanoic acid, heptanoic acid or octanoic acid); a C3.12 alkyl alcohol such as butyl alcohol or 2-ethylbutyl alcohol; a methanol ester or the previous alkyl alcohol with acetyl acid, or the previous carboxylic acid; a methanol ether and / or the previous alkyl alcohol (a dialkyl ether, such as dimethyl ether); and methane, and a hydrocarbon with two or more carbon atoms (for example, a € 2-12 alkane). These by-products are generally increased in proportion to the square and the cube of the acetaldehyde concentration. Methane and a hydrocarbon with two or more carbon atoms (for example, a C2.12 alkane) can be produced. Acetaldehyde and by-products derived from acetaldehyde (for example, other aldehydes, ketone, and aldol condensation product) belong to the permanganate reducing compounds (PRC’s). Thus, it is preferable to separate and remove acetaldehyde, which is a major by-product, from the reaction mixture and recover components (e.g., methyl iodide) from the process flow (s) for efficient use. . Incidentally, as used herein, methyl iodide is excluded from PRC's, although C2-12 alkyl iodide as well as methyl iodide also belong to PRC's.
[0059] According to the present invention, acetaldehyde is efficiently separated and removed to decrease the concentration of acetaldehyde in the reactor, even in a continuous reaction. With the decrease in acetaldehyde concentration or the elimination of acetaldehyde, the production of by-products derived from acetaldehyde is significantly prevented. For example, the complete liquid phase in the reactor can have a PRC concentration (in a representative way, acetaldehyde) of, for example, no more than 1,000 ppm (for example, 0 or limit detection to 700 ppm), preferably no more than 400 ppm (for example, 5 to 300 ppm), and more preferably about 10 to 250 ppm throughout the complete process.
The space and time yield of the target carboxylic acid (acetic acid) in the reaction system can be, for example, about 5 mol / Lh to 50 mol / Lh, preferably about 8 mol / Lh to 40 mol / Lh, and more preferably about 10 mol / Lh to 30 mol / Lh.
[0061] The reaction system is an exothermic reaction system that accompanies heat generation, and the reaction temperature can be controlled (or regulated) by recycling the condensate that has been cooled or from which the heat has been removed, installing a unit removable by heat (or that removes heat) or a cooling unit (for example, a cover). In order to remove part of the reaction heat, a vapor (ventilation gas) from the reactor can be cooled in a condenser, a heat exchanger, or other means to separate the vapor into liquid components and gaseous components, and the liquid components and / or the gaseous components can be recycled in the reactor. (2) Rapid evaporation step
[0062] In the rapid evaporation step (2), a portion of the reaction mixture is continuously removed from the LE reactor introduced or fed into an evaporator (catalyst separation column) (2) through a feed line 11 to separate the reaction mixture in a volatile phase (2A) and a less volatile one (2B); the volatile phase (2A) contains product of acetic acid, methyl iodide, acetaldehyde, methyl acetate, water or other compounds, and the less volatile phase (2B) contains the rhodium catalyst and lithium iodide. At least one first portion of the volatile phase (2A) is fed into a distillation column of the first distillation step (3) via a feed line 22, and the less volatile phase (2B) is recycled in the reactor of the reaction (1) by means of a recycling line 21.
[0063] A second portion of the volatile phase (2A) can be cooled and condensed in a condenser Cl in a line 23. The resulting condensate can be kept in an HT holding tank to recycle the condensate in the reaction step (reactor) ( 1). The cooled product (condensate and / or non-condensable component) in condenser Cl can be fed in the liquid-liquid separation step (4) via a line 26, and can be kept in a decanter (4) together with a suspended part (3A) from the first distillation step (separating column) (3), and a mixture of the cooled product and the suspended part (3A) can be separated into two phases in the decanter (4). [Volatile phase condensation]
[0064] The second portion of the volatile phase (2A) can be fed, without condensation, in the second distillation step (5) directly or indirectly through the liquid-liquid separation step (4), or it can be cooled and condensed in one or a plurality of capacitors C1 to form two phases (an aqueous phase or an organic phase), to subject the aqueous phase or the organic phase (at least the aqueous phase) to the second distillation step (5) directly or indirectly, by middle of the liquid-liquid separation step (4). For example, the second portion of the volatile phase (2A) can optionally be condensed in the manner described above (and optionally be separated liquid-liquid), and mixed with the condensate obtained in the liquid-liquid separation step (4), and the mixture it can be subjected to the second distillation stage (5).
[0065] If necessary, the catalyst component (metal catalyst component) and the catalyst stabilizer, or reaction accelerator, can be separated from the less volatile phase (2B) by one or a plurality of steps, and can be recycled into reaction step (1).
[0066] Rapid evaporation may include an instant thermostat, in which the reaction mixture is heated and depressurized, a rapid adiabatic agent in which the reaction mixture is depressurized without heating, or a combination of these rapid conditions. By rapid evaporation like this, the reaction mixture can be separated into the vapor phase and the liquid phase. For example, rapid distillation can be carried out at a temperature of the reaction mixture of about 80 to 200 ° C, a pressure (absolute pressure) of the reaction mixture of about 50 to 1,000 kPa (for example, about 100 to 1,000 kPa), preferably about 100 to 500 kPa, and more preferably about 100 to 300 kPa.
[0067] Rapid evaporation, for example, can be carried out at a temperature of about 100 to 250 ° C (for example, about 110 to 200 ° C), preferably about 120 to 180 ° C (for example, about 125 to 170 ° C), and more preferably about 130 to 160 ° C. The pressure (manometric pressure) can be about 0.01 to 1 MPa (for example, about 0.03 to 1 MPa), preferably about 0.05 to 0.5 MPa, and more preferably about 0.08 to 0.3 MPa (for example, about 0.1 to 0.2 MPa). The less volatile phase or liquid catalyst mixture can have a temperature of, for example, about 80 to 200 ° C (for example, about 90 to 180 ° C), preferably about 100 to 170 ° C (for example , about 120 to 160 ° C), and more preferably about 130 to 160 ° C. (3) First distillation step (Separating column)
[0068] In the first distillation step (separating column) (3), the volatile phase (2A) is separated into a first suspended part (3A), an acetate acid flow (3B), and a bottom flow (3C) ; the first suspended part (3A) (suspended gas, lower boiling point flow or lower boiling point fraction) and withdrawn from a top or upper position (or part) of the column by means of a withdrawal line 32, the flow of acetic acid (3B) is cut laterally by means of a line 38 and contains mainly acetate acid, and the bottom flow (3C) (higher boiling point flow or higher boiling point fraction) is taken from a deep or lower part of the column by means of a bottom line 31. The proportion of the first suspended flow or suspended part (3A) can be about 35 to 50% by weight in the complete volatile phase (2A).
The first suspended stream (3A), which corresponds to a mixed composition (3A), contains at least both the permanganate reducing compound (PRC) and methyl iodide. The PRC contains at least acetaldehyde by-product. The first suspended stream (3A) generally contains methyl acetate and contains practically acetate, methanol, water, dimethyl ether, by-products derived from acetaldehyde (for example, an aldehyde such as crotonaldehyde or butyraldehyde; an acetaldehyde derivative such as an iodide alkyl C2-12 or a C3.12 alkane carboxylic acid; and a 62-12 alkane).
[0070] The acetate acid flow or side flow (3B) is additionally fed in a purification step by a distillation column or other means (not shown) to remove water or impurities with a higher boiling point, or other impurities from the flow (3B), thus producing purified acetate acid with a high purity. The liquid flow (3C) generally contains at least water and acetate, and also contains practically methanol, propionic acid, or other compounds. The liquid stream (3C) can contain a coupled metal catalyst component. The liquid flow (3C) can be dispensed via line 31, or a portion or the entire liquid flow (3C) can be recycled in the reaction step (reactor) (1) via a line 90.
[0071] The process of the present invention can be applied to the mixed composition or suspended stream which contains at least one PRC and methyl iodide. The first suspended part (3A) can be subjected to the second distillation step (5) in a gaseous form. In a preferred embodiment, PRC's are efficiently extracted with a small amount of the extraction agent, in a small extraction space, and the process is efficiently applied to the mixed composition or suspended flow (3A) which contains a high concentration of at least iodide. methyl (in particular, high concentrations of at least methyl iodide and PRC's). Incidentally, the mixed composition or suspended flow (3A) may have a higher concentration of water. Thus, in the manner shown in figure 1, by a previous step or unit operation [for example, the distillation step (3), the liquid-liquid separation step (4)], the mixed composition (3A), in which methyl iodide and (in particular, both methyl iodide and PRC's are) concentrated, and produced. In this embodiment, the mixed composition (3A) is condensed and separated biphasically in the liquid-liquid separation step (4), and the resulting organic phase and / or aqueous phase is subjected to the second distillation step (5).
[0072] The internal temperature of the distillation column (separating column) of the first distillation step (3) depends on its internal pressure. At the internal pressure of an atmospheric pressure (1 atm = about 0.1 MPa), the distillation column can have a column top temperature of, for example, about 20 to 100 ° C (for example, about 30 at 80 ° C) and preferably about 40 to 70 ° C (for example, about 50 to 60 ° C), or it can have a column bottom temperature of, for example, about 40 to 120 ° C (for example for example, about 50 to 100 ° C) and preferably about 60 to 90 ° C (for example, about 70 to 85 ° C). The distillation column can have a pressure of, for example, about 0.1 to 0.5 MPa, preferably about 0.2 to 0.4 MPa, and more preferably about 0.25 to 0.35 MPa in terms of absolute pressure.
The distillation column may have a theoretical stage or plate (or the theoretical number of stages or plates) of, for example, about 2 to 100 (for example, about 5 to 70) and preferably about 7 to 50 (for example, about 10 to 30). The flow rate of the distillation column can be infinite or it can be, for example, about 1 to 5,000 (for example, about 10 to 4,000) and preferably about 100 to 3,000 (for example, about 500 to 2,000) .
[0074] The internal temperature of the distillation column (separating column) of the first distillation step (3) depends on its internal pressure. At the internal pressure of an atmospheric pressure (1 atm = about 0.1 MPa), the distillation column can have a column top temperature of, for example, about 50 to 180 ° C (for example, about 70 at 170 ° C) and preferably about 80 to 160 ° C (for example, about 90 to 140 ° C), or it can have a column bottom temperature of, for example, about 60 to 200 ° C (for example for example, about 80 to 180 ° C) and preferably about 90 to 170 ° C (for example, about 100 to 160 ° C). The distillation column can have a pressure (manometric pressure) of, for example, about 0.05 to 0.5 MPa, preferably about 0.08 to 0.4 MPa, and more preferably about 0.1 to 0 , 3 MPa.
[0075] The distillation column can have a theoretical stage or plate of, for example, about 2 to 100 (for example, about 5 to 70) and preferably about 7 to 50 (for example, about 10 to 30 ). The flow rate of the distillation column can be infinite or it can be, for example, about 1 to 1,000 (for example, about 5 to 500) and preferably about 10 to 100 (for example, about 15 to 50) (4) Liquid-liquid condensation / separation step
[0076] The first suspended part (3A) of the first distillation step (separating column or distillation column) (3) is cooled and condensed in a C2 condenser in a withdrawal line 32, and the condensate is separated biphasically in one aqueous phase rich in acetaldehyde and an organic phase rich in methyl iodide in a decanter (a decanter, a storage vessel) (4). A portion of the condensate (the aqueous phase and / or the organic phase) is returned to the separating column (3) by means of a reflux line 42 (42a, 42b) by reflux. At least one portion of the aqueous phase is fed into a distillation column of the second distillation step (5), and at least one portion of the organic phase is recycled in the reaction step (1) via a line 41. In the mode shown in figure 1, a portion of the aqueous phase is returned to the separating column (3) by means of reflux line 42b by reflux, the residual portion of the aqueous phase is fed into the distillation column of the second distillation step (5) by means of of a feed line 43b, a first portion of the organic phase is taken up to the separator column (3) via the reflux line 42a by reflux, and a second portion of the organic phase is fed into the distillation column of the second distillation stage (5) by means of a feed line 44, and the residual portion of the organic phase is recycled in the reaction step (1) by means of line 41.
[0077] By the way, in the distillation column of the second distillation stage (5) the aqueous phase (one portion or the total of the aqueous phase) can be fed, or at least one portion of the organic phase (or the complete organic), in that the lateral flow (5B) is separated into liquid-liquid (or biphasically). Each of the aqueous phase and the organic phase may have a methyl iodide concentration of, for example, not less than 1.5% by weight (for example, about 2 to 99% by weight, preferably about 3 to 95%) % by weight, and more preferably about 5 to 90% by weight). In a preferred embodiment, at least one portion of the organic phase (the organic phase rich in methyl iodide) is a general one fed into the distillation column of the second distillation step (5), and at least one portion of the aqueous phase can be fed in the distillation column of the second distillation step (5).
[0078] In addition to the liquid-liquid separation stage (decanter) (4) to temporarily maintain or retain the condensate and to separate the condensate biphasically, a buffer tank to temporarily hold (or retain) the condensate (the separate lower phase or phase in the decanter (4) can optionally be used to suppress the fluctuation of the flow of the process flow.
[0079] The condensate (as well as the aqueous phase and the organic phase) can have a temperature of, for example, about 20 to 110 ° C (for example, about 25 to 90 ° C) and preferably about 30 to 80 ° C (for example, about 35 to 70 ° C). [Liquid-liquid separable / condensable gas phase]
[0080] In the liquid-liquid separation step (4), a gas (gas generated) produced from the process can be condensed to separate the gas phase into two liquid phases; the gas produced from the process includes, for example, a gas phase (suspended part) which is produced from at least one stage selected from the group consisting of the reaction stage (1), the rapid evaporation stage (2), first distillation step (3), and subsequent distillation steps (5), (7) and (8) [for example, at least the first distillation step (3)], and contains at least acetaldehyde and methyl iodide . [Plurality of condensation steps]
[0081] Among acetyl acid, methyl acetate, methyl iodide, methanol, water, acetaldehyde, or other compounds, acetaldehyde has a boiling point close to that of methyl iodide, and has the lowest boiling point. Thus, in a case where the first suspended flow (3A) is cooled in stages, in a plurality of condensers (a plurality of successively smaller condensers in cooling temperature), to form a plurality of successively smaller condensates in temperature, a condensate formed by a subsequent condenser it has a higher concentration of acetaldehyde, which has a lower boiling point component, compared to a liquid process (a condensate) formed by a first condenser. Furthermore, in a case where the first suspended flow (3A) is cooled in stages in a plurality of condensers like this, in the first condenser the first suspended flow (3A) is separable into a first condensate and a first gas fraction ( non-condensable fraction) with a high concentration of acetaldehyde, in a second condenser the first gas fraction is separable in a second condensate with a high concentration of acetaldehyde and a second gas fraction (non-condensable fraction). In this way, a condensate with a high concentration of acetaldehyde can be fed in the second distillation step (5) to separate acetaldehyde from the condensate.
[0082] The gas fraction (non-condensable fraction) in the condenser (s) can be fed as a ventilation gas or generated gas (exhaust gas) in an absorption system to collect or recover additionally a used component such as methyl iodide. [Water extraction and liquid-liquid separation]
[0083] The process shown in figure 1 may additionally comprise, in addition to the liquid-liquid separation step (4), a water extraction step to bring the first suspended flow (3A) into contact with water [or submit the first suspended flow (3A) water extraction] to separate the first suspended flow (3A) into an organic phase rich in methyl iodide and an aqueous phase rich in acetaldehyde. In the extraction step, the first suspended stream (3A) can be placed directly in contact with water to provide an acetaldehyde extract, and can optionally be separated into an aqueous phase and an organic phase. In order to improve the efficiency of the extraction, the aqueous phase and / or the organic phase separated in the liquid-liquid separation step (4) can be brought into contact with water to form an acetaldehyde extract. At least one of the aqueous phase and the organic phase formed by the extraction of water can be subjected to a second distillation step (5). The organic phase, which is rich in methyl iodide, is generally subjected to the second stage of distillation (5). The aqueous phase, which is rich in acetaldehyde, can be used as an extraction agent for the second distillation step (5) or can be fed into a concentration zone between the top of the column (the zero plate when the upper plate is the first plate) and a plate which is a plate superior to the lateral flow (5B) (or lateral cutting plate).
[0084] The distillation of the suspended flow or mixed composition (3A) forms the lateral flow (5B), which is liquid-liquid separable. The mixed composition (3A) can be biphasically separable. In a case where the mixed composition (3A) is separated biphasically, at least a portion of the organic phase, at least a portion of the aqueous phase, or a feed liquid containing the mixture of the organic phase and the aqueous phase can be fed in the step distillation (5). Thus, in the mixed composition (3A), concentrations of methyl iodide, PRC’s, water or other compounds can be selected from wide concentration ranges.
[0085] In the following, with reference to process flow compositions, concentrations of typical components (acetaldehyde, methyl iodide, methyl acetate, acetate, water and dimethyl ether) will be described, although the process ends inevitably contain other components (including impurities) as described below. The process flows can include the mixed composition (3A) and separate phases (in phases), the second suspended flow (5A), the lateral flow (5B) and separate phases (in phases), suspended flows (7A) ( 8A) or condensates thereof, and net fund flows (7B) (8B). As used herein, each process flow (or each phase), including impurities, has a total amount of 100% by weight on the weight basis. The term “concentration of PRC’s” can be the concentration of each of the PRC’s or can be the concentration of all PRC’s (or the total concentration of PRC’s). The concentration of PRC’s is referred to simply as “concentration of PRC”. Representative PRC’s include acetaldehyde.
The mixed composition (3A) (a homogeneous liquid, or a mixture of an aqueous phase and an organic phase) may have a concentration of PRC (in a representative way, acetaldehyde) of, for example, about 10 ppm at 10 % by weight (for example, about 100 ppm to 5% by weight) and preferably about 500 ppm to 1% by weight (for example, about 0.1 to 0.5% by weight). According to the present invention, small amounts of PRC's (for example, acetaldehyde) can be efficiently separated and, thus, the mixed composition (3A) can have a concentration of PRC (for example, acetaldehyde) of about 100 to 5,000 ppm (for example, about 500 to 3,000 ppm) and in general about 750 to 2,500 ppm (for example, about 1,000 to 2,000 ppm). The mixed composition (3A) can have a methyl iodide concentration of, for example, about 10 to 85% by weight (for example, about 25 to 80% by weight) and preferably about 40 to 75% by weight (for example, about 50 to 70% by weight). The mixed composition (3A) can have a methyl acetate concentration of, for example, about 0 to 30% by weight (for example, about 0.1 to 25% by weight) and preferably about 1 to 20% by weight (for example, about 5 to 20% by weight) or it may have a concentration of methyl acetate of about 7 to 17% by weight (for example, about 10 to 15% by weight). The mixed composition (3A) can have an acetate acid concentration of, for example, about 0 to 12% by weight (for example, about 0.1 to 10% by weight) and preferably about 0.5 to 8 % by weight (for example, about 1 to 7% by weight); or it may have an acetic acid concentration of about 1 to 5% by weight (for example, about 1 to 3% by weight). The mixed composition (3A) can have a water concentration of, for example, not less than 1% by weight (for example, about 5 to 87% by weight), preferably not less than 10% by weight (for example, about 15 to 85% by weight), and more preferably not less than 20% by weight (e.g., about 30 to 83% by weight); or it may have a water concentration of about 5 to 50% by weight (for example, about 10 to 40% by weight) and preferably about 15 to 35% by weight (for example, about 17 to 30% by weight) Weight). The mixed composition (3A) can have a dimethyl ether concentration of, for example, about 0 to 1% by weight (for example, about 1 ppm to 0.5% by weight) and preferably about 5 ppm at 0 , 3% by weight (for example, about 10 to 500 ppm). The mixed composition (3A) can have a methanol concentration of, for example, about 10 ppm to 5% by weight (for example, about 50 ppm to 4% by weight) and preferably about 0.01 to 2, 5% by weight (for example, about 0.03 to 1.5% by weight).
[0087] In a case where the suspended flow or mixed composition (3A) is separated into liquid-liquid (or forms an organic phase and an aqueous phase), the organic phase (lines 41, 42a, and 44) may show a concentration of PRC (representatively, acetaldehyde) of, for example, about 1 ppm to 10% by weight (for example, about 100 ppm to 5% by weight) and preferably about 300 ppm to 2.1% by weight weight (for example, about 500 ppm to 0.5% by weight) or can have a PRC concentration of about 100 to 5,000 ppm (for example, about 250 to 4,000 ppm) and preferably about 500 to 3,000 ppm (for example, about 1,000 to 2500 ppm). The organic phase can have a methyl iodide concentration of, for example, about 10 to 95% by weight (for example, about 30 to 93% by weight), preferably about 50 to 90% by weight (for example , about 70 to 90% by weight), and more preferably about 75 to 85% by weight (e.g., about 80 to 85% by weight); or it may have a methyl iodide concentration of, for example, not less than 10% by weight (for example, about 15 to 90% by weight), preferably not less than 20% by weight (for example, about 25 to 90% by weight), more preferably not less than 30% by weight (e.g., about 30 to 80% by weight), and particularly about 40 to 70% by weight (e.g., about 50 to 65% by weight). The organic phase may have a methyl acetate concentration of, for example, about 1 to 30% by weight (for example, about 3 to 25% by weight), preferably about 5 to 20% by weight (for example , about 7 to 16% by weight), and more preferably about 10 to 18% by weight. The organic phase of the mixed composition (3A) can have an acetate acid concentration of, for example, about 0 to 10% by weight (for example, about 0.1 to 7% by weight) and preferably about 0, 3 to 5% by weight (for example, about 0.5 to 3% by weight) or may have a concentration of acetic acid of about 1 to 5% by weight (for example, about 1.5 to 3% by weight). The organic phase can have a water concentration of, for example, about 0 to 50% by weight (for example, about 0.01 to 40% by weight), preferably about 0.1 to 30% by weight ( for example, about 0.2 to 20% by weight), and more preferably about 0.5 to 10% by weight (for example, about 1 to 5% by weight); or it may have a water concentration of about 0 to 5% by weight (for example, about 0.1 to 3% by weight) and preferably about 0.3 to 2% by weight (for example, about 0 , 5 to 1.5% by weight). The organic phase can have a dimethyl ether concentration of, for example, about 0 to 1% by weight (for example, about 1 ppm to 0.5% by weight), preferably about 5 ppm to 0.3% by weight (for example, about 10 ppm to 0.1% by weight), and more preferably about 10 to 100 ppm (for example, about 15 to 70 ppm). The organic phase can have a methanol concentration of, for example, about 10 ppm to 4% by weight (for example, about 50 ppm to 3% by weight) and preferably about 0.01 to 1% by weight ( for example, about 0.03 to 0.5% by weight).
[0088] In a case where the suspended flow or mixed composition (3A) is separated into liquid-liquid (or forms an organic phase and an aqueous phase), the aqueous phase (lines 43a and 43b) may show a concentration of PRC ( representative, acetaldehyde) of, for example, about 500 ppm to 30% by weight (for example, about 1,000 ppm to 25% by weight), preferably about 2,000 ppm to 20% by weight (for example, about from 2,500 ppm to 15% by weight), and more preferably about 3,000 ppm to 5% by weight (e.g., about 3,000 ppm to 5% by weight). The aqueous phase can have a methyl iodide concentration of, for example, about 0.1 to 30% by weight (for example, about 1 to 25% by weight) and preferably about 3 to 20% by weight ( for example, about 5 to 15% by weight); or it may have a concentration of methyl iodide of not less than 1.5% by weight (for example, about 2 to 50% by weight), not less than preferably 2% by weight (for example, about 3 to 40%) % by weight), and more preferably not less than 4% by weight (for example, about 5 to 30% by weight); or it can have a methyl iodide concentration of about 0.1 to 10% by weight (for example, about 0.5 to 7% by weight) and more preferably about 1 to 5% by weight (for example, about 1.5 to 3.5% by weight). The aqueous phase can have a methyl acetate concentration of, for example, about 1 to 30% by weight (for example, about 3 to 25% by weight), preferably about 5 to 20% by weight (for example , about 7 to 15% by weight), or about 5 to 10% by weight. The aqueous phase can have an acetate acid concentration of, for example, about 5 to 60% by weight (for example, about 10 to 50% by weight), preferably about 20 to 40% by weight (for example, about 25 to 35% by weight), or it may have a concentration of acetic acid of about 15 to 35% by weight (for example, about 20 to 30% by weight). The aqueous phase can have a water concentration of, for example, about 10 to 90% by weight (for example, about 25 to 80% by weight) and preferably about 30 to 75% by weight (for example, about 40 to 70% by weight). The aqueous phase may have a concentration of dimethyl ether of, for example, about 0 to 0.3% by weight (for example, about 1 ppm to 0.2% by weight) and preferably about 5 ppm to 0, 1% by weight (for example, about 10 to 500 ppm). The aqueous phase can have a methanol concentration of, for example, about 100 ppm to 7% by weight (for example, about 500 ppm to 5% by weight) and preferably about 0.1 to 3% by weight ( for example, about 0.3 to 2% by weight).
The flow of acetic acid or lateral flow (3B) can have a concentration of PRC (such as acetaldehyde) of, for example, about 0 to 2,000 ppm (for example, about 0 to 1,000 ppm), preferably about from 0 to 500 ppm (for example, about 1 to 100 ppm), and more preferably about 0 to 50 ppm, or can have the PRC concentration of substantially no more than the detectable or measurable limit. The acetate acid stream (3B) can have a methyl iodide concentration of, for example, about 0 to 15% by weight (for example, about 0.3 to 10% by weight) and preferably about 0, 5 to 7% by weight (for example, about 1 to 5% by weight). The acetate acid stream (3B) can have a methyl acetate concentration of, for example, about 0 to 15% by weight (for example, about 0.3 to 10% by weight) and preferably about 0, 5 to 8% by weight (for example, about 1 to 5% by weight). The flow of acetic acid (3B) can have a water concentration of, for example, about 0 to 15% by weight (for example, about 0.3 to 10% by weight) and preferably about 0.5 to 5% by weight (for example, about 1 to 3% by weight). The acetate acid stream (3B) can have a dimethyl ether concentration of, for example, about 0 to 1,000 ppm (for example, about 0 to 100 ppm) and preferably about 0 to 50 ppm (for example, about from 0 to 10 ppm) or may have a dimethyl ether concentration of substantially no more than the detection limit. The acetate acid stream (3B) can have a methanol concentration of, for example, about 0 to 1% by weight (for example, about 0 to 0.5% by weight), preferably about 0 to 5,000 ppm (for example, about 0 to 1,000 ppm), and more preferably about 0 to 100 ppm, or can have a methanol concentration of substantially no more than the detection limit. The acetate acid flow or lateral flow (3B) contains these components, inevitable contaminants (including impurities or by-products) and acetate acid like the rest. The acetate acid stream (3B) can have an acetate acid concentration of, for example, about 87 to 99% by weight (for example, about 88 to 98% by weight) and preferably about 90 to 97% by weight weight (for example, about 90 to 95% by weight).
[0090] The bottom liquid flow (higher boiling point flow or higher boiling point fraction) (3C) (line 31) can have a PRC concentration (such as acetaldehyde) of, for example, about 0 to 2,000 ppm (for example, about 0 to 1,000 ppm), preferably about 0 to 500 ppm (for example, about 1 to 100 ppm), and more preferably about 0 to 50 ppm, or it may show the concentration of PRC substantially no more than the detection limit. The liquid bottom stream (3C) can have a methyl iodide concentration of, for example, about 0 to 15% by weight (for example, about 0.01 to 10% by weight), preferably about 0, 1 to 8% by weight (for example, about 0.2 to 5% by weight), and more preferably about 0.5 to 3% by weight. The liquid bottom flow (3C) can each have a concentration of methyl acetate and water concentration of, for example, about 0 to 15% by weight (for example, about 0.1 to 10% by weight) ), preferably about 0.3 to 8% by weight (for example, about 0.5 to 5% by weight), and more preferably about 0.7 to 3% by weight (for example, about 1 to 2% by weight). The liquid bottom stream (3C) can have a concentration of acetic acid of, for example, about 60 to 99% by weight (for example, about 70 to 99% by weight), preferably about 80 to 98% by weight weight (for example, about 85 to 98% by weight), and more preferably about 90 to 98% by weight. The liquid bottom stream (3C) can have a dimethyl ether concentration of, for example, about 0 to 1,000 ppm (for example, about 0 to 100 ppm) and preferably about 0 to 50 ppm (for example, about from 0 to 10 ppm) or may have a dimethyl ether concentration of substantially no more than the detection limit. The liquid bottom stream (3C) can have a methanol concentration of, for example, about 0 to 1% by weight (for example, about 0 to 0.5% by weight), preferably about 0 to 5,000 ppm (for example, about 0 to 1,000 ppm), and more preferably about 0 to 100 ppm, or it can have a methanol concentration of substantially no more than the detection limit. (5) Second distillation step (Distillation column)
[0091] In the second distillation step (distillation column) (5), the first suspended flow (3A) is fed through the feed lines 43b, 44 [in the illustrated embodiment, the condensate from the liquid-liquid separation step (4 )] and distilled to form a concentration zone (a zone with high concentrations of PRC's (in particular, acetaldehyde) and methyl iodide) at the top position of the distillation column. The concentration zone, an extraction agent that can extract PRC's (in particular, acetaldehyde) preferably in methyl iodide and added to extract at least PRC's (in particular, acetaldehyde), and an extraction mixture (liquefied fraction, liquid that falls off ) which falls from the concentration zone and is withdrawn as a lateral flow (5B) from the distillation column. The extraction mixture has a significantly higher concentration of PRC (in particular, acetaldehyde) than the first suspended flow or mixed composition (3A) fed into the distillation column (5). Removing the extraction mixture as the side flow (5B) allows PRC’s to be separated or removed efficiently.
[0092] Assuming that the total number of plates of the distillation column is "100" and the bottom is the plate "zero" (0), the position (feed port, or feed plate or tray) in which the composition is mixed or suspended flow (3A) [in the illustrated embodiment, the organic phase and / or the aqueous phase of the liquid-liquid separation step (4)] and fed into the second distillation column (5) can be selected from the range of about the loop the 70th plate at the bottom of the distillation column and, for example, it may be about 1 to 50th plate (for example, about the 3rd to 45th plate), preferably the 4th to 40th plate (for example, about the 5th to 35th plate ) from the bottom of the distillation column. In other words, assuming that the height level of the distillation portion of the distillation column is “1”, the mixed composition or suspended flow (3A), for example, can be fed at a height level of about 0.01 / 1 to 0.7 / 1 (for example, about 0.01 / 1 to 0.5 / 1), preferably about 0.03 / 1 to 0.45 / 1 (for example, about 0.04 / 1 to 0.4 / 1), and more preferably about 0.05 / 1 to 0.35 / 1 of the bottom. For example, for a column of distillation plates with the actual total number of stages (or plates) of 43, the feeding plate on which the mixed composition (3A) is fed can be about 1 to 20 plate, preferably about 2nd to 15th plate, and more preferably about the 4th to 10th plate at the bottom of the distillation column. For example, for a column of distillation plates with the actual total number of stages (or plates) of 10, the feed plate on which the mixed composition (3A) is fed can be about 1 to 7 plate, preferably about 1 there the 5th plate, and more preferably about the 3rd plate from the bottom of the distillation column.
[0093] The distillation column of the distillation step (5) is provided with a receiving or holding unit, for example, a receiver (for example, a flue pan) (51); the unit allows the upward transfer of vapor or evaporation fraction from the first suspended flow (3A) [in the illustrated embodiment, the condensate from the liquid-liquid separation step (4)] in the concentration zone and the participation of the total amount of the mixture of extraction (or liquid that falls) that falls from the concentration zone. By the way, the extraction mixture can be separable liquid-liquid in a receiver unit, capable of receiving the liquid that falls as a mixture of the refined (liquid methyl iodide) and the extract.
[0094] The receiver is disposed in a position higher than the feed port of the first suspended stream (3A), and a position lower than that of the extraction agent addition port. The receiver (for example, a chimney pan) has a common structure, for example, a pan capable of receiving the extraction mixture (liquid, liquid that falls) that falls from the concentration zone, and hollow cylindrical chimneys; each chimney projects or extends from the edge of the tray opening towards the top of the column (upstream), and allows the vapor or fraction evaporated from the first suspended flow (3A) to increase or be transferred to the concentration zone. The chimney has an upper opening in which a cover (a hood or a cover) is attached; the cover allows the vapor or evaporation fraction to move upwards or through. The receiver (for example, a flue pan) can be provided with a withdraw port or withdraw line to withdraw liquid from the tray. The structure of the receiver (e.g., flue pan) is not limited to the structure described above. The chimney, if necessary, may have a small portion that allows the vapor or evaporation fraction to pass. The tray may have a funnel structure, a curved structure, or other structures. The receiver (chimney tray) can have an opening ratio (an area ratio of the openings to the entire surface of the tray) of about 5 to 90%, for example, about 10 to 50% (for example, about 15 to 40%), and preferably about 15 to 35%.
[0095] In the distillation column (5) supplied with a unit or receiver (chimney tray) like this, the extraction agent is added to the concentration zone previously formed in the receiver. The concentration zone is formed in a space between the feed port and the top of the column. Due to a low boiling point of acetaldehyde and this of methyl iodide, the concentration zone can be formed in an upper space (the upper side of the column), in particular, a space at the top of the column or close to it. Thus, the receiver (for example, a flue pan) can be arranged in an upper position of the distillation column (5). The PRC's are efficiently extracted by removing the lateral flow (5B) from the concentration zone and, thus, the position of the receiver [the position of a lateral flow removal port (5B)] is practically superior to the composition feed port. mixed (3A). The receiver [a side flow withdrawal port (5B)] is not limited to a particular position, and can be arranged on the same height level as the height level of the feed port (or feed plate) of the first suspended stream or mixed composition (3A), or it can be arranged in a recovery zone smaller than the feed port. Specifically, the height level of the receiver can be the same as that of the feed port of the first suspended stream or mixed composition (3A), or it can be greater or less than that of the feed port of the mixed composition (3A). In a case where the receiver is arranged in a position smaller than the feed port of the first suspended stream or mixed composition (3A), the receiver is positioned in a location higher than the bottom stream.
[0096] The height level of the receiver (for example, a flue pan) in the distillation column is higher than the feed part or feed pan of the first suspended stream (3A). According to the number of plates of the distillation column, the height level of the receiver (for example, a flue pan) is in between the top plate of the column (the top plate of the column) and a plate, at least a top plate is the feed part or feed tray of the first suspended stream (3A), or is positioned at the top (or top) of the column or close to it. Assuming that the total number of plates in the distillation column is 100, the position (height level) of the receiver can be selected from the range that corresponds to about the 2nd to 70th plate in the top of the distillation column and, for example, can correspond about 2nd to 60th plate (e.g., about 2nd to 45th plate), preferably about 2nd to 30th plate (e.g., about 2nd to 25th plate), and most preferably about 2nd to 10th plate (e.g. , about the 2nd to 7th plate) at the top of the distillation column. In other words, assuming that the height level of the distillation portion of the distillation column is "1", the receiver can be formed at a height level of about 0.02 / 1 to 0.7 / 1 (for example , about 0.02 / 1 to 0.6 / 1), preferably about 0.02 / 1 to 0.45 / 1 (e.g., about 0.02 / 1 to 0.3 / 1), and more preferably about 0.02 / 1 to 0.25 / 1 (e.g., about 0.02 / 1 to 0.1 / 1) from the top of the distillation column. For example, in a case where the distillation column is a column of distillation plates with the actual total number of stages (or plates) of 43, the receiver (for example, a flue pan) may be arranged at the location of a plate between the upper column top plate (next to the column top plate), or the top of the column and a plate that is positioned on at least one plate above the feed part or feed tray of the first suspended stream (3A ) (for example, a plate that is at least 5 plates higher than the feed tray); or the receiver (for example, a flue pan) may be arranged at the location of a plate between the upper plate at the top of the column and a plate that is positioned on the lower 25 plates than the upper (the 25th plate) (preferably the 10th plate from the upper plate, more preferably the 5th plate of the upper plate, and particularly the 3rd plate of the upper plate). More specifically, the side cut-off plate (receiver) of the side flow (5B) can be positioned on the top plate of the distillation column (the 1st plate), the 2nd or 3rd upper plate (in particular, the upper plate or the 2nd top plate).
[0097] In a case where the distillation column and a column of distillation plates with the actual total number of stages (or plates) of 10, the receiver (for example, a flue pan) can be arranged at the location of a plate between the top column top plate (next to the column top plate) or the top of the column and a plate that is positioned on at least one plate above the feed part or feed tray of the first suspended stream (3A) (for example, a plate that is at least 5 plates higher than the feed tray); or the receiver (for example, a flue pan) may be arranged at the location of a plate between the upper plate at the top of the column and a plate that is positioned on 10 plates smaller than the upper plate (the 10th plate) (preferably the 5th plate of the upper plate, more preferably the 2nd plate from the upper plate, and particularly the plate from the upper plate). More specifically, the side cut-off plate (receiver) of the side flow (5B) can be positioned on the top plate of the distillation column (the 1st plate), the 2nd or 3rd upper plate (in particular, the upper plate or the 2nd top plate).
[0098] The extraction agent can in general be added to the top of the distillation column (5) [for example, the top column plate, or between the top of the column and a plate that is positioned on at least one upper plate the feed part or feed tray of the first suspended stream (3A)]. Assuming that the distillation column has the total number of plates of 100, the extraction agent feed plate can be a plate on top of or near the distillation column (5), for example, about 0 to 50th plate (e.g., about the loop at the 25th plate), preferably about the loop at the 20th plate (e.g., about the loop at the 15th plate), and more preferably about the loop at the 10th plate at the top of the distillation column. In other words, assuming that the height of the distillation portion of the distillation column is "1", the extraction agent can be fed, for example, at a height of about 0/1 (the top of the column ) to 0.5 / 1 (for example, about 0.01 / 1 to 0.25 / 1), preferably about 0.01 / 1 to 0.2 / 1 (for example, 0.01 / 1 to 0.15 / 1), and more preferably about 0.01 / 1 to 0.1 / 1 of the top of the column. For example, in a case where the distillation column is a column of distillation plates with the actual total number of stages (or plates) of 43, the extraction agent can be added to a plate at the top of the distillation column or next to this (5) (e.g., the 0 to the 20th plate, preferably the highest to the 10th plate, most preferably the most to the 5th plate, and particularly the highest to the 3rd plate). In a case where the distillation column is a column of distillation plates with the actual total number of stages (or plates) of 10, the extraction agent can be added to a plate at or near the top of the distillation column ( 5) (for example, the 0 to the 7th plate, preferably the highest to the 5th plate, most preferably the highest to the 3rd plate, and particularly the highest to the 2nd plate). In order to increase the extraction efficiency by counteracting the extraction agent to increase the vapor or evaporation fraction, the extraction agent can be added in general to the upper plate of the distillation column (5). In order to increase the extraction efficiency, the extraction agent can be added in a drop form, in particular, it can be added by spraying or spraying. The extraction agent can have a temperature of, for example, about 0 to 60 ° C, preferably about 10 to 50 ° C, and more preferably about 20 to 40 ° C, or it can have a common temperature (for example , about 15 to 25 ° C). The extraction agent can be added as a heated or hot extraction agent (for example, heated to about 30 to 150 ° C and preferably about 50 to 110 ° C), or in the form of steam (including superheated steam).
[0099] The extraction agent is capable of extracting PRC's (in particular, acetaldehyde) preferably from methyl iodide. The extraction agent is preferably separable from the methyl iodide phase by liquid-liquid separation. Specifically, the preferred extraction agent can separate the extraction mixture (5B) into an upper and a lower phase. In particular, the extraction agent preferably includes an aqueous extraction agent containing at least water, for example, water and a mixed solvent containing water, and a water-soluble organic solvent [for example, an alcohol (a monol) such as methanol , a glycol such as ethylene glycol, a polyhydric alcohol such as glycerin, acetone, an ester and an ether]. Among these extraction agents, water is preferred. Feeding water as the extraction agent preserves or maintains the extraction mixture (or drop extraction mixture) in a separate liquid-liquid stage to advantageously separate the extraction mixture into two stages.
[00100] The extraction agent may contain water and at least one component selected from the group consisting of PRC's, methyl iodide, acetate, methyl acetate, dimethyl ether and a component present in the process (all components including the impurities described previously). An extraction agent like this can be an aqueous solvent produced in the process [for example, an aqueous phase 43a produced in the liquid-liquid separation step (4) of the first suspended flow (3A), an aqueous process flow such as extracts 62, 67, and 69 produced in the second liquid-liquid separation step (6) (for example, an aqueous process flow containing acetaldehyde), and other aqueous process flows containing acetaldehyde (for example, an aqueous phase formed by extracting PRC's with Water)]. The extraction agent can also include an aqueous solution (for example, an aqueous solution containing acetaldehyde and methyl iodide) obtainable by treatment with absorption of a gas generated with water, the gas generated being produced from the process. The generated gas may include, for example, generated gases produced in a variety of operation of units in the process, such as generated gases produced in the reactor (1), the instantaneous evaporator (2), the first distillation column (3), the second distillation column (5) or separation unit 6a, third distillation column (7), fourth distillation column (8), or others.
[00101] According to the present invention, not the total of the distillation column, but a space (or zone) between the extraction agent addition port (or position) and the receiver (lateral position) can be used as a extraction space (an extraction zone); the vapor or fraction vaporized in the concentration zone (in particular, at least acetaldehyde and methyl iodide contained in the zone) can be extracted with the extraction agent. Thus, PRC's (in particular, acetaldehyde) can be efficiently extracted with a lesser amount of the extraction agent compared to the amount of the extraction agent used for a process that removes the extraction mixture (5B) as the bottom flow ( 5C). For example, the flow weight ratio of the extraction agent to the flow of the first suspended flow (3A) (in terms of liquid flow) [the first / the last] can be selected from a range of about 0.0001 / 100 to 100/100 (for example, about 0.001 / 100 to 50/100), or it can generally be about 0.0001 / 100 to 20/100 (for example, about 0.001 / 100 to 10/100 ), preferably about 0.01 / 100 to 8/100, and more preferably about 0.1 / 100 to 5/100. Thus the extraction mixture or the liquid that falls [or the side flow (5B)] in the distillation column can form a liquid flow [or side flow (5B)] with a small extraction agent content; the liquid flow is biphasically separable by forming an aqueous phase (a small amount of an aqueous phase or extract) and an organic phase (a large amount of an organic or refined phase).
[00102] By the way, according to the conventional distillation combination that removes acetaldehyde (AD) with water extraction, an organic phase concentrated in PRC (or methyl iodide phase) and extracted with substantially the same amount of water for water extraction as the organic phase concentrated in PRC. In contrast, according to the present invention, the amount of water extraction is about 0.1% to 10% of the organic phase concentrated in PRC (or methyl iodide phase). Thus, in a case where the concentration of PRC in the organic phase is substantially the same, the concentration of PRC in the aqueous phase can be significantly higher compared to conventional extractive distillation with water. In other words, PRC's can be efficiently extracted with water, even if the organic phase has a low concentration of PRC and, thus, the separation zone (the actual number of stages (or plates) or the theoretical number of stages ( or plates)) of the distillation column can be reduced compared to conventional technique, removing acetaldehyde at a lower cost. However, regardless of the amount of the organic phase, the organic phase has a high concentration (substantially equivalent in high) of methyl iodide; in the same concentration of acetaldehyde (AD) in the aqueous phase, the concentration of methyl iodide (Mel) dissolved in the aqueous phase is small and is hardly altered, regardless of the ratio of quantity of aqueous phase and organic phase after extraction. Thus, according to the present invention, although a much smaller amount of the extraction agent with respect to the amount of the organic phase to be extracted is used, the ratio (Mel / AD ratio) of methyl iodide (Mel) to acetaldehyde (AD) can be reduced, compared to conventional combination of distillation that removes acetaldehyde with water extraction, and PRC's can be removed efficiently in the condition to reduce a loss of methyl iodide out of the system with a small distillation zone and a low cost.
[00103] By the way, examples of document associated with patent 2 (TABLE 2) describe that, in extractive distillation with water using a second distillation column, the water is fed in a top of the column, a liquid of feeding with a concentration of acetaldehyde of 31% by weight is distilled in the second distillation column, and an aqueous bottom flow is removed from the bottom of the column, and that the concentration of acetaldehyde of 31% by weight in the feed liquid is reduced to 22.4% in weight in the bottom stream. However, the extractive distillation with water described in the document associated with patent 2 requires 100 or more times the amount of the extraction agent than the second distillation step (5), according to the present invention. By the way, according to the present invention, methyl iodide can be removed as the suspended stream or mixed composition (3A) on one side of the distillation column (5), whereas according to the patent document 2, iodide methyl and removed mainly from the top of the column; both are very different in the way of methyl iodide separation. According to the present invention, a bottom flow with a high concentration of methyl iodide is obtained by removing the side flow from the distillation column (5) and resuming the flow removed from the distillation column (5). If, according to the document process associated with patent 2, the amount of the extraction agent (for example, water) fed at the top of the distillation column is 100 or more times greater than that of the extraction agent in the present invention (for example, example, the amount of the extraction agent is substantially the same or greater than the amount of the feed liquid), the ratio of the fund rate / the feed rate according to the patent document 2 and 100 or more times higher that the lateral aqueous phase rate / feed rate in the present invention. Thus, in a case where the aqueous bottom stream is directly discharged into the form of the System, or is additionally distilled for the separation of acetaldehyde and methyl iodide from water, at least 5 to 10 or more times the amount of iodide of methyl and discharged out of the system in comparison to the present invention, due to the methyl iodide dissolved in the bottom stream (aqueous stream). Furthermore, unlike the present invention, according to the document associated with patent 2, most of the methyl iodide from the feed is removed from the top of the column and thus a large amount of energy is required, which is not economical .
[00104] Additionally, since the extraction mixture, not as the bottom flow or bottom flow (5C), but as the side flow (5B), and removal from a receiver removal port (for example, a flue tray), PRC's (in particular, acetaldehyde) and methyl iodide can be separated from each other, even if the number of plates in the distillation column is significantly less. For example, assuming that the total number of distillation column plates is 100 in the conventional process, the number of distillation column plates in the present invention can be reduced by about 5 to 80 (for example, about 10 to 80) , preferably about 7 to 70 (for example, about 12 to 60), more preferably about 8 to 50 (for example, about 15 to 50), and particularly about 10 to 40 (for example, about 20 to 40). Even if a distillation column has about 8 to 20 (for example, about 10 to 15) plates, PRC’s and methyl iodide can be separated efficiently. In other words, supposing that the common distillation column has a separation space (distillation space) of “100”, a distillation column with a separation space of, for example, about 5 to 80 (for example, about 10 to 80), preferably about 7 to 50 (for example, about 8 to 30), and more preferably about 10 to 30 (for example, about 10 to 20) also allows efficient separation of PRC's and iodide of each other's methyl.
[00105] In a case where a membrane separation of PRC's is additionally conducted after extractive distillation in the distillation column (5), assuming that the total number of plates in the distillation column (5) is 100, as the same as that of the distillation column of the document associated with patent 2, the number of plates of the distillation column in the present invention can be reduced by about 5 to 20. For example, in a case where an aqueous phase with a higher ratio of methyl iodide / PRC's that a process flow before removing PRC's and withdrawn in extractive distillation by the distillation column (5), and then PRC's are separated from the withdrawal phase in a subsequent step (for example, membrane separation), the number of distillation column plates (5) can be further reduced significantly, as previously described.
[00106] From the distillation column, at least a portion of the extraction mixture (5B) is removed. The extraction mixture kept in the tray can generally be removed continuously. Specifically, the extraction mixture can be removed from the distillation column depending on the amount of liquid that falls from the concentration zone (the total amount of liquid that falls).
[00107] In a process like this, even if the first suspended stream (3 A) contains an amphipathic component (such as methyl acetate or acetate acid) with a high affinity, both with PRC's (such as acetaldehyde) and with iodide methyl, the PRC's (such as acetaldehyde) in the first suspended flow (3A) can be efficiently extrated into the side flow or extraction mixture (5B) and thus the PRC's (such as acetaldehyde) can be separated and removed. For example, the concentration of acetaldehyde in the lateral flow (5B) is greater than in the first suspended flow (3A) and that of the bottom flow (5C). For example, the concentration of PRC (such as acetaldehyde) in the lateral flow (5B) [the aqueous phase of the lateral flow (5B)] is about 10 to 1,000 times (for example, about 20 to 800 times), preferably about 30 to 500 times (for example, about 50 to 200 times), and more preferably about 50 to 170 times (for example, about 60 to 150 times) greater than that in the first suspended flow (gas flow or a flow condensate) (3A).
[00108] The ratio of acetaldehyde to methyl iodide in the side flow (5B) is greater than that in the first suspended flow (3A) and is greater than that in the bottom flow (5C).
[00109] The internal temperature of the distillation column of the second distillation step (5) depends on its internal pressure. At the internal pressure of an atmospheric pressure, the distillation column can have a column top temperature of, for example, about 15 to 120 ° C (for example, about 18 to 100 ° C), preferably about 20 to 90 ° C (for example, about 20 to 80 ° C), and more preferably about 20 to 70 ° C (for example, about 25 to 70 ° C), or it can have a column bottom temperature of, for example, about 35 to 150 ° C (preferably about 40 to 120 ° C). The distillation column can have a top column pressure (absolute pressure) of, for example, about 0.1 to 0.5 MPa. In the second distillation step (5), other distillation conditions (for example, the theoretical number of stages of the distillation column, and the flow rate) can be the same as that in the first distillation step (3).
[00110] The second suspended flow (5A) (a mixture of an aqueous phase and an organic phase when the flow is separated into these phases; a mixture in a line 53, a mixture of a flow in a line 61 and a flow in a line 62) may have a PRC concentration (such as acetaldehyde) of, for example, about 1 to 75% by weight (for example, about 10 to 70% by weight), preferably about 20 to 65% by weight ( for example, about 25 to 60% by weight), and more preferably about 30 to 55% by weight (for example, about 35 to 50% by weight); or it may have a PRC concentration of about 50 to 95% by weight (e.g., about 75 to 90% by weight) and preferably about 80 to 90% by weight. The second suspended stream (5A) may have a methyl iodide concentration of, for example, about 1 to 85% by weight (for example, about 10 to 80% by weight), preferably about 20 to 80% by weight weight (for example, about 30 to 75% by weight), and more preferably about 40 to 75% by weight (for example, about 50 to 70% by weight); or it may have a concentration of methyl iodide of about 5 to 30% by weight (for example, about 7 to 25% by weight) and preferably about 10 to 20% by weight. The second suspended stream (5 A) can have a methyl acetate concentration of, for example, about 0 to 10% by weight (for example, about 0.01 to 7% by weight), preferably about 0, 02 to 5% by weight (for example, about 0.03 to 2% by weight), and more preferably about 0.05 to 1% by weight (for example, about 0.1 to 0.5% by weight) weight), or it may have a concentration of methyl acetate of about 0.2 to 1% by weight (for example, about 0.3 to 0.7% by weight). The second suspended stream (5A) can have an acetic acid concentration of, for example, about 0 to 5% by weight (for example, about 1 ppm to 3% by weight) and preferably about 0 to 2% by weight. weight (for example, about 10 ppm to 1% by weight), or it can have a concentration of acetate acid of substantially no more than the detection limit. In addition, the second suspended stream (5A) can have a water concentration of, for example, about 0 to 30% by weight (for example, about 0.02 to 10% by weight), preferably about 0.05 to 5% by weight (for example, about 0.07 to 1% by weight), and preferably about 0.1 to 0.5% by weight. The second suspended stream (5A) may have a dimethyl ether concentration of, for example, about 0 to 2.5% by weight (for example, about 10 ppm to 2% by weight) and preferably about 100 ppm at 1.5% by weight (for example, about 0.1 to 1% by weight). The second suspended stream (5A) may have a methanol concentration of, for example, about 0 to 0.5% by weight, preferably about 0 to 0.3% by weight, and more preferably about 0 to 2500 ppm (for example, about 0 to 1,000 ppm), or it can have a methanol concentration of substantially no more than the detection limit. The reduction in the number of distillation stages (or plates) of the second distillation column (5) (for example, the reduction in the actual number of stages (or plates) from 100 to no more than 15% (or by about 10 to 15)) may tend to increase the concentration of PRC (representatively, acetaldehyde) in the second suspended stream (5A) and to decrease the concentration of methyl iodide in the second suspended stream (5A).
[00111] The second suspended stream (5A) (line 53 just before a C3 condenser) (a mixture of an aqueous phase and an organic phase when the second suspended stream is separated in these phases) can have a temperature at atmospheric pressure from, for example, about 15 to 110 ° C (for example, about 18 to 90 ° C) and preferably about 20 to 80 ° C (for example, about 20 to 70 ° C).
[00112] The gas generated from the C3 condenser is rich in dimethyl ether, PRC’s (in particular, acetaldehyde) and methyl iodide. The gas generated from the C3 condenser can have a PRC concentration (such as acetaldehyde) of, for example, about 1 to 75% by weight (for example, about 10 to 70% by weight), and preferably about 20 to 65% by weight (for example, about 30 to 60% by weight), or it can have a PRC concentration of about 35 to 65% by weight. The gas generated may have a methyl iodide concentration of, for example, about 1 to 55% by weight (for example, about 5 to 50% by weight) and preferably about 7 to 45% by weight (for example , about 10 to 40% by weight). The gas generated may have a concentration of methyl acetate of, for example, about 0.1 to 20% by weight (for example, about 0.5 to 15% by weight) and preferably about 1 to 12% by weight weight (for example, about 2 to 10% by weight). The gas generated may have an acetic acid concentration of, for example, about 0 to 5% by weight (for example, about 0.0001 to 3% by weight), preferably about 0 to 2.5% by weight (about 0.001 to 2% by weight), and preferably about 0.01 to 1% by weight, or it can have a concentration of acetate acid of substantially no more than the detection limit. The gas generated can have a water concentration of, for example, about 0 to 5% by weight (for example, about 0.01 to 2.5% by weight) and preferably about 0 to 2% by weight ( for example, about 0.1 to 1.5% by weight), or it can have a water concentration of substantially no more than the detection limit. The gas generated may have a concentration of dimethyl ether of, for example, about 0.1 to 90% by weight (for example, about 1 to 80% by weight), preferably about 3 to 80% by weight (eg for example, about 5 to 70% by weight), and more preferably about 10 to 60% by weight (for example, about 20 to 50% by weight). The gas generated can have a methanol concentration of, for example, about 0 to 5% by weight (for example, about 0.01 to 3% by weight) and preferably about 0 to 2.5% by weight ( for example, about 0.1 to 2% by weight).
[00113] The lateral flow (5B) (a mixture of an aqueous phase and an organic phase when the flow is separated in these phases; a mixture in a line 63, a mixture of a flow in line 61 and a flow in line 62) may have a PRC concentration (such as acetaldehyde) of, for example, about 0.1 to 90% by weight (for example, about 0.2 to 70% by weight), preferably about 0.3 to 60 % by weight (for example, about 0.4 to 50% by weight), more preferably about 0.5 to 40% by weight (for example, about 1 to 20% by weight), and particularly about 2 to 10% by weight (for example, about 3 to 7% by weight); or it may have a PRC concentration of about 0.1 to 10% by weight, preferably about 0.5 to 7% by weight, and more preferably about 1 to 5% by weight; or it can have a PRC concentration of about 3 to 10% by weight (for example, about 5 to 8% by weight). The side flow (5B) can have a methyl iodide concentration of, for example, about 1 to 99% by weight (for example, about 5 to 97% by weight), preferably about 10 to 95% by weight (for example, about 20 to 95% by weight), and more preferably about 30 to 95% by weight; or it may have a concentration of methyl iodide of about 50 to 99% by weight (for example, about 65 to 98% by weight), preferably about 75 to 98% by weight (for example, about 85 to 97 wt%), and more preferably about 90 to 97 wt%; it can have a methyl iodide concentration of about 75 to 95% by weight (for example, about 80 to 93% by weight). The side flow (5B) can have a methyl acetate concentration of, for example, about 0.1 to 20% by weight (for example, about 0.5 to 10% by weight) and preferably about 0, 7 to 7% by weight (for example, about 0.7 to 5% by weight), it may have a concentration of methyl acetate of about 0.5 to 5% by weight (for example, about 0.5 to 3% by weight), or it may have a concentration of methyl acetate of about 1 to 5% by weight (for example, about 2.5 to 5% by weight). The lateral flow (5B) can have an acetate acid concentration of, for example, about 0 to 5% by weight (for example, about 0.01 to 3% by weight) and preferably about 0.1 to 2 % by weight, or it may have a concentration of acetic acid of substantially no more than the detection limit. The lateral flow (5B) can have a water concentration of, for example, about 0.1 to 20% by weight (for example, about 0.3 to 10% by weight), preferably about 0.5 to 5 wt%, and more preferably about 0.8 to 3 wt% (for example, about 1 to 2 wt%). The lateral flow (5B) can have a dimethyl ether concentration of, for example, about 0 to 3% by weight (for example, about 0.0001 to 2% by weight) and preferably about 0.001 to 1.7 % by weight (for example, about 0.01 to 1.5% by weight), or a concentration of dimethyl ether of about 0.005 to 1% by weight (for example, about 0.01 to 0.5% by weight) or about 0.1 to 1% by weight. The side flow (5B) can have a methanol concentration of, for example, about 0 to 3% by weight (for example, about 0.001 to 2% by weight) and preferably about 0.01 to 1.5% by weight (for example, about 0.05 to 1% by weight). The reduction in the number of distillation stages (or plates) of the second distillation column (5) (for example, the reduction is the actual number of stages (or plates) from 100 to no more than 15% (or by about 10 to 15)) may tend to slightly increase the concentration of PRC (in a representative way, acetaldehyde) and the concentration of methyl acetate in the lateral flow (5B) (a mixture of an aqueous phase and an organic phase when the flow is separated in these phases, a mixture on line 63, a mixture of a flow on line 61 and a flow on line 62).
[00114] In a case where the lateral flow (5B) is separated into liquid-liquid (or forms an organic phase and an aqueous phase), the organic phase (lines 64, 68) may have a PRC concentration of, for example , about 0.1 to 90% by weight (for example, about 0.2 to 70% by weight) and preferably about 0.3 to 60% by weight (for example, 0.4 to 50% by weight ), or it may have a PRC concentration of about 0.1 to 20% by weight (for example, about 0.5 to 20% by weight) and preferably about 1 to 10% by weight (for example, about 2 to 5% by weight), or it may have a PRC concentration of about 3 to 10% by weight (for example, about 5 to 8.5% by weight). The organic phase can have a methyl iodide concentration of, for example, about 50 to 99% by weight (for example, about 60 to 98% by weight) and preferably about 70 to 97% by weight (for example , about 80 to 95% by weight), or it may have a concentration of methyl iodide of about 85 to 98% by weight (for example, about 90 to 97% by weight), or it may have a concentration of iodide methyl content of about 85 to 93% by weight. The organic phase may have a methyl acetate concentration of, for example, about 0.1 to 20% by weight (for example, about 0.5 to 10% by weight) and preferably about 0.7 to 7% % by weight (for example, about 1 to 5% by weight), or it may have a concentration of methyl acetate of about 2 to 4.54% by weight (for example, about 3 to 4% by weight), or it may have a concentration of methyl acetate of about 0.3 to 7% by weight (for example, about 0.5 to 5% by weight). The organic phase can have an acetate acid concentration of, for example, about 0 to 5% by weight (for example, about 0.001 to 3% by weight), preferably about 0.01 to 2% by weight, and about 0.1 to 0.5% by weight, or it can have a concentration of acetic acid of substantially no more than the detection limit. The organic phase can have a water concentration of about 0 to 5% by weight (for example, about 0.01 to 3% by weight) and preferably about 0.05 to 1% by weight (for example, about 0.1 to 0.3% by weight). The organic phase may have a dimethyl ether concentration of, for example, about 0 to 2.5% by weight (for example, about 0 to 5,000 ppm), preferably about 1 ppm to 2% by weight (for example , about 1 to 3,000 ppm), more preferably about 10 ppm to 1.5% by weight (for example, about 10 to 2,500 ppm), and more preferably about 100 ppm to 1% by weight (for example, about 100 to 2,000 ppm). The organic phase can have a methanol concentration of, for example, about 0 to 3% by weight (for example, about 0.001 to 2% by weight) and preferably about 0 to 1.5% by weight (for example , about 0.05 to 0.5% by weight), or it may have a methanol concentration of substantially no more than the detection limit. The reduction in the number of distillation stages (or plates) of the second distillation column (5) (for example, the reduction is the actual number of stages (or plates) from 100 to no more than 15% (or by about 10 to 15)) may tend to slightly increase the concentration of PRC (in a representative way, acetaldehyde) and the concentration of methyl acetate in the organic phase (lines 64, 68) liquid-liquid separated from the lateral flow (5B).
[00115] In a case where the lateral flow (5B) is separated into liquid-liquid (or forms an organic phase and an aqueous phase), the aqueous phase (lines 66, 69) may have a PRC concentration of about 1 to 50% by weight (for example, about 5 to 40% by weight) and preferably about 10 to 30% by weight (for example, about 15 to 25% by weight). The aqueous phase can have a methyl iodide concentration of, for example, about 0.01 to 10% by weight (for example, about 0.1 to 5% by weight) and preferably about 0.5 to 4 % by weight (for example, about 0.8 to 3% by weight), or it may have a concentration of methyl iodide of about 1 to 2% by weight. The aqueous phase can have a methyl acetate concentration of, for example, about 0.1 to 10% by weight (for example, about 0.2 to 5% by weight) and preferably about 0.3 to 2 % by weight (for example, about 0.5 to 1% by weight), or it can have a concentration of methyl acetate of about 0.1 to 1.5% by weight, or it can have a concentration of acetate of methyl of about 0.5 to 3% by weight (for example, about 1 to 2% by weight). The aqueous phase can have an acetate acid concentration of, for example, about 0 to 5% by weight (for example, about 0.001 to 3% by weight) and preferably about 0.01 to 2% by weight, or it can have a concentration of acetate acid substantially of no more than the detection limit (0% by weight). The aqueous phase may have a dimethyl ether concentration of, for example, about 0 to 1.5% by weight (for example, about 1 ppm to 1.2% by weight) and preferably about 0.001 to 1% by weight ( for example, about 0.01 to 1% by weight). The aqueous phase may have a methanol concentration of, for example, about 0.1 to 10% by weight (for example, about 0.5 to 8% by weight) and preferably about 1 to 6% by weight ( for example, about 1.5 to 5% by weight). The aqueous phase in general contains these components, inevitable contaminants (including impurities or by-products), and water like the rest. The aqueous phase can have a water concentration of, for example, about 50 to 95% by weight (for example, about 60 to 93% by weight) and preferably about 70 to 90% by weight (for example, about from 75 to 85% by weight), or it may have a water concentration of about 65 to 85% by weight (for example, about 70 to 85% by weight). The reduction in the number of distillation stages (or plates) of the second distillation column (5) (for example, the reduction is the actual number of stages (or plates) from 100 to no more than 15% (or by about 10 to 15)) may tend to slightly increase the concentration of methyl acetate in the aqueous phase (lines 66, 69) liquid-liquid separated from the lateral flow (5B).
[00116] The concentration of PRC in the extraction mixture or lateral flow (5B) (line 63) [for example, the concentration of acetaldehyde in the aqueous phase (aqueous extract) (lines 66, 69) formed in liquid-liquid separation ] has a greater influence on the ratio of methyl iodide to acetaldehyde (Mel / AD ratio), that is, the amount of methyl iodide to be discarded along with acetaldehyde out of the system. The amount of methyl iodide to be discarded out of the system is higher in both an excessively low and a high concentration of acetaldehyde. In order to reduce the amount of methyl iodide to be discarded (or to make the Mel / AD ratio smaller), the concentration of PRC in the extraction mixture or side flow (5B) (line 63) (for example, the concentration of acetaldehyde in the aqueous phase (aqueous extract)) can be about 0.1 to 45% by weight (for example, about 0.5 to 30% by weight), preferably about 1 to 25% by weight (for example, about 1.5 to 15% by weight), and more preferably about 2 to 10% by weight. The efficient concentration of PRC in the extraction mixture or side flow (5B) (line 63) (in particular, the concentration of acetaldehyde in the aqueous phase (aqueous extract) (lines 66, 69)) can be about 5 to 45 % by weight, preferably about 10 to 40% by weight, and more preferably about 15 to 35% by weight (e.g., about 20 to 30% by weight) or it can also be 10 to 25% by weight (e.g. example, about 12 to 25% by weight).
[00117] The aqueous phase (lines 66, 69), which is a liquid-liquid phase separated from the lateral flow (5B), contains enriched PRC's (for example, acetaldehyde) and has a concentration of PRC (for example, acetaldehyde) greater than a concentration of methyl iodide. The aqueous phase may have a ratio (AD / Mel) of acetaldehyde (AD) to methyl iodide (Mel) of, for example, about 3/1 to 50/1 (for example, about 4/1 to 40/1) and preferably about 5/1 to 30/1 (for example, about 7/1 to 20/1), or it can be about 8/1 to 15/1 (for example, about 10 / 1 to 1/15).
[00118] The lateral flow (5B) (line 63) can have a temperature at an atmospheric pressure of, for example, about 15 to 110 ° C (for example, about 20 to 90 ° C) and preferably about 25 to 80 ° C (for example, about 30 to 70 ° C).
