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    • 专利摘要:
    final extractive treatment of a methanol-mma mixture containing sodium salt The present invention relates to a process for preparing methyl methacrylate by direct oxidative esterification of methcrolein. methyl methacrylate is used in large amounts to prepare polymers and copolymers with other polymerizable compounds. furthermore, methyl methacrylate is an important synthetic unit for a variety of specialized esters based on methacrylic acid (maa) which can be prepared by transesterification with the appropriate alcohol. there is therefore a great interest in environmentally friendly, very simple and economical processes for preparing this starting material. in particular, the present invention relates to an optimized reactor effluent procedure of the oxidative esterification of methacrolein whereby process waste streams can be minimized and process water can be ideally recycled. the methacrylic acid generated in the process is also ideally recovered and isolated or converted to the alkyl methacrylate as a consumable. furthermore, this process has the advantage that less demands than those described in the prior art are required in installation apparatus configuration.
    公开号:BR112018005076B1
    申请号:R112018005076-8
    申请日:2016-09-14
    公开日:2021-06-29
    发明作者:Matthias Grömping；Steffen Krill；Alexander LYGIN；Milica LUKIC；Steffen FINGER
    申请人:Röhm Gmbh；
    IPC主号:
    专利说明:

    field of invention
    [0001] The present invention relates to a process to prepare methyl methacrylate by direct oxidative esterification of methcrolein. Methyl methacrylate is used in large amounts to prepare polymers and copolymers with other polymerizable compounds. In addition, methyl methacrylate is an important synthetic unit for a variety of specialized methacrylic acid (MAA) based esters that can be prepared by transesterification with the appropriate alcohol. There is, therefore, a great interest in environmentally friendly, very simple and economical processes for preparing this starting material.
    [0002] In particular, the present invention relates to an optimized procedure of the reactor effluent of the oxidative esterification of methacrolein by means of which process waste streams can be minimized and process water can be ideally recycled. The methacrylic acid generated in the process is also ideally recovered and isolated or converted to alkyl methacrylate as a consumer good. Furthermore, this process has the advantage that less demands than those described in the prior art are required in installation apparatus configuration. prior technique
    [0003] Methyl methacrylate (MMA) is currently produced by a variety of processes coming from C2, C3 or C4 synthesis units. In one of the processes, MMA is obtained by gas-phase oxidation of isobutylene or tert-butanol with atmospheric oxygen through a heterogeneous catalyst to produce methacrolein and subsequent oxidative esterification of methacrolein using methanol. This process, developed by ASAHI, is described, among others, in publications US 5,969,178 and US 7,012,039. A particular disadvantage of this process is the very high energy requirement. In a process development, methacrolein is obtained from propanal and formaldehyde in the first stage. Such a process is described in WO 2014/170223.
    [0004] The document US 5,969,178 describes such a process for oxidative conversion of isobutene or tert-butanol into methacrolein and subsequent oxidative esterification for MMA. In this second stage, a liquid mixture of methacrolein and methanol with reduced water content is reacted with molecular oxygen and a palladium catalyst, wherein said catalyst is generally in a form compatible with a palladium-lead catalyst. In a first stage of distillation, a mixture of methcrolein and methanol is then removed from the crude product from the oxidizing esterification below the top of the column, while low boiling constituents are removed by suspension. The bottoms product containing MMA is then passed to a second stage of distillation in which an azeotrope of methanol and saturated hydrocarbons is removed by suspension. The bottoms product comprising the crude MMA is sent to a further procedure, while methanol is isolated from the suspended fraction by means of a phase separator and a third distillation column and passed back to the reactor. It is important to realize that methanol can contain relatively large amounts of water due to the azeotrope formed and must therefore be sent to a runoff.
    [0005] As an alternative to this process, the document US 5,969,178 discloses a procedure in only one column, in which in said column it is imperative that the supply is located above the bottom of the column. The low boiling constituents of the reactor effluent are removed from this suspended column. The remainder at the bottom of the column is a mixture of raw MMA and water that must be sent for further processing. By means of a side stream, the exact position of which must first be determined, wherein said position is adjustable by adding several perforated trays, a mixture of methacrolein and methanol destined to return to the reactor is finally removed from the column . The document US 5,969,178 itself indicates that such a process is difficult to be carried out due to a variety of azeotropes. Particularly, methacrylic acid, which is always present as a by-product, moreover plays an important role. According to this process, regardless of the absence of information in document US 5,969,178 on this issue, the methacrylic acid would be removed in such a way that it remains in a phase to be sent for disposal and an isolation would be of only limited attractiveness. However, this results in a drop in the overall yield of methacrylic products from this process.