[00119] The lower flow (5C) (a line 52) in general contains methyl iodide as a major component, and is rich in methyl iodide. In a case where the first suspended flow (3A) to be fed into the distillation column (5) is a homogeneous liquid or a mixture of an aqueous phase and an organic phase, the lower flow (5C) (line 52) may show a concentration of PRC (representatively, acetaldehyde) of, for example, about 0 to 1% by weight (for example, about 1 to 5,000 ppm), preferably about 0 to 2,500 ppm (for example, about 10 to 1,000 ppm), and more preferably about 50 to 500 ppm, or it can have a PRC concentration of about 30 to 2,500 ppm (for example, about 100 to 2,000 ppm), or it can have a PRC concentration of substantially no more than the detection limit. The lower flow (5C) can have a methyl iodide concentration of, for example, about 10 to 85% by weight (for example, about 25 to 80% by weight) and preferably about 40 to 75% by weight (for example, about 50 to 70% by weight); it may have a concentration of methyl iodide of about 50 to 99% by weight (for example, about 60 to 95% by weight) and preferably about 70 to 90% by weight (for example, about 75 to 88% by weight), or it may have a methyl iodide concentration of about 1 to 75% by weight (for example, about 5 to 65% by weight). The lower flow (5C) can have a methyl acetate concentration of, for example, about 0 to 30% by weight (for example, about 0.1 to 25% by weight) and preferably about 1 to 20% by weight (for example, about 5 to 20% by weight), or it may have a concentration of methyl acetate of about 7 to 17% by weight (for example, about 10 to 15% by weight); or it may have a concentration of methyl acetate of about 0 to 40% by weight (for example, about 1 to 30% by weight) and preferably about 3 to 25% by weight (for example, about 5 to 20%) % by weight), or it can have a concentration of methyl acetate of about 7 to 18% by weight (for example, about 10 to 17% by weight), or it can have a concentration of methyl acetate of about 5 to 15% by weight. The lower flow (5C) can have an acetic acid concentration of, for example, about 0 to 12% by weight (for example, about 0.1 to 10% by weight) and preferably about 0.5 to 8 % by weight (for example, about 1 to 7% by weight); or it can have an acetic acid concentration of about 1 to 5% by weight (for example, about 1 to 3% by weight), or it can have an acetic acid concentration of about 5 to 30% by weight (eg example, about 7 to 25% by weight). The lower flow (5C) can have a water concentration of, for example, about not less than 1% by weight (for example, about 5 to 89% by weight), preferably not less than 10% by weight (for example, for example, about 15 to 87% by weight), and more preferably not less than 20% by weight (for example, about 30 to 85% by weight); or it may have a water concentration of about 5 to 52% by weight (for example, about 10 to 42% by weight) and preferably about 15 to 37% by weight (for example, about 17 to 32% by weight) Weight); or it may have a water concentration of about 0 to 10% by weight (for example, about 0.001 to 5% by weight), preferably about 0.01 to 3% by weight (for example, about 0.1 to 2% by weight), and more preferably about 0.2 to 1% by weight or more (for example, about 0.3 to 0.8% by weight), or it may have a water concentration of about 5 to 65% by weight (for example, about 15 to 60% by weight). The lower flow (5C) can have a dimethyl ether concentration of, for example, about 0 to 2,000 ppm (for example, about 1 to 1500 ppm) and preferably about 10 to 1,000 ppm (for example, about 50 at 500 ppm); or it may have a dimethyl ether concentration of about 0.01 to 1,000 ppm and preferably about 0.1 to 500 ppm (for example, about 1 to 100 ppm), or it can have a dimethyl ether concentration of substantially no more than the detection limit. The lower flow (5C) can have a methanol concentration of, for example, about 0 to 2% by weight (for example, about 0.0001 to 1% by weight) and preferably about 0.001 to 0.5% by weight (for example, about 0.01 to 0.3% by weight) or may have a methanol concentration of about 0.1 to 1.5% by weight (for example, about 0.2 to 1 % by weight). In a case where the concentration of water in the first suspended stream (3A) to be fed into the second distillation column (5) (or the ratio of the aqueous phase 43b to the organic phase 44) is higher, the lower flow (5C) (line 52) may show a tendency to decrease the concentration of methyl iodide and the concentration of methyl acetate, and to increase the water content, and to slightly increase the concentration of methanol.
[00120] In a case where the first suspended flow (3A) to be fed into the distillation column (5) and a mixture of an aqueous phase and an organic phase, the lower flow (5C) (line 52) may show a concentration of PRC (representatively, acetaldehyde) of, for example, about 0 to 1% by weight (for example, about 1 to 5,000 ppm), preferably about 0 to 2,500 ppm (for example, about 10 to 1,000 ppm), and more preferably about 50 to 500 ppm; or it may have a PRC concentration of about 50 to 5,000 ppm (for example, about 100 to 3,000 ppm) and preferably about 150 to 2,000 ppm (for example, about 170 to 1500 ppm); or it may have a PRC concentration of substantially no more than the detection limit. The lower flow (5C) can have a methyl iodide concentration of, for example, about 1 to 80% by weight (for example, about 3 to 70% by weight), preferably about 5 to 60% by weight (for example, about 7 to 50% by weight), and more preferably about 10 to 40% by weight, or it may have a methyl iodide concentration of about 7 to 60% by weight (for example, about 10 to 55% by weight). The lower flow (5C) can have a methyl acetate concentration of, for example, about 0 to 40% by weight (for example, about 1 to 30% by weight) and preferably about 3 to 25% by weight (for example, about 5 to 20% by weight); or it may have a concentration of methyl acetate of about 7 to 18% by weight (for example, about 8 to 17% by weight); or it may have a concentration of methyl acetate of about 5 to 15% by weight (for example, about 7 to 13% by weight). The lower flow (5C) can have an acetic acid concentration of, for example, about 0 to 40% by weight (for example, about 1 to 30% by weight) and preferably about 2 to 25% by weight ( for example, about 3 to 23% by weight), or it can have a concentration of acetate acid of about 5 to 30% by weight (for example, about 8 to 25% by weight). The lower flow (5C) can have a water concentration of, for example, about 1 to 95% by weight (for example, about 2 to 90% by weight), preferably about 5 to 85% by weight (eg for example, about 7 to 80% by weight), more preferably about 10 to 75% by weight (for example, about 20 to 70% by weight), and more preferably about 30 to 65% by weight, or can have a water concentration of about 20 to 60% by weight. The lower flow (5C) can have a dimethyl ether concentration of, for example, about 0 to 2,000 ppm (for example, about 0.01 to 1,000 ppm) and preferably about 0.1 to 500 ppm (for example , about 1 to 100 ppm), or it may have a concentration of dimethyl ether substantially no more than the limit of detection. The lower flow (5C) can have a methanol concentration of, for example, about 0 to 2% by weight (for example, about 0.0001 to 1% by weight) and preferably about 0.001 to 0.5% by weight (for example, about 0.01 to 0.3% by weight), or it may have a methanol concentration of about 0.1 to 2% by weight (for example, about 0.2 to 1, 5% by weight) and preferably about 0.3 to 1% by weight.
[00121] In a case where the first suspended flow (3A) to be fed into the distillation column (5) and an organic phase formed in the liquid-liquid separation, the lower flow (5C) can present a concentration of PRC (in a representative, acetaldehyde) of, for example, about 0 to 1% by weight (for example, about 1 to 5,000 ppm) and preferably about 0 to 2,500 ppm (for example, about 10 to 1,000 ppm), or present a PRC concentration of substantially no more than the detection limit. The lower flow (5C) can have a methyl iodide concentration of, for example, about 10 to 95% by weight (for example, about 30 to 93% by weight) and preferably about 50 to 90% by weight (for example, about 70 to 90% by weight); for example, or it may have a concentration of methyl iodide of not less than 10% by weight (for example, about 15 to 90% by weight), preferably not less than 20% by weight (for example, about 25 to 90% by weight), more preferably not less than 30% by weight (for example, about 30 to 80% by weight), and particularly about 40 to 70% by weight (for example, about 50 to 65% by weight) Weight). The lower flow (5C) can have a concentration of methyl acetate of, for example, about 1 to 30% by weight (for example, about 3 to 25% by weight) and preferably about 5 to 20% by weight (for example, about 7 to 16% by weight). The lower flow (5C) can have an acetate acid concentration of, for example, about 0 to 10% by weight (for example, about 0.1 to 7% by weight) and preferably about 0.3 to 5 % by weight (for example, about 0.5 to 3% by weight). The lower flow (5C) can have a water concentration of about 0 to 52% by weight (for example, about 0.01 to 42% by weight), preferably about 0.1 to 32% by weight (eg for example, about 0.2 to 22% by weight), and more preferably about 0.5 to 11% by weight (for example, about 1 to 6% by weight); or it may have a water concentration of about 0 to 6% by weight (for example, about 0.1 to 4% by weight) and preferably about 0.3 to 3% by weight (for example, about 0 , 5 to 2% by weight). The lower flow (5C) can have a dimethyl ether concentration of, for example, about 0 to 2,000 ppm (for example, about 1 to 1500 ppm) and preferably about 10 to 1,000 ppm (for example, about 50 at 500 ppm); or it may have a dimethyl ether concentration of about 5 to 500 ppm (for example, about 10 to 100 ppm); or it may have a concentration of dimethyl ether substantially of no more than the detection limit. The lower flow (5C) can have a methanol concentration of, for example, about 0 to 1% by weight (for example, about 0.001 to 0.8% by weight) and preferably about 0.005 to 0.5% by weight (for example, about 0.01 to 0.5% by weight).
[00122] In a case where the first suspended flow (3A) to be fed into the distillation column (5) and an aqueous phase formed in the liquid-liquid separation, the lower flow (5C) can present a concentration of PRC (in a representative, acetaldehyde) of, for example, about 0 to 1% by weight (for example, about 1 to 5,000 ppm) and preferably about 0 to 2,500 ppm (for example, about 10 to 1,000 ppm), or present a PRC concentration of substantially no more than the detection limit. The lower flow (5C) can have a methyl iodide concentration of, for example, about 0.1 to 30% by weight (for example, about 0.5 to 25% by weight) and preferably about 1 to 20% by weight (for example, about 3 to 15% by weight); or it may have a concentration of methyl iodide of not less than 1.5% by weight (for example, about 2 to 50% by weight), preferably not less than 2% by weight (for example, about 3 to 40%) % by weight), and more preferably not less than 4% by weight (for example, about 5 to 30% by weight). The lower flow (5C) can have a methyl acetate concentration of, for example, about 1 to 30% by weight (for example, about 3 to 25% by weight) and preferably about 5 to 20% by weight (for example, about 7 to 15% by weight). The lower flow (5C) can have an acetic acid concentration of, for example, about 5 to 60% by weight (for example, about 10 to 50% by weight) and preferably about 20 to 40% by weight ( for example, about 25 to 35% by weight). The lower flow (5C) can have a water concentration of, for example, about 10 to 92% by weight (for example, about 25 to 82% by weight) and preferably about 30 to 77% by weight (eg example, about 40 to 72% by weight). The lower flow (5C) can have a dimethyl ether concentration of, for example, about 0 to 2,000 ppm (for example, about 0.1 to 1500 ppm) and preferably about 1 to 1,000 ppm (for example, about from 5 to 500 ppm); or it may have a dimethyl ether concentration of about 1 to 500 ppm (for example, about 5 to 100 ppm); or it may have a concentration of dimethyl ether substantially of no more than the detection limit. The lower flow (5C) can have a methanol concentration of, for example, about 0 to 5% by weight (for example, about 0.001 to 3% by weight), preferably about 0.1 to 2.5% by weight. weight (for example, about 0.5 to 2% by weight).
[00123] The lower flow (5C) can have a temperature at an atmospheric pressure of, for example, about 30 to 160 ° C (for example, about 35 to 120 ° C) and preferably about 40 to 100 ° C (for example, about 40 to 80 ° C).
[00124] The lower flow (5C) shows a concentration of PRC (such as acetaldehyde) significantly lower than that of the first suspended flow (3A). For example, the lower flow (5C) can have a PRC concentration of about 1 ppm to 0.3% by weight (for example, about 1 to 800 ppm), preferably about 10 ppm to 0.2% by weight. weight (for example, about 20 to 1,000 ppm), and more preferably about 30 to 500 ppm, or it can have a PRC concentration of substantially no more than the detection limit (0% by weight). Thus the lower flow (5C) can be recycled in the reaction system via line 52. If necessary, via line 52 the lower flow (5C) can be subjected to further distillation, and then optional water extraction to remove and separating PRC's (for example, acetaldehyde).
[00125] According to the present invention, the first suspended flow (3A) is distilled in the second distillation step (5) to form the second suspended flow (5A), the lateral flow (5B), and the lower flow or flow background (5C). The distillation column of the second distillation step (5) can function as a column that removes aldehyde. Thus, the first suspended stream (3A) contains at least one PRC (e.g., acetaldehyde) and methyl iodide, and has a composition that corresponds to the composition of the mixed composition. The first suspended stream or mixed composition (3A) may additionally contain methyl acetate. In the manner described above, the first suspended stream or mixed composition (3A) may additionally contain at least one selected from acetate, methanol, water, dimethyl ether, an acetaldehyde derivative (for example, an aldehyde, a ketone, an iodide of alkyl, a higher boiling point alkanocarboxylic acid and an alkane), a dialkyl ether or other compounds.
[00126] The distillation column of the second distillation step (5) is provided with at least one receiver (for example, a flue pan). The distillation column can be provided with a plurality of receivers (chimney tray). For a distillation column with a plurality of receivers (chimney tray), the extraction agent is added to a concentration zone that is formed below the highest chimney tray. (6) Liquid-liquid separation step
[00127] In the embodiment shown in figure 1, the second suspended flow (5A) is cooled and condensed in the condenser C3, in the withdrawal line 53, and is separated biphasically in the separation unit (decanter) 6a to form an organic phase (a lower phase, a refined phase) and an aqueous phase (an upper phase, an extract). The organic phase is refluxed or recycled in the distillation column (for example, the top of the column) of the second distillation step (5) via the reflux line 61. The aqueous phase of the decanter 6a is fed into the retention tank 6b by middle of line 62. The extraction mixture (5B) as the side flow is also fed into the holding tank 6b via line 63. The liquid in the holding tank 6b is separated biphasically. The holding tank 6b also functions as a capping tank or a decanter.
[00128] The organic phase (the refined) of the retention tank 6b is recycled in the distillation column of the second distillation step (5) by means of line 64 and a recycling line 65, in a position less than a position that removes the lateral flow (5B). The lateral flow and extraction mixture (5B) has a relatively high temperature, and a portion of the aqueous phase (the extract) of the retention tank 6b is cooled in a cooling unit (chiller) C4 in line 66, and is separated biphasically in the decanter 6c. The residual portion of the aqueous phase (the extract) of the retention tank 6b is recycled in the distillation column of the second distillation step (5) via line 67 in a position lower than a position that removes the lateral flow (5B). As shown by a dotted line, a portion of the aqueous phase (extract) on line 66 can be recycled as an extraction agent.
[00129] In decanter 6c, a small amount of methyl iodide can be separated by biphasic separation (or formation of an organic phase and an aqueous phase). The organic phase (a heavy phase rich in methyl iodide or a lower phase) formed in the decanter 6c and recycled in the distillation column of the second distillation step (5) via line 68. The aqueous phase (a light phase rich in acetaldehyde or an upper phase) formed in the decanter 6c and fed to the third distillation step (distillation column) (7) via line 69 to further separate PRC's and methyl iodide.
[00130] Each condensate (the aqueous phase, the organic phase, or a mixture of these) cooled in the condenser C3 and the liquid flow (and the aqueous phase and the organic phase) cooled in the cooling unit C4 can have a temperature of, for example, for example, about 0 to 60 ° C (for example, about 1 to 50 ° C), preferably about 3 to 30 ° C (for example, about 3 to 20 ° C), and more preferably about 5 to 15 ° C.
[00131] In practical cases, at least the extraction mixture (5B) is separated biphasically. The extraction mixture (5B) and the suspended flow (5A) can be separated biphasically independently or in combination. Specifically, in the manner described above, each extraction mixture (5B) and the suspended flow (5A) can be separated liquid-liquid; or, without liquid-liquid separation of the suspended flow (5A) in the decanter 6a, the suspended flow (5A) can be mixed or mixed with the extraction mixture (5B), and the resulting mixture can be separated liquid-liquid.
[00132] The extract (aqueous phase) and / or the refined (organic phase) formed in the liquid-liquid separation can be recycled in several ways (through several ways) in the second distillation step (5). In this embodiment, in the manner described above, a portion of the aqueous phase formed in the holding tank 6b and the organic phases (the organic phase formed in the holding tank 6b and the organic phase formed in the decanter 6c) are mixed together via line 67 and lines 64, 68, respectively, to recycle the resulting mixture in the second distillation step (5).
[00133] In the second distillation step (5), a portion of the refine (or organic phase) can be recycled, practically at least a portion of the refine (or organic phase), for example, the entire refine (or organic phase).
[00134] In the third stage of distillation (distillation column) (7), the extract (or aqueous phase) formed in the second stage of liquid-liquid separation (6) is fed and, in general, at least one portion or all extract (or aqueous phase) and fed. If necessary, a portion of the refined (or organic phase) can also be fed in the third distillation stage (distillation column) (7).
[00135] Recycling at least the extract (or aqueous phase) on a plate that is in a lower position of the distillation column (5) to a withdrawal port to remove the lateral flow (5B) increases the concentrations of acetaldehyde and water, in a position higher than the feed plate on the distillation column (5), to prevent the formation of an azeotropic composition containing a combination of a plurality of components, such as methyl iodide, methyl acetate, acetaldehyde and water, and in some cases, to reduce the concentration of acetic acid by increasing the concentration of water. Thus, the concentration of methyl acetate can be reduced in a space greater than the distillation column feed plate (5). In addition, acetate acid present in a space greater than the distillation column feed plate (5) can be converted to methyl iodide or methyl acetate to decrease the concentration of acetate. For example, the concentration of methyl acetate or acetate acid in a space greater than the distillation column feed plate (recycling plate) (5) can be reduced: by feeding the aqueous phase and the organic phase into the distillation column (5 ) through feed lines 43b and 44; recycling the organic phase or medium from lines 64, 68 and the aqueous phase through line 67 in the distillation column (5); and / or feeding the aqueous phase into the distillation column (5) via the feed line 43b. In addition, recycling a stream (including an aqueous phase, an organic phase, or the like) in the second distillation step (5) increases the concentration of the components of the recycle stream in the distillation column to prevent an increase in the concentration of the amphipathic compound, such as methyl acetate, independent of the position of the withdrawal port to withdraw the lateral flow (5B). Thus, the concentration of methyl acetate or acetate in the aqueous phase [for example, the side flow (5B), the aqueous phase in tank 6b, and in addition, the aqueous phase via line 67] can be reduced to decrease the amount of methyl iodide dissolved in the aqueous phase. The amount of recycling of the aqueous phase can be selected appropriately, considering the stability of the process. A very large amount of recycling of the aqueous phase causes a large amount of water to flow from the bottom stream (5C) (line 52) of the second distillation column (5) to undesirably increase the water concentration in the reaction system. or in the process. In a case where a large amount of acetate is incorporated with the side flow (5B) by addition and distillation, and recycling of acetate (miscible solvent) as the amphipathic component (mentioned below), the amount of methyl iodide, as well as methyl acetate, dissolved in the aqueous phase and greater to induce a loss of methyl iodide.
[00136] It is not necessary to cool and condense the second suspended flow (5A) to separate liquid-liquid from the condensate in the separation unit 6a. The entire second suspended flow (5A) can be refluxed in the distillation column of the second distillation step (5).
[00137] According to the present invention, the extraction mixture (5B) can be fed in the third distillation stage (distillation column) (7) without being subjected to the liquid-liquid separation stage (6) (or without condensation) and / or liquid-liquid separation).
[00138] The extraction mixture (5B) is generally separable in an upper phase (aqueous phase) and a lower phase (organic phase). Thus, in a case where the extraction mixture is separated biphasically in the distillation column of the distillation step (5), the extraction mixture (5B) can be kept in a tray (or a decanter in the distillation system) for biphasic separation , or an aqueous phase formed in the column can be selectively removed by lateral cutting. In a preferred embodiment, the total amount of liquid that falls or the extraction mixture (5B) can be removed from the distillation column in the distillation step (5) by side cutting and, if necessary, after being cooled, the removed mixture can be removed. be separated biphasically in a decanter which is disposed outside the distillation system. In addition, the extraction mixture (5B) and the suspended flow (5A) can be separated biphasically, independently or in combination.
[00139] The total retention time of the extraction mixture in the extractive distillation zone formed in the distillation column, and in the decanter disposed outside the distillation system is sufficient for biphasic separation of the extraction mixture. The total retention time can be, for example, no less than 10 seconds (for example, about 30 seconds at 120 minutes) and preferably about 1 to 100 minutes (for example, about 5 to 60 minutes), or be about 10 to 120 minutes (for example, about 15 to 60 minutes).
[00140] In the liquid-liquid separation step (6), at least the lateral flow or extraction mixture (5B) between the second suspended flow (5A) and the lateral flow or extraction mixture (5B) can be separated biphasically to additionally separate PRC's and methyl iodide from each other.
[00141] The liquid-liquid separation step (6) can comprise one or two liquid-liquid separation steps (or a holding tank and / or a decanter) without using a plurality of units (the separation unit 6a, the retention tank 6b, and decanter 6c). At least a portion of the aqueous phase (aqueous phase enriched with acetaldehyde) can be separated or removed to form the process; it can be used as an extraction agent in the distillation step (5); or it can be recycled in the reaction step (reactor) (1). At least a portion of the organic phase (an organic phase containing methyl iodide) can be recycled in the distillation step (5) directly or indirectly. For example, the organic phase rich in methyl iodide can be recycled in an appropriate position of the distillation column of the second distillation step (5); it can be recycled in a position higher than the withdrawal port for lateral flow (5B); or it can preferably be recycled at a lower position than the withdrawal port for lateral flow (5B) to form a concentration zone in the second distillation step (5).
[00142] As previously described, the lateral flow (5B) is practically obtained from the concentration zone, in order to extract PRC's efficiently. In a case like this, the extraction mixture (such as the organic phase) can be recycled in the concentration zone of the distillation column (5), or it can be recycled on a plate with the same height as that of the feed port (or feed plate) for the first suspended flow or mixed composition (3A), or can be recycled in a plate below the feed port. [Miscellaneous solvent]
[00143] The end of efficiently separates methyl iodide and PRC's (for example, acetaldehyde) from each other, in the presence of methyl acetate, a miscible solvent, which is miscible with an organic phase, can be fed in a stream (an organic phase and / or an aqueous phase) which is recycled in the second distillation step (5). The miscible solvent can include a solvent with a high affinity for both an amphipathic compound (such as methyl acetate) and PRC's; a solvent capable of inhibiting the formation of an azeotropic composition of an amphipathic compound (such as methyl acetate) and other compounds (in particular, water, PRC's such as acetaldehyde); and a solvent which is less than decreases the volatility (vapor pressure) of an amphipathic compound (such as methyl acetate); or other solvents. The miscible solvent generally alters an azeotropic composition (or gaseous composition) of PRC's and methyl iodide in the presence of methyl acetate, or prevents the formation of an azeotropic composition and causes a distribution of methyl acetate concentration towards the height of the distillation column; and / or decreases the volatility (vapor pressure) of methyl acetate. Thus, the addition of the miscible solvent reduces the concentration of methyl acetate in the aqueous phase and prevents methyl iodide from being mixed in the aqueous phase.
[00144] The miscible solvent can be an internal miscible solvent present in the system [for example, a solvent present in the acetic acid production process or a solvent produced in the process, or a process flow (for example, an aqueous solvent such as an aqueous extract 67)] or it can be an external miscible solvent from outside the system (for example, at least one selected from water, acetic acid and other compounds). The miscible solvent may have a boiling point greater than that of methyl iodide and PRC's (for example, acetaldehyde). The process flow can be a process flow (for example, a crude acetate acid flow, a suspended flow, a bottom flow and a recycling flow) capable of decreasing the volatility (vapor pressure) of methyl acetate. The miscible solvent can be an amphipathic solvent. The miscible solvent in general contains at least one element selected from water, acetate, methyl iodide and methanol. The miscible solvent that is fed extremally can be water or other solvents and is, in general, an organic miscible solvent, for example, a miscible solvent containing acetate (such as acetate or crude acetate). A preferred miscible solvent can be an aqueous phase separated from the second suspended flow (5A) and / or the lateral flow (5B) [for example, an aqueous phase produced in the second liquid-liquid separation step (6)] or it can be a process flow containing acetate (for example, a flow of crude acetate).
[00145] In the process shown in figure 1, in the distillation column of the second distillation stage (5) and the miscible solvent is fed through a feed line 70 and / or the aqueous phase (or extract), through the line 67, and distillation in the presence of the miscible solvent separates methyl iodide and PRC's (for example, acetaldehyde) in the presence (coexistence) of an amphipathic compound (such as methyl acetate).
[00146] The miscible solvent can be fed directly into the distillation column of the second distillation stage (5), via feed line 70, or it can be fed indirectly into the distillation column of the second distillation stage (5), by through a recycling line 65, or other lines. The miscible and general solvent is fed at a lower position than the receiver (such as a flue pan) in height, in order to prevent condensation of methyl acetate in a space between the lower feed port and the feed plate from the first suspended flow (3A) (in the process shown in the drawing, the condensate from the liquid-liquid separation step (4)) in practical cases. The miscible solvent can be fed in a position higher than or over the receiver (such as a flue pan), in height (for example, in the concentration zone or extraction zone). By the way, condensation of ethyl acetate in the space can be prevented by preventing (or inhibiting) the formation of the azeotropic composition, decreasing the volatility (vapor pressure) of methyl acetate, or by other means, in the manner described above.
[00147] Assuming that the total number of plates in the distillation column is 100, feed the miscible solvent (such as acetate) into a plate below the recycling line 65 (for example, a plate that is positioned on 10 to 30 plates less than a recycling plate, in which a recycling stream is fed through the recycling line 65) can efficiently prevent the miscible solvent (for example, acetic acid) from mixing with the extraction mixture (5B) from the line 63. Thus, it is possible to reduce the amount of methyl iodide dissolved in the aqueous phase separated in the liquid-liquid separation step (6). Assuming that the total number of plates in the distillation column is 100, the miscible solvent such as acetic acid can be fed into a plate that is below the side flow plate (receiver) of the side flow (5B), and is 10a to 50a ( for example, the 20th to 40th) plate from the top plate. For example, assuming the height level of the distillation portion of the distillation column is "1", the miscible solvent, for example, can be fed at a height level of about 0.1 / 1 to 0.5 / 1 (for example, about 0.15 / 1 to 0.45 / 1) and preferably about 0.2 / 1 to 0.4 / 1 (for example, about 0.25 / 1 to 0.3 / 1) 1) from the top of the column. For example, for a column of distillation plates with the actual total number of stages (or plates) of 43, the miscible solvent can be fed between the upper plate at the top of the column and a plate that is positioned 40 plates below the plate upper (the 40th plate) (preferably the 35th plate from the upper plate, more preferably the 25th plate from the upper plate, and particularly the 15th plate from the upper plate). For a column of distillation plates with the actual total number of stages (or plates) of 10, the miscible solvent can be fed between the upper plate at the top of the column and a plate positioned 10 plates lower than the upper plate (the 10th plate ) (preferably the 7th plate from the upper plate, more preferably the 5th plate from the upper plate, and particularly the 3rd plate from the upper plate).
[00148] The miscible solvent can have the same temperature as the extraction agent does. The miscible solvent can be added to the distillation column as a solvent heated to the same temperature as the temperature of the extraction agent, or as a vaporized (or vapor) form.
[00149] The amount to be added of the miscible solvent can be no more than 30% by weight, for example, about 0.01 to 20% by weight (for example, about 0.1 to 15% by weight), and preferably about 0.5 to 10% by weight (e.g., about 1 to 5% by weight) with respect to the amount of liquid that falls from the concentration zone (the amount of liquid that falls into the tray (s) ( s)) in the second distillation stage (5). The total amount of the extraction mixture (5B) recycled in the second distillation step (5) [for example, the recycled amount of the aqueous phase separated biphasically in the extraction mixture (5B)], and / or the added amount of the miscible solvent it can be no more than 30% by weight [for example, about 0.01 to 20% by weight (for example, about 0.1 to 15% by weight) and preferably about 0.5 to 10% by weight (for example, about 1 to 5% by weight)] with respect to the amount of liquid that falls from the concentration zone in the second distillation step (5), in the same manner as described above.
[00150] In a case where the miscible solvent (for example, acetic acid) is distilled in the distillation column of the second distillation step (5) together with an organic phase from the liquid-liquid separation step (6) or others steps [for example, distillation of the organic phase formed in the retention tank 6b and the miscible solvent (eg, acetic acid) of line 70, or distillation of the organic phase and the miscible solvent (eg, acetic acid) fed from a distillation plate less than a lateral flow-removing position (5B)], the combination of a plurality of components such as methyl iodide, methyl acetate, acetaldehyde and water can be avoided by forming an azeotrope (or an azeotropic composition), or the methyl acetate vapor pressure can be simply decreased (or reduced) in the second distillation column (5). Even in a case like this, the concentration of methyl acetate in the liquid process (a condensate, an upper phase and / or a lower phase, in particular, an upper phase containing acetaldehyde) is fed into the third distillation step (7) through line 69 can be decreased to result in a reduction in the concentration of methyl iodide dissolved in the aqueous phase.
[00151] In the acetic acid production process, although it is preferable to use water in the system as a balanced (or internal) water without providing water outside the system, the recycling of the aqueous phase (for example, the aqueous phase by means of line 67) in the distillation column (5) slightly increases the concentration of water in the bottom stream (5C) (line 52) of the distillation column (5), thereby altering the water balance in the system. In contrast, the use of miscible organic solvent such as acetate reduces the concentration of methyl acetate in the distillation column, while maintaining the water balance in the system, thereby reducing the amount of methyl iodide to be discarded. For example, the aqueous phase (for example, the aqueous phase in the system, as in line 67) is recycled in the distillation column (5) while the miscible solvent (for example, acetic acid) is added to the distillation column (5 ), and the bottom flow (5C) (line 52) of the distillation column (5) is recycled in the reaction system; a process like this reduces the concentration of methyl acetate in the distillation column to the maximum limit, to reduce the amount of methyl iodide to be discharged out of the system, while preventing the accumulation of water in the reaction system.
[00152] Addition of the miscible solvent (for example, acetic acid) can induce aldol condensation in the distillation column of the second distillation step (5) to produce substances with a higher boiling point from acetaldehyde, which must be concentrated on top of the column, and thus may decrease the separation of acetaldehyde. However, acetic acid exhibits only extremely weak acidity in a system with a high concentration of methyl iodide and a low concentration of water. In a system like this, condensation of aldol in an acidic condition is minimized and affects only the concentration of acetaldehyde.
Thus, the introduction of the aqueous solvent (for example, aqueous extract 67) produced in the process and / or the miscible solvent in the distillation column of the second distillation step (5) prevents a formation of two or three components azeotrope selected from methyl iodide, water, methyl acetate and acetaldehyde, or simply decrease the methyl acetate vapor pressure to significantly decrease the concentration of methyl acetate in the aqueous phase.
[00154] Incidentally, in a case where a quantity of acetate as the miscible solvent is very high, there is a possibility of increasing a concentration of acetate in the lateral flow (5B) and extract 67, and of increasing a concentration of methyl iodide in the aqueous phase. However, such a situation is avoided by feeding an appropriate amount of acetic acid.
[00155] If necessary, the liquid (the condensate, the aqueous phase and / or the organic phase) formed in the liquid-liquid separation step (6) can be temporarily stored or kept in a buffer tank to reduce flow fluctuation process flow. (7) Distillation step
[00156] The aqueous phase (a light phase rich in acetaldehyde or an upper phase) of the liquid-liquid separation step (6) and separated into a third suspended flow (lower boiling point flow) (7A) rich in a permanganate reducing compound (in particular, acetaldehyde) and methyl iodide, and a liquid flow rich in the extraction agent (higher boiling point flow, lower flow or bottom flow) (7B) in the third distillation step (column distillation) (7). The third suspended flow (lowest boiling point flow) (7A) is cooled and condensed in a C5 condenser; a first portion of the condensate is taken up to the distillation column (7) of the third distillation stage by means of a reflux line 73 per reflow, and a second portion of the condensate is fed into a fourth distillation stage (8) by means of of a 74 power line.
[00157] The internal temperature of the distillation column of the third distillation step (7) depends on its internal pressure. At the internal pressure of an atmospheric pressure, the distillation column can have a column top temperature of, for example, about 10 to 90 ° C (for example, about 15 to 80 ° C) and preferably about 20 to 70 ° C (for example, about 20 to 60 ° C), or it can have a column bottom temperature of, for example, about 70 to 170 ° C (for example, about 80 to 160 ° C) and preferably about 90 to 150 ° C (for example, about 95 to 140 ° C). The distillation column can have a top column pressure of, for example, about 0.1 to 0.5 MPa, preferably about 0.2 to 0.4 MPa and more preferably about 0.25 to 0, 35 MPa in terms of absolute pressure.
[00158] The distillation column can have a theoretical stage (or plate) of, for example, about 1 to 50 (for example, about 2 to 40) and preferably about 3 to 30 (for example, about 5 to 10). The flow rate of the distillation column can be, for example, about 1 to 1,000 (for example, about 2 to 500), preferably about 3 to 100 (for example, about 4 to 50), and more preferably about 5 to 30.
[00159] The suspended stream (7A) or a condensate thereof (lines 72, 73, 74) is rich in acetaldehyde and has a lower concentration of methyl iodide. The suspended stream (7A) or the condensate thereof also contains methyl acetate. The suspended flow condensate (7A) can have a PRC concentration (in a representative manner, acetaldehyde) of, for example, about 50 to 99.9% by weight (for example, about 60 to 99% by weight), preferably about 70 to 98% by weight (for example, about 75 to 97% by weight), and more preferably about 80 to 95% by weight (for example, about 85 to 95% by weight). The condensate may have a methyl iodide concentration of, for example, about 0.1 to 20% by weight and preferably about 0.5 to 10% by weight (for example, about 1 to 7% by weight) , or it can have a methyl iodide concentration of about 2 to 10% by weight (for example, about 3 to 10% by weight). The condensate may have a concentration of methyl acetate of, for example, about 0.1 to 20% by weight, preferably about 0.5 to 15% by weight (for example, about 0.7 to 12% by weight) weight), and more preferably about 1 to 10% by weight (e.g., about 1 to 5% by weight). The condensate from the suspended stream (7A) can have an acetic acid concentration of, for example, about 0 to 5% by weight, preferably about 0 to 3% by weight, and more preferably about 0 to 1% by weight . In some embodiments, the suspended flow condensate (7A) does not substantially contain any acetic acid (or has an acetic acid concentration no more than the detection limit). The suspended flow condensate (7A) can have a water concentration of, for example, about 0 to 5% by weight (for example, about 0 to 3% by weight), preferably 0 to 1% by weight (for example, example, 0 to 0.1% by weight), or it may have a water concentration no more than the detection limit. The condensate can have a dimethyl ether concentration of, for example, about 1 ppm to 5% by weight (for example, about 0.001 to 3% by weight), preferably about 0.01 to 2.5% by weight (for example, about 0.1 to 2% by weight), and more preferably about 0.5 to 1.5% by weight. The suspended flow condensate (7A) can have a methanol concentration of, for example, about 0.1 to 40% by weight (for example, about 1 to 30% by weight), preferably about 2 to 25% by weight (for example, about 5 to 20% by weight), and more preferably about 7 to 18% by weight (for example, about 10 to 15% by weight).
[00160] The suspended flow (7A) can have a temperature at an atmospheric pressure of, for example, about 15 to 110 ° C (for example, about 20 to 90 ° C) and preferably about 25 to 80 ° C (for example, about 30 to 70 ° C), or it can have a temperature at an atmospheric pressure of about 20 to 55 ° C. The condensate (lines 73, 74) of the suspended stream (7A) cooled in condenser C5 can have a temperature of, for example, about 0 to 60 ° C (for example, about 5 to 45 ° C) and preferably about from 7 to 30 ° C (for example, about 10 to 30 ° C).
[00161] The net bottom flow (7B) (a line 71) generally contains an extraction agent as a major component. The liquid bottom stream (7B) may contain, in addition to the extraction agent, small amounts of components such as acetaldehyde, methyl iodide, acetate, methyl acetate, methanol, dimethyl ether (DME), and impurities present in the system. The liquid flow (7B) can have a PRC concentration (in a representative way, acetaldehyde) (on a weight basis) of, for example, no more than 0.1% by weight (for example, about 1 ppb to 0, 1% by weight), preferably not more than 500 ppm (for example, about 10 ppb to 300 ppm), and more preferably not more than 100 ppm (for example, about 0.1 ppm to 100 ppm), or present a PRC concentration of substantially no more than the detection limit (0% by weight). The liquid flow (7B) may have a methyl iodide concentration of, for example, not more than 1% by weight (for example, about 1 ppm to 0.8% by weight) and preferably not more than 0.5 % by weight (for example, about 10 ppm to 0.1% by weight), or it may have a methyl iodide concentration of substantially no more than the detection limit (0% by weight). The liquid flow (7B) can have a methyl acetate concentration of about 1 ppm to 4% by weight (for example, about 5 ppm to 2% by weight) and preferably about 0.001 to 1% by weight (eg example, about 0.005 to 0.7% by weight). The liquid flow (7B) can have an acetic acid concentration of, for example, not more than 10% by weight (for example, about 1 ppm to 10% by weight) and preferably not more than 7% by weight (by for example, about 0.001 to 5% by weight), or it may have a concentration of acetate acid of substantially no more than the detection limit (0% by weight). The liquid stream (7B) can have a dimethyl ether concentration of, for example, about 0 to 1,000 ppm (for example, about 0 to 100 ppm) and preferably about 0 to 50 ppm (for example, about 0 at 10 ppm), or it may have a dimethyl ether concentration of substantially no more than the detection limit (0% by weight). The liquid flow (7B) can have a methanol concentration of, for example, about 0 to 5% by weight (for example, about 1 ppm to 3% by weight), preferably about 10 ppm to 2% by weight (for example, about 50 ppm to 1% by weight), and more preferably about 100 ppm to 0.5% by weight (for example, about 200 to 2,000 ppm), or it can have a methanol concentration of substantially no more than the detection limit. The liquid bottom flow (7B) generally contains these components, unavoidable contaminants (including impurities or by-products) and water like the rest. The liquid bottom flow (7B) can have a water concentration of, for example, about 90 to 99.99% by weight (for example, about 93 to 99.98% by weight) and preferably about 95 to 99.95% by weight (for example, about 97 to 99.9% by weight). The liquid bottom stream (7B) can be recycled, as an extraction agent in the second distillation step (5), in the distillation step (5) via the bottom line 71.
[00162] The liquid bottom flow (7B) can have a temperature at an atmospheric pressure of, for example, about 70 to 160 ° C (for example, about 80 to 120 ° C) and preferably about 85 to 110 ° C (for example, about 90 to 110 ° C), or it can have a temperature at an atmospheric pressure of about 95 to 105 ° C.
[00163] Probably, due to the fact that acetate acid and methyl acetate are predominantly transferred to the liquid bottom flow (7B), the third suspended flow (7A) seems to each present a ratio (Mel / AC ratio) of iodide to methyl (Mel) with respect to acetic acid (AC), and a ratio (Mel / MA ratio) of methyl iodide (Mel) with respect to methyl acetate (MA) greater than the liquid fed from line 69.
[00164] In the process shown in figure 1, the aqueous phase formed in the liquid-liquid separation step (6) is distilled. As described above, the lateral flow (5B) can be distilled in the third distillation step (7) without going through the liquid-liquid separation step (6). The liquid flow (7B) can be removed or discarded out of the system. (8) Distillation step
[00165] As previously described, the suspended flow (7A) still contains methyl iodide, although the methyl iodide concentration is low. Thus, the suspended flow (7A) can be further distilled in the fourth distillation step (8) to reduce the concentration of methyl iodide. Specifically, the suspended flow (7A) of the distillation step (7) can be further distilled in the distillation step (8) to separate the suspended flow (7A) into a suspended flow (8A) and a liquid bottom flow (8B) . Since the suspended flow (7A) contains a concentrated (enriched) acetaldehyde, the distillation step (8) can preferably be conducted in an extractive distillation with water. In more detail, water is added to the top of the distillation column (separation column) of the fourth distillation stage (8) via a feed line 82, to conduct the extractive distillation with water, and the suspended flow (8A) and directly or indirectly recycled in the reaction step (1), and the liquid bottom flow (8B) containing acetaldehyde is removed via a line 81. In the process shown in figure 1, the suspended flow (8A) is cooled and condensed in a condenser C6 in a line 83, a first portion of the condensate is taken up or refluxed in the distillation column (separation column) (8) by means of a reflux line 84, and a second portion of the condensate and removed by means of a line 85 for recycling in the reaction step (1).
[00166] For an extractive distillation with water like this, the suspended flow (8A) or a condensate thereof, which has a ratio of methyl iodide to acetaldehyde greater than that of the liquid flow (8B), can produce a condensate with a high concentration of methyl iodide. The concentrate can be recycled in the reaction step (reactor) (1) via a line 85.
[00167] For the extractive distillation with water, the water can have the same temperature as the extraction agent. The water can be added as a heated or hot water with the same temperature as the extraction agent, or as a spray water (or steam).
[00168] The liquid bottom stream or aqueous bottom stream (8B) is rich in extraction agent (in particular, water) and acetaldehyde. Thus, the liquid bottom flow (8B) can be discarded out of the system; or it can be further distilled to separate a fraction of PRC's and a fraction of water from each other, the fraction of PRC's can be discarded out of the system, and the fraction of water can be recycled as an extraction agent for the distillation step (5); or it can be recycled in the reaction step (reactor) (1).
[00169] The internal temperature of the distillation column of the fourth distillation step (8) depends on its internal pressure. At the internal pressure of an atmospheric pressure, the distillation column can have a column top temperature of, for example, about 10 to 90 ° C (for example, about 15 to 80 ° C) and preferably about 20 to 70 ° C (for example, about 20 to 65 ° C), or it can have a column bottom temperature of, for example, about 15 to 110 ° C (for example, about 20 to 100 ° C) and preferably about 25 to 80 ° C (for example, about 30 to 70 ° C). The distillation column can have a top column pressure of, for example, about 0.1 to 0.5 MPa, preferably about 0.2 to 0.4 MPa, and more preferably about 0.25 to 0 , 35 MPa in terms of absolute pressure.
[00170] The distillation column can have a theoretical stage (or plate) of, for example, about 1 to 50 (for example, about 2 to 40) and preferably about 3 to 30 (for example, about 5 to 10). The flow rate of the distillation column can be, for example, about 1 to 1,000 (for example, about 3 to 500), preferably about 5 to 100 (for example, about 10 to 70), and more preferably about 15 to 50 (for example, about 15 to 30).
[00171] The weight ratio of the flow of the extraction agent (water) to the flow of condensate 74 from the third suspended flow (lowest boiling point flow) (in terms of liquid flow) [the first / the last] it can be selected from the range of about 0.1 / 100 to 1,000 / 100 (for example, about 10/100 to 500/100), or it can generally be about 25/100 to 250/100 (for example, about 50/100 to 200/100) and preferably about 70/100 to 150/100 (e.g., about 75/100 to 125/100).
[00172] For extractive distillation with water, the extraction agent (water) can have a temperature of, for example, about 0 to 60 ° C, preferably about 10 to 50 ° C, and more preferably about 20 to 40 ° C or can have a common temperature (for example, about 15 to 25 ° C). The extraction agent (water) can be added as a heated or hot extraction agent, or as a vapor.
[00173] The internal temperature of the extractive distillation column with water depends on its internal pressure. At the internal pressure of an atmospheric pressure, the distillation column can have a column top temperature of, for example, about 10 to 90 ° C (for example, about 15 to 80 ° C) and preferably about 20 to 70 ° C (for example, about 20 to 65 ° C), or it can have a column bottom temperature of, for example, about 15 to 110 ° C (for example, about 20 to 100 ° C) and preferably about 25 to 80 ° C (for example, about 30 to 70 ° C). The distillation column can have a top column pressure (absolute pressure) of, for example, about 0.1 to 0.5 MPa, preferably about 0.2 to 0.4 MPa, and more preferably about 0 , 25 to 0.35 MPa. The distillation column can have a top column pressure (gauge pressure) of about 0.0 to 0.5 MPa, preferably about 0.1 to 0.4 MPa, and more preferably about 0.15 to 0 , 35 MPa.
[00174] The distillation column may have a theoretical stage (or plate) of, for example, about 0.5 to 30 (for example, about 1 to 20) and preferably about 2 to 10 (for example, about 3 to 5). The flow rate of the distillation column can be, for example, about 0.01 to 500 (for example, about 0.1 to 100), preferably about 0.5 to 50 (for example, about 1 to 30), and more preferably about 2 to 20 (e.g., about 3 to 10). the suspended stream (8A) or a condensate thereof (lines 83, 84, 85) is rich in acetaldehyde and methyl iodide. The suspended flow condensate (8A) can have a PRC concentration (representative, acetaldehyde) of, for example, about 1 to 70% by weight (for example, about 10 to 65% by weight) and preferably about from 30 to 60% by weight (for example, about 35 to 55% by weight); or it may have a PRC concentration of about 5 to 20% by weight (for example, about 10 to 15% by weight). The condensate may have a methyl iodide concentration of, for example, about 20 to 80% by weight (for example, about 30 to 75% by weight) and preferably about 40 to 65% by weight (for example, about 45 to 60% by weight); or it may have a concentration of methyl iodide of about 50 to 90% by weight (for example, about 60 to 85% by weight) and preferably about 70 to 80% by weight. The condensate can have a methyl acetate concentration of, for example, about 0.01 to 20% by weight (for example, about 0.1 to 15% by weight) and preferably about 1 to 10% by weight (for example, about 2 to 8% by weight); or it may have a concentration of methyl acetate of about 3 to 20% by weight (for example, about 5 to 15% by weight). The condensate from the suspended stream (8A) may have an acetic acid concentration of, for example, about 0 to 5% by weight, preferably about 0 to 3% by weight, and more preferably about 0 to 1% by weight , or it may have a concentration of acetic acid substantially of no more than the detection limit. The condensate may have a water concentration of, for example, about 0 to 10% by weight (for example, about 0.01 to 8% by weight) and preferably about 0.1 to 5% by weight (eg example, about 0.3 to 3% by weight).
[00175] The suspended flow condensate (8A) may have a concentration of dimethyl ether that can be selected from a wide range of about 10 ppm to 80% by weight, and may have a concentration of dimethyl ether of, for example, about 100 ppm to 60% by weight (for example, about 0.5 to 50% by weight) and preferably about 1 to 40% by weight (for example, about 5 to 30% by weight). The concentration of dimethyl ether in the suspended flow (8A), which varies depending on the conditions of the process, may be increased in some cases. The suspended flow condensate (8A) can have a methanol concentration of, for example, about 0 to 5% by weight (for example, about 0 to 3% by weight), preferably about 0 to 1% by weight (for example, about 0 to 0.5% by weight), and more preferably about 0.001 to 0.3% by weight (for example, about 0.01 to 0.1% by weight), or it may have a methanol concentration of substantially no more than the detection limit.
[00176] The suspended flow (8A) (refhix line 83) can have a temperature at an atmospheric pressure of, for example, about 10 to 90 ° C (for example, about 15 to 80 ° C) and preferably about 20 to 70 ° C (for example, about 20 to 65 ° C). The condensate (lines 84, 85) of the suspended stream (8A) cooled in condenser C6 can have a temperature of, for example, about 0 to 45 ° C (for example, about 3 to 35 ° C) and preferably about from 5 to 30 ° C (for example, about 7 to 25 ° C).
[00177] The liquid bottom flow or aqueous bottom flow (8B) (line 81) generally contains water as a major component and may contain acetaldehyde. The liquid flow (8B) can have a PRC concentration (representative, acetaldehyde) (on a weight basis) of, for example, about 1 to 50% by weight (for example, about 5 to 45% by weight) ) and preferably about 10 to 40% by weight (for example, about 20 to 40% by weight), or it can have a PRC concentration of about 2 to 15% by weight (for example, about 5 to 10 % by weight). The liquid flow (8B) can have a methyl iodide concentration of, for example, no more than 1% by weight (for example, about 1 ppm to 0.8% by weight), no more than preferably 0.5 % by weight (for example, about 0.001 to 0.2% by weight), and more preferably not more than 0.005 to 0.15% by weight. The liquid flow (8B) can have a methyl acetate concentration of, for example, about 1 ppm to 5% by weight (for example, about 50 ppm to 2% by weight) and preferably about 0.01 to 1.5% by weight (for example, about 0.05 to 1% by weight). The liquid flow (8B) can have an acetic acid concentration of, for example, no more than 5% by weight (for example, about 1 ppm to 3% by weight) and preferably no more than 1% by weight (for example, example, about 50 ppm at 0.5% by weight), or it can have a concentration of acetate acid of substantially no more than the detection limit (0% by weight). The liquid flow (8B) can have a water concentration of, for example, about 40 to 90% by weight (for example, about 50 to 85% by weight) and preferably about 55 to 80% by weight (eg example, about 60 to 80% by weight); or it can have a water concentration of about 80 to 98% by weight (e.g., about 85 to 97% by weight) and preferably about 90 to 95% by weight. The liquid flow (8B) can have a dimethyl ether concentration of, for example, about 0 to 2% by weight (for example, about 0.0001 to 1.5% by weight), preferably about 0.001 to 1 % by weight (for example, about 0.01 to 0.5% by weight), and more preferably about 0.1 to 0.5% by weight. The liquid flow (8B) can have a methanol concentration of, for example, about 0 to 5% by weight (for example, about 0 to 3% by weight), preferably about 0 to 1% by weight (for example, for example, about 0 to 0.5% by weight), and more preferably about 0.001 to 0.3% by weight (for example, about 0.01 to 0.1% by weight), or it may have a concentration of methanol substantially of no more than the detection limit.
The liquid bottom flow or aqueous bottom flow (8B) can have an atmospheric pressure temperature of, for example, about 15 to 110 ° C (for example, about 20 to 100 ° C) and preferably about 25 to 80 ° C (for example, about 30 to 70 ° C).
[00179] Regardless of the use of acetic acid as the miscible solvent, the second suspended flow (5A) and / or the lateral flow (5B), as well as the flow of the next process, for example, the condensate (the aqueous phase and / or the organic phase, in particular the aqueous phase) of the liquid-liquid separation step (6) generally contains acetyl acid and methyl acetate, in addition to acetaldehyde and methyl iodide. The distillation of the process flow containing such components in the previous third distillation step (7) distributes acetic acid or methyl acetate to the extraction agent (in particular, water) from the bottom liquid flow (7B), to separate acetaldehyde and iodide of acetic acid methyl. Specifically, the distillation column (7) allows efficient separation of acetate and methyl acetate from the process flow. Thus, the extractive distillation with water in the fourth distillation stage (8) after the third distillation stage (7) prevents methyl iodide from being mixed in the liquid bottom flow (8B), due to an affinity between water and acetaldehyde, to provide the liquid bottom stream or aqueous solution (8B) with a very high ratio (AD / Mel) of acetaldehyde (AD) to methyl iodide (Mel). Specifically, after acetic acid and methyl acetate are removed in the third distillation step (7), in addition to the second distillation step (5), additionally, extractive distillation with water and conducted in the fourth distillation step (8) to achieve savings of energy and equipment cost reduction, in comparison with the conventional process and, moreover, to reduce a loss of methyl iodide disposal out of the system. The AD / Mel ratio in the liquid bottom stream or aqueous solution (8B) can be, for example, about 20/1 to 2,000 / 1 (for example, about 50/1 to 1500/1), preferably about 100 / 1 to 1,000 / 1 (for example, about 150/1 to 750/1), and more preferably about 200/1 to 500/1 (for example, about 250/1 to 450/1).
[00180] In the manner described above, each of the process flows (for example, a process flow, such as the mixed composition (3A) or separate phases thereof, or the lateral flow (5B) or separate phases thereof) in general inevitably contains other components (including impurities). The process flow can have a methanol concentration of, for example, about 0 to 5% by weight (for example, about 0.0001 to 3% by weight), preferably about 0.001 to 1% by weight (eg example, about 0.01 to 0.5% by weight), and more preferably about 0.1 to 0.5% by weight. The process flow may have a hydrogen iodide concentration of about 0 to 5,000 ppm (for example, about 1 to 1,000 ppm) and preferably about 5 to 500 ppm (for example, about 10 to 300 ppm). The process flow can have a concentration of each formic acid and C3-8 alkane carboxylic acids (such as propidonic acid) of, for example, about 0 to 500 ppm (for example, about 1 to 300 ppm) and preferably about 0 to 100 ppm (for example, about 5 to 50 ppm). The process flow may have a concentration of each of aldehydes derived from acetaldehyde (such as crotonaldehyde and 2-ethylcrotonaldehyde) of, for example, about 0 to 500 ppm (for example, about 1 to 300 ppm) and preferably about from 0 to 100 ppm (for example, about 5 to 50 ppm). The process flow can have a concentration of each of the alkyl iodides (C2-12 alkyl iodides, such as hexyl iodide) of, for example, about 0 to 100 ppm (for example, about 1 ppb to 50 ppm) and preferably about 0 to 10 ppm (for example, about 10 ppb to 5 ppm).
[00181] The condensate (the aqueous phase and / or the organic phase, for example, the aqueous phase) of the liquid-liquid separation step (6) can be subjected to extractive distillation with water in the fourth distillation step (8) without undergo the third stage of distillation (7).
[00182] By separating the acetic acid or methyl acetate as a component in the liquid bottom flow (7B), the third suspended flow (7A) of the third distillation step (7) has a reduced distribution or dissolution capacity of methyl iodide for water. Thus, if necessary, acetaldehyde can be extracted with water from the third suspended stream (7A) by one or a plurality of water extraction units provided with a mixer and a sedimenter, or by an extraction column, instead of the fourth distillation step (8).
[00183] Additionally, the aqueous phase obtained by biphasically separating the extraction mixture (5B) and the suspended flow (5A) also contains methyl iodide. Thus, at least a portion of the aqueous phase obtained by biphasically separating the extraction mixture (5B) and / or the suspended flow (5A) can be subjected to water extraction in the extraction or extractive distillation step (8). By the way, at least a portion of the aqueous phase obtained by biphasically separating at least the extraction mixture (5B), between the extraction mixture (5B) and the suspended flow (5A), can be practically subjected to the extraction step (8) . The previous aqueous phase and / or the suspended flow (7A) of the distillation step (7) can be subjected to water extraction in the extraction step (8).
[00184] According to the present invention, in the manner described above, various changes and modifications to the process unit and / or the process flow can be carried out. For example, in the second liquid-liquid separation step (6), the separation unit 6a is not necessarily required. For example, as shown in figure 2, the suspended flow (5A) of the distillation step (5) can be cooled and condensed in condenser C3, and the total condensate can be refluxed in the distillation column (5) using a reflux 106, instead of the separation unit 6a. Refluxing the entire suspended flow (5A), the reflux unit 106 is not necessarily required. The second liquid-liquid separation step (6) does not necessarily require a plurality of liquid-liquid separation units 6b and 6c. The second liquid-liquid separation step (6) can use a single liquid-liquid separation unit (such as a tank, a decanter, a holding tank, or a capping tank).
[00185] The lateral flow (5B) or the fluid (such as the aqueous phase) of the second liquid-liquid separation step (6) can be distilled in the fourth distillation step (8). The third distillation step (7) and / or the fourth distillation step (8) are not necessarily required. Instead of the fourth distillation step (8), an extraction unit (such as an extraction column or an extraction agent) can be used. An aqueous solvent produced in the process can be used as an extraction agent in the second distillation step (5).
[00186] Although the first suspended flow (3A) (including a condensate of this, and an aqueous phase and / or a liquid-liquid organic phase separated from it) corresponds to a mixed composition (or mixture), from which PRC's (for example, example, acetaldehyde) are separated and removed according to the present invention, the mixed composition (or mixture) according to the present invention is not limited to the first suspended flow (3A) or a condensate thereof and can be any mixture containing at least a PRC (such as acetaldehyde) and methyl iodide, for example, a mixture produced from the reaction step (reaction system or reactor) (1), the rapid evaporation step (evaporator) (2), or the first distillation (3); and a mixture produced from each of the steps after the second distillation step (5) [for example, the second liquid-liquid separation step (6), the third distillation step (third distillation column) (7), and the fourth distillation stage (fourth distillation column) (8)]. According to the present invention, PRC's (e.g., acetaldehyde) and methyl iodide can be efficiently separated from each other, even in a mixture like this (in particular, a mixture containing methyl acetate).
[00187] The process of the present invention is applicable to any mixed composition (or mixture), or suspended flow containing at least one PRC and methyl iodide (in particular, a mixed composition or suspended flow, of which a side flow produced by distillation with the extraction agent and liquid-liquid separable), and is applicable not only to the second distillation column (5), but also one or a plurality of distillation columns after the first distillation column (3) to separate in a way selective PRC's, using extractive distillation in the concentration zone. In particular, the process of the present invention is efficiently applicable to a mixed composition or suspended stream containing concentrated methyl iodide, in the manner described above, in order to efficiently extract PRC's with a small amount of the extraction agent in a small extraction space. In the mixed composition or suspended flow, at least methyl iodide, between permanganate reducing compounds (PRC's) and methyl iodide, can be concentrated, PRC's can also be concentrated or the water concentration can be reduced, compared to a mixed flow produced in a previous unit operation [for example, a flow fed into the first distillation column (3)]. The operation of the previous unit may include one or a plurality of several operation units, for example, a quick step, a distillation step (including an extractive water distillation step), an extraction step, a condensation and separation step liquid-liquid (biphasic), an absorption step and a membrane separation step. EXAMPLES
[00188] The following examples are intended to further describe this invention in detail, and should in no way be interpreted as defining the scope of the invention.
[00189] Next, the results of experiments carried out using an Oldershaw distillation column with a diameter of 40 mm (|), according to an example process flow shown in figure 3, will be shown. In experiments according to the example processes shown in figure 3, the process shown in figure 1, which comprises a second distillation step (5), a liquid-liquid separation step (6), a third distillation step (7 ), and a fourth distillation step (8), was modified by replacing a separation unit 6a, after the second distillation step (5) with a reflux unit 106, eliminating a decanter 6c without using a decanter 6a and a water tank. holding 6b, and connecting or joining a line 63 for an extraction mixture (5B) to a cooling unit (refrigerator) C4. Thus, without using a line 64 and a line 67, shown in figure 1, an organic phase in the decanter 6c was recycled in the distillation step (5) by means of a line 68. In addition, an aqueous phase in the decanter 6c was recycled in a predetermined flow (a flow corresponding to a flow in a line 67 shown in figure 1) of tank 6c in the distillation step (5), through a line 69a branched from a line 69. Acetic acid, as a miscible solvent, it was fed through a feed line 70 in an intermediate height position between a recycling line 65 and a feed line 44.
[00190] In a process of comparative example 1, a second distillation column (acetaldehyde-removing column) 206, an extraction column 207, and a distillation column 208 were used, as shown in figure 4.
[00191] In comparative example 1 and examples 1 to 8, an organic phase (liquid rich in honey) in a decanter (4) was fed into the distillation column of the second distillation step (5), through a line feed 44 shown in figure 1. In examples 9 and 10, an aqueous phase (water-rich feed liquid) in the decanter (4) was also fed into the distillation column of the second distillation step (5), via a feed line 43b shown in figure 1. The aqueous phase in feed line 43b was mixed (or mixed) with the organic phase in feed line 44, and the resulting mixture was fed to the same plate in the distillation column.
[00192] In the comparative example and examples below, the numerical values were expressed as follows. The measured values were rounded up to the second last digit. With respect to the values measured in the comparative example and examples, the concentration values were expressed basically as a decimal place, and the flow values expressed were determined by rounding the measured values. In the tables, the concentration of each component was basically expressed as one or two decimal places; for a component with a lower concentration, the concentration was expressed as three or four decimal places. In the tables, the sum total of the concentrations of the components described is not strictly 100% by weight in some cases. In such cases, the amount of the component with the maximum concentration is used as a balanced amount, such that the total sum is expressed as 100% by weight. The amount of the component with the maximum concentration was shown as a balanced amount "BL". In the balanced “BL” quantity, impurities or other components are also contained. Comparative example 1
[00193] A second distillation column 206 with the actual number of stages of 100 [column that removes acetaldehyde; column top temperature of 22 ° C, column bottom temperature of 48 ° C, atmospheric pressure column top pressure +10 mmfUO (about 100 Pa)] was provided. The 32nd bottom plate of the distillation column 206, a feed liquid (a line 44, temperature: 20 ° C) was fed at 1,295 g / h. A suspended part 262 (temperature: 22 ° C) produced by the distillation was cooled to 7 ° C in a C3 condenser. A portion of the condensate was refluxed at a rate of 987 g / h (by means of a reflow line 263), and the residual portion of the condensate was distilled through a line 264 at a rate of 6.0 g / h. The feed liquid was a solution (or mixture) of methyl iodide (Honey) with an acetaldehyde (AD) concentration of 1,960 ppm, a concentration of methyl acetate (MA) of 14.9% by weight, a concentration of water is 0.7% by weight, and a concentration of acetic acid (AC) of 1.9% by weight. The condensate (line 264) of the suspended part showed an AD concentration of 41.4% by weight (solution or Mel mixture). The Mel solution was fed on the top of an extraction column 207 with the theoretical number of stages of 1 [column top temperature 15 ° C, column bottom temperature 15 ° C, absolute pressure of about 0 ° C, 1 MPa (atmospheric pressure)] through line 264, water (temperature: 15 ° C) was fed at a rate of 6.0 g / h at the bottom of the extraction column 207 through line 271, and a mixture aqueous extraction (temperature: 15 ° C) with an AD concentration of 26.4% by weight was removed at a flow rate of 8.5 g / h from the top of the column (a line 275). The aqueous extraction mixture containing AD was fed into a distillation column (separation column AD) 208 (column top temperature 21 ° C, column bottom temperature 102 ° C, pressure top of the atmospheric pressure column +10 mmLUO) through a feed line 275 and distilled to form a suspended part 282 with a temperature of 21 ° C. The suspended part 282 was cooled in a C6 condenser to provide a condensate (temperature: 7 ° C). A portion of the condensate was refluxed at a rate of 25.3 g / h (by means of a reflux line 283), and the residual portion of the condensate, which showed an AD concentration of 88.8% by weight and a concentration of Honey of 10.8% by weight (temperature: 7 ° C), was removed in a flow of 2.53 g / h through a removal line 284. From a bottom of the column, a bottom flow (temperature : 102 ° C) was removed by means of a 281. line. According to the process, AD and Mel were removed from the process at a flow rate of 2.25 g / h and a flow rate of 0.27 g / h, respectively. The second distillation column (column that removes acetaldehyde) 206 required an amount of heat in the reflector of 100.2 kcal / h, separation column AD 208 required an amount of heat in the reflector of 4.3 kcal / h.
[00194] Table 1 shows a component analysis on each line represented in figure 4.
Table 1
[00195] In table 1, AD indicates acetaldehyde, Mel indicates methyl iodide, MA indicates methyl acetate, and AC indicates acetate (the same applies below) .Example 1
[00196] A second distillation column 5 with the actual number of stages of 43 [column top temperature 23 ° C, column bottom temperature 47 ° C, atmospheric pressure top pressure + 10 mmH2O ( about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 20 ° C) was fed to the 7th plate at the bottom of the distillation column at a rate of 1,295 g / h, and water (temperature: 20 ° C) was fed to the 43rd plate of the distillation column. bottom of the distillation column at a rate of 12.5 g / h. A suspended part (temperature: 23 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 576 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1960 ppm, an MA concentration of 14.8% by weight, a water concentration of 0.7% by weight, and an AC concentration of 1.8% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 36 ° C). The side flow was cooled in a C4 cooling unit at 15 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase (Mel phase). A bottom stream from a 52 line (temperature: 47 ° C) was withdrawn at a rate of 1,285 g / h. The total amount of the aqueous phase (temperature: 15 ° C) with an AD concentration of 15.8% by weight was removed at a rate of 15.6 g / h from tank 6c out of the system, through a line 69 without recycling in the second distillation column 5, and AD was thus removed. The total amount (808.9 g / h) of the Mel phase (a 68 line, temperature: 15 ° C) in tank 6c was recycled on the first plate below the chimney tray (the fourth plate below the top of the column) of the second distillation column (column that removes acetaldehyde) 5. According to the process, AD and Mel in the aqueous phase (line 69) were removed from the process at a rate of 2.47 g / h and a rate of 0.22 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 56.1 kcal / h. The rate taken from the bottom (line 52) of the second distillation column 5 was 1,285 g / h.
[00197] The following table shows the results of the component analysis on each line represented in figure 3.

[00198] A second distillation column 5 with the actual number of stages of 43 [column top temperature 22 ° C, column bottom temperature 47 ° C, atmospheric pressure column top pressure + 10 mmfUO ( about 100 Pa)] was provided. A liquid feed (a line 44, temperature: 20 ° C) was fed to the 7th plate at the bottom of the distillation column at a rate of 1,302 g / h, and water (temperature: 20 ° C) was fed to the 43 plate of the distillation column. bottom of the distillation column at a rate of 12.5 g / h. A suspended part (temperature: 22 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 937 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1,940 ppm, an MA concentration of 14.8% by weight, a water concentration of 0.7% by weight, and an AC concentration of 2.1% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 34 ° C). The side flow was cooled in a C4 cooling unit at 15 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A bottom stream of a 52 line (temperature: 47 ° C) was withdrawn at a rate of 1,294 g / h. A first portion of the aqueous phase with an AD concentration of 20.5% by weight was removed at a rate of 11.9 g / h from tank 6c out of the system via a line 69 without recycling in the second distillation column 5, and AD was thus removed. A second portion of the aqueous phase (a line 69a, temperature: 15 ° C) was removed at a flow rate of 7.4 g / h from tank 6c and mixed (or mixed) with the total amount (1,345 g / h) of the phase Honey (a line 68, temperature: 15 ° C) taken from tank 6c (a line 65), and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column).
[00199] According to the process, AD and Mel in the aqueous phase (line 69) were removed from the process at a flow rate of 2.44 g / h and a flow rate of 0.18 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 89.7 kcal / h. The rate taken from the bottom (line 52) of the second distillation column 5 was 1,294 g / h.
[00200] The following table shows the results of the component analysis on each line represented in figure 3.

[00201] A second distillation column 5 with the actual number of stages of 43 [column top temperature of 22 ° C, column bottom temperature of 47 ° C, pressure of the top of the atmospheric pressure column + 10 mmHzO ( about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 20 ° C) was fed to the 7th plate at the bottom of the distillation column at a rate of 1,279 g / h, and water (temperature: 20 ° C) was fed to the 43th plate of the distillation column. bottom of the distillation column at a rate of 12.6 g / h. A suspended part (temperature: 22 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 688 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1960 ppm, an MA concentration of 14.8% by weight, a water concentration of 0.7% by weight, and an AC concentration of 1.8% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 34 ° C). The side flow was cooled in a C4 cooling unit at 15 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase (Mel phase). A bottom stream of a 52 line (temperature: 47 ° C) was removed at a rate of 1,299 g / h. The total amount of the aqueous phase (temperature: 15 ° C) with an AD concentration of 16.0% by weight was removed at a rate of 15.3 g / h from tank 6c out of the system via a line 69 without recycling in the second distillation column 5, and AD was thus removed. The total amount of the Mel phase (a line 68, temperature: 15 ° C) in tank 6c was recycled at a rate of 1,013 g / h on the first plate below the chimney tray (the fourth plate below the top of the column) on the second distillation column (column that removes acetaldehyde) 5.
[00202] Additionally, acetic acid (temperature: 20 ° C) was fed at a flow rate of 30.0 g / h into the 21st plate below the top of the second distillation column 5 (the 17th plate below the recycling plate) through of a line 70.
[00203] According to the process, AD and Mel in the aqueous phase (line 69) were removed from the process at a rate of 2.45 g / h and a rate of 0.18 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 66.1 kcal / h. The rate taken from the bottom of the second distillation column 5 was 1,299 g / h.
[00204] The following table shows the results of the component analysis on each line represented in figure 3.

[00205] A second distillation column 5 with the actual number of stages of 43 [column top temperature 22 ° C, column bottom temperature 47 ° C, atmospheric pressure top pressure + 10 mmLUO ( about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 20 ° C) was fed to the bottom plate of the distillation column at a rate of 1,290 g / h, and water (temperature: 20 ° C) was fed to the 43 plate of the distillation column. bottom of the distillation column at a rate of 12.5 g / h. A suspended part (temperature: 22 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 899 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1,940 ppm, an MA concentration of 14.8% by weight, a water concentration of 0.70% by weight, and an AC concentration of 2.1% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 34 ° C). The side flow was cooled in a C4 cooling unit at 15 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase (temperature: 15 ° C) with an AD concentration of 20.3% by weight was removed at a rate of 11.9 g / h from tank 6c via a line 69 without recycling in the second distillation column 5, and AD was thus removed. A second portion of the aqueous phase (a line 69a) was removed at a flow rate of 7.4 g / h from tank 6c and mixed with the total amount (1,305 g / h) of the Mel phase (a line 68, temperature: 15 ° C) removed from tank 6c (a line 65), and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The rate taken from the bottom flow (line 52, temperature: 47 ° C) of the second distillation column 5 was 1,312 g / h.
[00206] Additionally, acetic acid (temperature: 20 ° C) was fed at a flow rate of 30.0 g / h into the 21st plate below the top of the second distillation column 5 (the 17th plate below the recycling plate) through of a line 70.
[00207] Next, the aqueous phase (line 69) in decanter 6c was fed into a third distillation column with the actual number of stages of 6 [column removing AD; column top temperature: 21 ° C, column bottom temperature: 99 ° C, column top pressure: atmospheric pressure + 10 mmEffect (about 100 Pa)] 7. A suspended part (temperature: 21 ° C) of a line 72 was cooled in a C5 condenser at 7 ° C and refluxed at a reflux rate of 12.5 g / h per distillation. A distillate (condensate) with an AD concentration of 92.4% by weight was removed in a flow rate of 2.62 g / h using a 74 line. An aqueous mixture (temperature: 99 ° C) with a concentration of 0.1% by weight methyl acetate was removed from the bottom by means of a line 71 for removing methyl acetate. A fourth distillation column with the actual number of stages of 6 [extractive distillation column with water; column top temperature: 28 ° C, column bottom temperature: 35 ° C, column top pressure: atmospheric pressure +10 mmH2O (about 100 Pa)] 8 was provided. The distillate after removing methyl acetate was fed to the bottom plate of the distillation column 8 via a line 74, and water (temperature: 20 ° C) was fed at a rate of 5.2 g / h in the top of the column. A suspended part (temperature: 28 ° C) of line 83 was cooled in a C6 condenser at 7 ° C and refluxed at a reflux rate of 6.0 g / h for extractive distillation with water. A condensed solution (a line 85) with an AD concentration of 42.9 wt% and a Honey concentration of 51.7 wt% was removed at a rate of 0.3 g / h from the top of the column, and an aqueous mixture (temperature: 35 ° C) with an AD concentration of 30.3% by weight and a concentration of Honey of 0.073% by weight was removed at 7.6 g / h from the bottom (a line 81).
[00208] According to the process, AD and Mel in the aqueous phase (line 69) were removed from the process at a flow rate of 2.42 g / h and a flow rate of 0.16 g / h, respectively. In addition, AD and Mel at the bottom (line 81) were removed from the process at a flow rate of 2.29 g / h and a flow rate of 0.0055 g / h, respectively. The second distillation column 5 required an amount of heat in the refiller of 86.4 kcal / h. The third distillation column (column that removes AD) 7 required an amount of heat in the reflector of 3.0 kcal / h. The extractive distillation column with water 8 required an amount of heat in the reflector of 0.7 kcal / h.
[00209] The following table shows the results of the component analysis on each line represented in figure 3.

[00210] A second distillation column 5 with the actual number of stages of 43 [column top temperature 22 ° C, column bottom temperature 47 ° C, atmospheric pressure top pressure + 10 mmfUO ( about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 20 ° C) was fed to the bottom plate of the distillation column at a rate of 1,290 g / h, and water (temperature: 20 ° C) was fed to the 43 plate of the distillation column. bottom of the distillation column at a rate of 12.5 g / h. A suspended part (temperature: 22 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 899 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1,940 ppm, an MA concentration of 14.8% by weight, a water concentration of 0.7% by weight, and an AC concentration of 2.1% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 34 ° C). The side flow was cooled in a C4 cooling unit at 15 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase (temperature: 15 ° C) with an AD concentration of 20.3% by weight was removed at a rate of 11.9 g / h from tank 6c via a line 69, and was fed in the fourth distillation column mentioned above (extractive distillation column with water) 8. A second portion of the aqueous phase (a line 69a) was removed at a flow rate of 7.4 g / h from tank 6c and mixed with the total amount ( 1,305 g / h) of the Mel phase (a line 68, temperature: 15 ° C) taken from tank 6c, and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The rate taken from the bottom flow (line 52, temperature: 47 ° C) of the second distillation column 5 was 1,312 g / h.
[00211] Additionally, acetic acid (temperature: 20 ° C) was fed at a flow rate of 30.0 g / h into the 21st plate below the top of the second distillation column 5 (the 17th plate below the recycling plate) through of a line 70.
[00212] Next, the aqueous phase (line 69) removed from decanter 6c at a rate of 11.9 g / h was fed directly into the first bottom plate of a fourth distillation column with the actual number of stages of 6 [extractive distillation column with water; column top temperature 32 ° C, column bottom temperature 70 ° C, column top pressure: atmospheric pressure + 10 mmH2O (about 100 Pa)] 8 without being fed into the third distillation column (column that removes AD) 7, and water (temperature 20 ° C) was fed at the top of the fourth distillation column at a rate of 23.9 g / h. A suspended part (temperature 32 ° C) of a line 83 was cooled in a C6 condenser at 15 ° C and refluxed at a reflux rate of 1.8 g / h for extractive distillation with water. A condensed solution with an AD concentration of 12.5% by weight and a concentration of Honey of 76.4% by weight was removed from the top of the column at 0.20 g / h, and an aqueous mixture (temperature 70 ° C) with an AD concentration of 6.7 wt% and a Honey concentration of 0.022 wt% was removed from the bottom (a line 81) at a rate of 35.6 g / h.
[00213] According to the process, AD and Mel at the bottom (line 81) were removed from the process at a flow rate of 2.40 g / h and a flow rate of 0.0078 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 86.4 kcal / h. The extractive distillation column with water 8 required 2.1 kcal / h of heat in the reflector.
[00214] The following table shows the results of the component analysis on each line represented in figure 3. The compositions of lines 44, 52, 53/61, 63, 69a, 69, and 68 are the same as those in example 4 and are omitted from the table below. The composition of line 69 is the same as that of feed line 74, which is fed into the distillation column 8 without going through the distillation column 7.

[00215] Table 7 and table 8 represent the operation of distillation of feed liquid, the efficiency of separation of PRC's and methyl iodide, and the energy efficiency.


[00216] In comparative example 1, the amount of AD removal and the amount of honey lost indicates the amount of AD and the amount of honey in the aqueous extract 275 of the extractive distillation column with water 207 in figure 4. In the examples, the amount of AD removal and the amount of lost Honey indicate the amount of AD and the amount of Honey in the aqueous phase 69 formed by a mixture of the second distillation column (5). In comparative example 1, the methyl iodide / acetaldehyde ratio (Mel / AD ratio) was calculated from the amount of AD and the amount of Honey in aqueous extract 275. In examples 1 to 4, the ratio of methyl iodide / acetaldehyde (Mel / AD ratio) was calculated from the amount of AD and the amount of Mel in the aqueous phase 69.

[00217] In comparative example 1, the amount of AD removal and the amount of lost Honey indicate the amount of AD and the amount of Honey in distillate 284, which was obtained by further distilling, through distillation column 208, aqueous extract 275 of the extractive distillation column with water 207 in figure 4. In examples 4 and 5, the amount of AD removal and the lost amount of Honey indicates the amount of AD and the amount of Honey in the bottom flow 81 of the fourth distillation column (8). In comparative example 1, the methyl iodide / acetaldehyde ratio (Mel / AD ratio) was calculated from the amount of AD and the amount of Honey in the distillate 284. In examples 4 and 5, the methyl iodide / acetaldehyde ratio (Mel / AD ratio) was calculated from the amount of AD and the amount of Mel in the liquid bottom 81.
[00218] The comparison between comparative example 1 and examples 1 to 3 in table 7 show that the extractive distillation with water by the second distillation column (column that removes acetaldehyde) (5), according to the present invention, reduces the number of stages required for the distillation column from 100 to 43 and also reduces the amount of steam required. The comparison of example 1 with example 2, and the comparison of example 1 with example 3 show that not only remove the aqueous phase from the side flow out of the System, but also recycle a portion of the aqueous phase in the distillation or food column additionally acetic acid in the second distillation column, reduces the concentration of methyl acetate in the second distillation column (5) to decrease the methyl iodide leak out of the system. The comparison of examples 2 and 3 with example 4 shows that the combination of the recycling of the aqueous phase and the feeding of acetic acid further reduces the loss of the amount of methyl iodide, compared with the recycling of the aqueous phase in the second distillation column ( 5) alone or the acetic acid feed alone.
[00219] Furthermore, evidently in table 8, the extractive distillation with water through the fourth distillation column (8) reduces the loss of the amount of methyl iodide. The comparison between example 4 and example 5 shows that the removal of methyl acetate by the third distillation column (column that removes AD) (7), before the extractive distillation with water by the fourth distillation column (8), further reduces a loss of methyl iodide in the extractive distillation with water.Example 6
[00220] A second distillation column 5 with the actual number of stages of 30 [column top temperature of 21.2 ° C, column bottom temperature of 49.1 ° C, pressure of the top of the atmospheric pressure column + 10 mmH2O (about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 21 ° C) was fed to the 7th plate at the bottom of the distillation column at a rate of 1,282 g / h, and water (temperature: 20 ° C) was fed to the 30th plate of the distillation column. bottom of the distillation column at a rate of 6.7 g / h. A suspended part (temperature: 21.2 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 295 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1840 ppm, a honey concentration of 82.6% by weight, a MeOH concentration of 0.07% by weight, an MA concentration of 13 , 9% by weight, a water concentration of 0.69% by weight, and an AC concentration of 2.5% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of the liquid that fell was removed as a side flow 63 (temperature: 37.6 ° C). The side flow was cooled in a C4 cooling unit at 6.8 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase with an AD concentration of 22.2% by weight (temperature: 6.8 ° C) was removed at a rate of 9.4 g / hr from tank 6c via a line 69. One second portion of the aqueous phase (a line 69a) was removed in a flow of 9.3 g / h from tank 6c and mixed (or mixed) with the total amount (968 g / h) of the Mel phase (a line 68, temperature : 7 ° C) removed from tank 6c, and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The rate taken from the bottom stream (line 52, temperature: 49.1 ° C) of the second distillation column 5 was 1,279 g / h.
[00221] According to the process, removing the aqueous phase (line 69) formed by the lateral flow of the second distillation column 5, AD and Mel were removed from the process at a flow rate of 2.09 g / h and a flow rate of 0.167 g / h, respectively. The second distillation column 5 required an amount of heat in the A-IJ kcal / h.
[00222] The following table shows the results of the component analysis in each line represented in figure 3. The aqueous phase in line 69 was fed in the fourth distillation column 8 without being fed in the third distillation column 7. Thus, the composition of the aqueous phase in line 69 is the same as the composition of the feed line 74 connected in the distillation column 8.

[00223] In Table 9, DME indicates dimethyl ether, and MeOH indicates methanol (the same applies below). Example 7
[00224] A second distillation column 5 with the actual number of stages of 15 [column top temperature of 21.0 ° C, column bottom temperature of 45.1 ° C, pressure of the top of the atmospheric pressure column + 10 mmH2O (about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 21 ° C) was fed to the 7th plate at the bottom of the distillation column at a rate of 1,295 g / h, and water (temperature: 21 ° C) was fed to the 15th plate of the distillation column. bottom of the distillation column at a rate of 4.2 g / h. A suspended part (temperature: 21.0 ° C) of a line 53 was cooled in a C3 condenser at 5.8 ° C and refixed at a reflux rate of 298 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1,710 ppm, a Honey concentration of 83.1% by weight, a MeOH concentration of 0.08% by weight, an MA concentration of 14 , 0% by weight, a water concentration of 0.61% by weight, and an AC concentration of 2.0% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 36.7 ° C). The side flow was cooled in a C4 cooling unit at 5.8 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase with an AD concentration of 18.3% by weight (temperature: 7 ° C) was removed at a rate of 10.1 g / h from tank 6c by means of a line 69. A second portion of the aqueous phase (a line 69a) was removed at a flow rate of 3.0 g / h from tank 6c and mixed (or mixed) with the total amount (971 g / h) of the Mel phase (a line 68, temperature: 5 , 8 ° C) removed from tank 6c, and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The rate taken from the bottom flow (line 52, temperature: 45.1 ° C) of the second distillation column 5 was 1,289 g / h.
[00225] According to the process, removing the aqueous phase (line 69) formed by the lateral flow of the second distillation column 5, AD and Mel were removed from the process at a flow rate of 1.85 g / h and a flow rate of 0 , 17 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 42.7 kcal / h.
[00226] The following table shows the results of the component analysis in each line represented in figure 3. The aqueous phase in line 69 was fed into the fourth distillation column 8 without being fed into the third distillation column 7. Thus, the composition of the aqueous phase in line 69 is the same as the composition of the feed line 74 connected in the distillation column 8.


[00227] A second distillation column 5 with the actual number of stages of 10 [column top temperature of 21.1 ° C, column bottom temperature of 45.2 ° C, pressure of the top of the atmospheric pressure column + 10 mmEUO (about 100 Pa)] was provided. A feed liquid (a line 44, temperature: 21 ° C) was fed to the 3rd plate at the bottom of the distillation column at a rate of 1,303 g / h, and water (temperature: 21 ° C) was fed to the 10th plate of the distillation column. bottom of the distillation column at a rate of 6.3 g / h. A suspended part (temperature: 21.1 ° C) of a line 53 was cooled in a C3 condenser at 5.8 ° C and refluxed at a reflux rate of 300 g / h for extractive distillation with water in the column. The feed liquid was a methyl iodide solution with an AD concentration of 1790 ppm, a Honey concentration of 83.2% by weight, a MeOH concentration of 0.09% by weight, an MA concentration of 13 , 9% by weight, a water concentration of 0.66% by weight, and an AC concentration of 1.95% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 36.7 ° C). The side flow was cooled in a C4 cooling unit at 5.8 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase with an AD concentration of 21.0% by weight (temperature: 5.8 ° C) was removed at a rate of 8.8 g / h from tank 6c via a line 69. One second portion of the aqueous phase (a line 69a) was removed in a 9.5 g / h flow from tank 6c and mixed (or mixed) with the total amount (971 g / h) of the Mel phase (a line 68, temperature : 5.8 ° C) removed from tank 6c, and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The rate taken from the bottom stream (line 52, temperature: 45.2 ° C) of the second distillation column 5 was 1,300 g / h.
[00228] According to the process, removing the aqueous phase (line 69) formed by the lateral flow of the second distillation column 5, AD and Mel were removed from the process at a flow rate of 1.84 g / h and a flow rate of 0.145 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 44.1 kcal / h.
[00229] The following table shows the results of the component analysis in each line represented in figure 3. The aqueous phase in line 69 was fed into the fourth distillation column 8 without being fed into the third distillation column 7. Thus, the composition of the aqueous phase in line 69 is the same as the composition of the feed line 74 connected in the distillation column 8.

[00230] A second distillation column 5 with the actual number of stages of 13 [column top temperature of 21.4 ° C, column bottom temperature of 47.4 ° C, pressure of the top of the atmospheric pressure column + 10 mmfUO (about 100 Pa)] was provided. A water-rich feed liquid (a 43b line, temperature: 21 ° C) and a honey-rich feed liquid (a line 44, temperature: 21 ° C) were fed at 360 g / h and 639 g / h, respectively , on the 7th plate at the bottom of the distillation column, and water (temperature: 21 ° C) was fed on the 13th plate at the bottom of the distillation column at the rate of 3.8 g / h. A suspended part (temperature: 21.4 ° C) of a line 53 was cooled in a C3 condenser at 7 ° C and refluxed at a reflux rate of 250 g / h for extractive distillation with water in the column. The water-rich feed liquid showed an AD concentration of 3,840 ppm, a Honey concentration of 2.6% by weight, a MeOH concentration of 0.99% by weight, an MA concentration of 8.3% by weight. weight, a water concentration of 63.7% by weight, and an AC concentration of 24.0% by weight. The Honey-rich feed liquid was a methyl iodide solution with an AD concentration of 1860 ppm, a Honey concentration of 82.0% by weight, a MeOH concentration of 0.084% by weight, an MA concentration of 13.6% by weight, a water concentration of 0.85% by weight, and an AC concentration of 3.3% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 37.2 ° C). The side flow was cooled in a C4 cooling unit at 7.1 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase with an AD concentration of 23.7% by weight (temperature: 7.1 ° C) was removed at a rate of 8.7 g / hr from tank 6c via a line 69. One second portion of the aqueous phase (a line 69a) was removed in a flow of 3.9 g / h from tank 6c and mixed with the total amount (746 g / h) of the Mel phase (a line 68, temperature: 7.1 ° C) removed from tank 6c, and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The bottom flow (line 52, temperature: 47.4 ° C) from the second distillation column 5 was removed at a rate of 994 g / h in total with the supplied water and Mel phase.
[00231] According to the process, removing the aqueous phase (line 69) formed by the lateral flow of the second distillation column 5, AD and Mel were removed from the process at a flow rate of 2.06 g / h and a flow rate of 0.156 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 43.5 kcal / h.
[00232] The following table shows the results of the component analysis in each line represented in figure 3. The aqueous phase in line 69 was fed into the fourth distillation column 8 without being fed into the third distillation column 7. Thus, the composition the aqueous phase in line 69 is the same as the composition of the feed line 74 connected to the distillation column 8.

[00233] A second distillation column 5 with the actual number of stages of 13 [column top temperature of 21.4 ° C, column bottom temperature of 47.9 ° C, pressure of the top of the atmospheric pressure column + 10 mmH2O (about 100 Pa)] was provided. A water-rich feed liquid (a line 43b, temperature: 21 ° C) and a honey-rich feed liquid (a line 44, temperature: 21 ° C) were fed at 932 g / h and 105 g / h, respectively , on the 7th plate at the bottom of the distillation column, and water (temperature: 20 ° C) was fed on the 13th plate at the bottom of the distillation column at 6.5 g / h. A suspended part (temperature: 21.4 ° C) of a line 53 was cooled in a C3 condenser at 6.9 ° C and refluxed at a reflux rate of 259 g / h for extractive distillation with water in the column. The water-rich feed liquid showed an AD concentration of 3,840 ppm, a Honey concentration of 2.4% by weight, a MeOH concentration of 0.99% by weight, an MA concentration of 8.3% by weight. weight, a water concentration of 63.2% by weight, and an AC concentration of 24.5% by weight. The Honey-rich feed liquid was a methyl iodide solution with an AD concentration of 1,860 ppm, a Honey concentration of 81.9% by weight, a MeOH concentration of 0.10% by weight, a concentration of MA is 13.7% by weight, a water concentration of 0.85% by weight, and an AC concentration of 3.3% by weight. A chimney pan was installed instead of the third plate below the top of the column, and the total amount of liquid that fell was removed as a side flow 63 (temperature: 37.1 ° C). The side flow was cooled in a C4 cooling unit at 6.9 ° C and was then introduced into a holding tank 6c to form two phases of an aqueous phase and an organic phase. A first portion of the aqueous phase with an AD concentration of 22.0% by weight (temperature: 6.9 ° C) was removed at 10.4 g / h from tank 6c via a line 69. A second portion of the aqueous phase (a line 69a) was removed in a flow of 6.2 g / h from tank 6c and mixed (or mixed) with the total amount (746 g / h) of the Mel phase (a line 68, temperature: 6, 9 ° C) removed from tank 6c, and the resulting mixture was recycled on the first plate below the flue pan (the fourth plate below the top of the column). The bottom flow (line 52, temperature: 47.9 ° C) from the second distillation column 5 was removed at a rate of 1,033 g / h in total with the aqueous phase and the supplied Mel phase.
[00234] According to the process, removing the aqueous phase (line 69) formed by the lateral flow of the second distillation column 5, AD and Mel were removed from the process at a flow rate of 2.28 g / h and a flow rate of 0.183 g / h, respectively. The second distillation column 5 required an amount of heat in the reflector of 39.2 kcal / h.
[00235] The following table shows the results of the component analysis in each line represented in figure 3. The aqueous phase in line 69 was fed in the fourth distillation column 8 without being fed in the third distillation column 7. Thus, the composition of the aqueous phase in line 69 is the same as the composition of the feed line 74 connected in the distillation column 8.

[00236] Table 14 shows the results obtained in examples 1 to 10. Table 14 also shows the number of distillation stages, the separation efficiency of PRC's and methyl iodide, and the energy efficiency.

[00237] The extraction of water was carried out in the same way as the previous examples, with different numbers of stages of the second distillation column 5 (10 stages to 43 stages), different amounts of water-rich feed liquid (line 43b) in the second distillation column 5 (0 to 1,000 g / h), different amounts of the honey-rich food liquid (line 44) (0 to 1,000 g / h), different reasons for the water-rich food liquid with respect to the Honey-rich feed liquid (first / last (weight ratio) = 5/95 to 100/0), different amounts of water supply at the top of the column (0 to 8 g / h), and different amounts of recycling of the aqueous phase in line 69a (0 to 8 g / h). The correlation between the concentration of AD in the aqueous extract (line 69) and the methyl iodide / acetaldehyde ratio (Mel / AD ratio) was examined. The results are shown in figure 5. The curve in figure 5 is a polynomial approximation curve prepared by an “Excel” software.
[00238] Table 14 and figure 5 show the fact that the concentration of AD in the aqueous extract has an ideal value and a very low or very high AD concentration increases the disposal of Honey out of the system.
[00239] In comparative example 1, the amount of AD removal and the amount of honey lost indicates the amount of AD and the amount of honey in the aqueous extract 275 of the extractive distillation column with water 207 in figure 4. In the examples, the amount of AD removal and the amount of lost Honey indicate the amount of AD and the amount of Honey in the aqueous phase 69 formed by the side flow of the second distillation column 5. In comparative example 1, the ratio of methyl iodide / acetaldehyde ( Mel / AD ratio) was calculated from the amount of AD and the amount of Mel in aqueous extract 275. In examples 1 to 10, the ratio of methyl iodide / acetaldehyde (Mel / AD ratio) was calculated from the amount of AD and the amount of honey in the aqueous phase 69. [Consideration]
[00240] The comparison between comparative example 1 and examples 1 to 8, in each case where the honey-rich feed liquid (line 44) was fed, shows that AD is condensed by the 100-stage distillation column and separated by water extraction in the comparative example, while AD is efficiently separated with a small number of stages, according to the conditions of extractive distillation with water from the examples. Among these examples, according to Example 8, AD is separated sufficiently in just 10 stages, and the amount of steam (energy) required per AD removal unit is only 24 kcal / g-AD against 44.5 kcal / g-AD for comparative example 1. Thus, the amount of steam consumption and significantly reduced.
[00241] Additionally, from comparing comparative example 1 with example 10, the amount of steam (energy) required per AD removal unit is only 17.2 kcal / g-AD, for example 10, where the water-rich feed liquid (line 43b) was fed against 44.5 kcal / g-AD for comparative example 1. Thus, AD is removed with 39% of the energy required in conventional technique. This reason is probably that the liquid feed rich in the aqueous phase, which has a higher concentration of AD compared to the liquid feed rich in methyl iodide, allows efficient removal of AD. Furthermore, compared to comparative example 1, all examples have a lower Mel / AD ratio and also reduce the discharge of Mel out of the system.
[00242] In a case where the water-rich feed liquid (line 43b) and the honey-rich feed liquid (line 44) are fed into the second distillation column 5, AD is efficiently separated with a smaller energy, even for a small number of stages along with the increase in the ratio of the water-rich food liquid (Example 9: the weight ratio of the water-rich food liquid (aqueous phase) to the honey-rich food liquid (Mel phase) = 36/64; Example 10: the weight ratio of the aqueous phase to Mel phase = 90/10). The reason is probably as follows: the presence of methyl iodide throughout the entire area from the bottom to the top of the distillation column 5 improves the efficiency of AD separation, and the concentration of AD in the water-rich feed liquid It is larger than that in the liquid of food in Mel. INDUSTRIAL APPLICABILITY
[00243] According to the present invention, PRC's (e.g., acetaldehyde) can be efficiently separated and removed from a process flow, and a process significantly used to produce stably high quality acetate acid can be provided. REFERENCE1 Reactor2 Evaporator (Vaporizer) 3 Separator column (First distillation column) 4 Decanter5 Second distillation column (Column to separate PRC's such as acetaldefdo) 6th Separation unit6b Retention tank and Decanter6c Decanter7 Third distillation column8 Fourth column extractive distillation) n

权利要求:
Claims (15)
[0001]
1. Process for separating or removing a permanganate reducing compound (PRC) from a mixed composition, such as a first flow suspended from a first distillation step, containing at least PRC and media iodide, the process comprising deploying the mixed composition into a second distillation step to form a second suspended flow, a side flow, and a lower flow, characterized by the fact that the PRC includes at least acetaldehyde, and the process further comprises the steps of: adding an extraction agent that extracts a PRC preferably of methyl iodide in a concentration zone of a PRC and methyl iodide, in a distillation column of the second distillation step, and remove an extraction mixture that falls from the concentration zone as the lateral flow.
[0002]
2. Process according to claim 1, characterized by the fact that the mixed composition contains methyl iodide in a concentration of not less than 1.5% by weight.
[0003]
3. Process according to claim 1 or 2, characterized by the fact that the mixed composition is biphasically separated, and comprises at least a portion of an organic phase, at least a portion of an aqueous phase, or a mixed composition containing the organic phase and the aqueous phase.
[0004]
Process according to any one of claims 1 to 3, characterized by the fact that the extraction mixture or lateral flow satisfies the following conditions (i), (ii), and / or (iii) :( i) a concentration of PRC in the extraction mixture or the side flow is greater than a concentration of PRC in each mixed composition and lower flow, (ii) the extraction mixture or the side flow has a PRC concentration of 0.1 to 45% in weight, (iii) a ratio of the PRC to the methyl iodide in the extraction mixture or to the side flow is greater than a ratio of the PRC to the methyl iodide in each mixed and lower flow composition.
[0005]
Process according to any one of claims 1 to 4, characterized by the fact that the mixed composition comprises, in addition to acetaldehyde and methyl iodide, (a) methyl acetate and / or (b) at least one component selected from the group consisting of acetate, methanol, water, dimethyl ether and an acetaldehyde derivative.
[0006]
Process according to any one of claims 1 to 5, characterized in that the weight ratio of a flow of the extraction agent with respect to a flow of the mixed composition is 0.0001 / 100 to 100/100 in the first / lastly, in terms of liquid material.
[0007]
Process according to any one of claims 1 to 6, characterized in that the distillation column of the second distillation step is provided with a receiver, the receiver being disposed in a position lower than an adjoining port for the extraction agent, allowing a vapor or evaporation fraction from the mixed composition to ascend to the concentration zone, and being able to receive the extraction mixture that falls from the concentration zone; the extraction agent is added to the concentration zone formed before from the receptor, the extraction agent being separated from methyl iodide to form an extract phase; and the extraction and withdrawal mixture as the lateral flow of a withdrawal port that communicates with the receiver.
[0008]
Process according to any one of claims 1 to 7, characterized by the fact that the distillation column of the second distillation stage is provided with at least one chimney pan; the extraction agent is added to the concentration zone, the agent of extraction being an aqueous extraction agent, the concentration zone being formed below or above a higher chimney pan, and containing a vapor or evaporation fraction from the mixed composition; the extraction mixture that falls from the concentration zone is received in a section of the pan or flue pan area; and the extraction mixture is kept in the tray and removed as the side flow.
[0009]
Process according to any one of claims 1 to 8, characterized in that the extraction agent comprises at least one aqueous solvent selected from the group consisting of (i) water, (ii) an aqueous process flow produced in the process, and (iii) an aqueous mixture produced by water absorption treatment of a gas generated from the process, and the extraction mixture is separated into an upper and a lower phase.
[0010]
Process according to any one of claims 1 to 9, characterized in that it additionally comprises recycling an organic phase containing at least methyl iodide in the second distillation step by the following method (a), (b) or (c ) :( a) Biphasically separate the extraction mixture taken from the distillation column of the second distillation stage into an aqueous phase containing at least acetaldehyde and an organic phase containing at least methyl iodide, separate the aqueous phase, and recycle the organic phase in the distillation column of the second distillation stage, (b) biphasically separate the extraction mixture removed from the distillation column of the second distillation stage into an aqueous phase containing at least acetaldehyde and an organic phase containing at least methyl iodide, and recycle a portion of the aqueous phase and the organic phase in the distillation column of the second distillation step, (c) biphasically separating at least the extraction mixture, between the extraction mixture and the second suspended flow, in an aqueous phase and an organic phase containing at least methyl iodide, subject at least a portion of the aqueous phase to distillation and / or extractive distillation with water in a subsequent distillation step, and to recycle directly or indirectly to organic phase in the distillation column of the second distillation step from a position lower than a withdrawal port to withdraw the lateral flow.
[0011]
Process according to any one of claims 1 to 10, characterized in that it additionally comprises the steps of: biphasically separating at least the extraction mixture, between the extraction mixture and the second suspended flow, to form an aqueous phase and an organic phase, distilling the aqueous phase in a subsequent distillation step to form another suspended flow containing acetaldehyde and methyl iodide, and a liquid flow containing the extraction agent, and using the liquid flow containing the extraction agent as an agent extraction to obtain the extraction mixture in the second distillation step.
[0012]
Process according to any one of claims 1 to all, characterized in that it additionally comprises the steps of: biphasically separating at least the extraction mixture, between the extraction mixture and the second suspended flow, in an aqueous phase and a organic phase, distill at least a portion of the aqueous phase in a subsequent distillation step, directly or indirectly recycle the organic phase in the second distillation step from a position lower than a withdrawal port for lateral flow, feed directly or indirectly a miscible solvent in the second distillation step from a position lower than the withdrawal port for lateral flow, the miscible solvent being miscible with the organic phase separated from the extraction mixture and comprising at least one component selected from the group consisting of in water, acetate, methyl iodide, and methanol.
[0013]
Process according to any one of claims 1 to 12, characterized in that it further comprises: a reaction step of continuously carbonylating methanol in the presence of a catalyst system comprising a metal catalyst, a metal halide, and methyl iodide; a rapid evaporation step of continuously separating the reaction mixture into a volatile phase and a less volatile phase, the volatile phase containing acetate acid product and methyl iodide, and the less volatile phase containing the metal catalyst and the metal halide; first distillation step of continuously separating the volatile phase into a first suspended part containing methyl iodide and acetaldehyde by-product, and a flow containing acetate acid; In a step of condensing a gas phase to form an organic phase and an aqueous phase, the gas phase being produced from at least one step selected from the group consisting of these steps and containing at least acetaldehyde and methyl iodide, in which at least a portion of the organic phase and / or at least a portion of the aqueous phase is subjected to a second distillation step mentioned in claim 1, and water or at least a portion of the aqueous phase is fed as the extraction agent in a second step of distillation mentioned in claim 1.
[0014]
14. Process to produce acetic acid, characterized by the fact that it comprises the steps of: distilling a mixed composition containing at least one permanganate reducing compound (PRC), methyl iodide, methyl acetate, and acetate acid in a first stage of distillation to separate the mixed composition into a first suspended part and a flow of acetate, the first suspended part containing at least one PRC and methyl iodide, and the flow of acetate containing product of acetate, and at least a portion of the the first part suspended to a second distillation step, in which the PRC includes at least acetaldehyde, and the process additionally comprises the steps of: adding an extraction agent that extracts a PRC preferably from methyl iodide in a concentration zone of a PRC and methyl iodide, in a distillation column of the second distillation step, to erect an extraction mixture that falls from the concentration zone as the lateral flow.
[0015]
15. Process according to claim 14, characterized by the fact that it comprises: a reaction step of carbonyl continuously methanol in the presence of a catalyst system comprising a metal catalyst, a metal halide and methyl iodide; a rapid evaporation step of continuously separate the reaction mixture into a volatile phase and a less volatile phase, the volatile phase containing acetate acid product and methyl iodide, and the less volatile phase containing the metal catalyst and the metal halide; a first distillation step of separating continuously the volatile phase in a first suspended part containing methyl iodide and acetaldehyde by-product, and a flow containing acetyl acid; a second distillation step cited in claim 14 of distilling at least a first portion of the suspended part.

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WO2021247854A1|2020-06-03|2021-12-09|Celanese International Corporation|Production and purification of acetic acid|

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WO2021247853A1|2020-06-03|2021-12-09|Celanese International Corporation|Process for acetic acid production by removing permanganate reducing compounds|

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WO2021247855A1|2020-06-03|2021-12-09|Celanese International Corporation|Removal of acetals from process streams|

法律状态:
2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/05/2016, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2015111750|2015-06-01|

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JP2015-111750|2015-06-01|

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PCT/JP2016/065822|WO2016194850A1|2015-06-01|2016-05-27|Process for producing acetic acid|

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