    [0006] The document US 7,012,039 discloses a reactor effluent procedure of the oxidative esterification which is somewhat of a departure. In the present document, in a first stage of distillation through sweep pans, methacrolein is suspension distilled and the mixture comprising aqueous MMA from the bottom of the column is passed into a phase separator. In said phase separator, the mixture is pH adjusted to a pH of about 2 by addition of sulfuric acid. The separation of the water acidified by sulfuric acid from the oil/organic phase is then affected by means of centrifugation. This oil phase is separated in further distillation into high-boiling constituents and a phase containing suspended MMA. The MMA-containing phase is then separated from the low-boiling constituents in a third distillation. This is further followed by a fourth distillation for final purification.
    [0007] The problem with this process is the sulfuric acid that needs to be added in large amounts and can have corrosive effects on parts of the installation. Consequently, these parts, such as in particular the phase separator or otherwise the second distillation column, must be manufactured from suitable materials. Furthermore, the document US 7,012,039 does not present information related to the handling of the methacrylic acid generated simultaneously or the residual methanol that remains in the product. However, it can be assumed that the aforementioned is removed from the core in the distillation stages, while methanol can be obtained and returned with methcrolein only partially, while the remainder is probably lost in the third stage of distillation.
    [0008] The document WO 2014/170223 describes a process similar to the document US 7,012,039. The only difference is that in the actual reaction, the pH is adjusted in a loop by adding a methanolic sodium hydroxide solution. This serves, among others, to protect the catalyst. Furthermore, the removal of the aqueous phase in phase separation is simpler due to the salt content. However, another consequence is that the methacrylic acid formed is in the form of the sodium salt and is later removed and discarded with the aqueous phase. Admittedly, in the variant where sulfuric acid is added in phase separation, the free acid is recovered. However, instead, sodium sulfate (hydrogen) is generated, which can lead to other problems at the time of disposal.
    [0009] In summary, the following aspects of the prior art processes, especially in combination with each other, need improvement in: - highest possible yield - obtaining the by-products generated in the form of methacrylic acid and isolating them or returning for oxidizing esterification - most possible extent of recycling of unconverted methanol - reduction of amounts of sulfuric acid and water to be added - cleanest possible waste flue streams/gases Problem
    [0010] The problem addressed by the present invention in view of the prior art is, therefore, that of providing a technically improved process for oxidative esterification of methacrolein that is not affected by the disadvantages of conventional processes.
    [0011] A particular problem addressed by the present invention was that of providing an improvement in the procedure of the crude product of an oxidizing esterification of methacrolein and methanol to produce MMA and thereby improving the overall yield of such a process compared to the prior art .
    [0012] An additional problem addressed was that of recycling and converting in the process into the target products, to the greatest extent possible, the greatest possible number of unconverted reagents or by-products or intermediates formed in the process, in particular, methanol, methcrolein, methacrylic acid and water and optionally isolating the methacrylic acid as such.
    [0013] An additional problem addressed was that of isolating/recycling methacrylic acid from the system using the smallest possible amounts of added acid. The local concentration and overall consumption of this acid should be kept as low as possible.
    [0014] An additional problem addressed by the present invention was that of designing the procedure so as to ensure the least possible number of contact points with strong acids and, therefore, corrosive in the installation. A subsequent problem addressed by the present invention was, in turn, to ensure that, in terms of the material of construction, the general installation needs to be provided with adequate acid protection only to a limited extent.
    [0015] A particular additional problem addressed was that of providing a process that can be operated with the lowest possible disposal cost, in particular, through reduced generation of organic constituents and acids in the waste stream.
    [0016] The process should, moreover, be inexpensive, in particular, in terms of the materials to be employed for the construction of the installation, compared to the prior art. Solution
    [0017] The problems are solved by a process to produce MMA, in which in a first reaction stage (A) in a reactor I (1), methacrolein is produced and in a second reaction stage (B) in a reactor II (10), said methcrolein is oxidatively esterified with an alcohol, preferably with methanol, to produce an alkyl methacrylate, thereby preferably to produce MMA, wherein the process comprises an innovative procedure (C ) of the crude product discarded from the second reactor (10). In this procedure (C), a low boiling fraction comprising mainly alcohol is obtained from a mixture comprising water, alcohol, at least one alkali metal salt, methacrylic acid and a strong acid in a distillation column IV. This alcohol is then used again to produce alkyl methacrylates.
    [0018] According to the invention, a strong acid is to be understood as meaning an acid stronger than methacrylic acid. This means that the acid has a lower PKA than methacrylic acid under standard conditions. A particularly preferred inorganic acid is, in this case, sulfuric acid. Less preferred organic acids can be, for example, methanesulfonic acid or toluenesulfonic acid. An example of an additional suitable mineral acid is phosphoric acid.
    [0019] Preferably, in this procedure (C), a stream comprising water, alcohol, at least one alkali metal salt, an organic and/or inorganic acid, preferably inorganic and methacrylic acid is separated in a stage of distillation (21), hereinafter referred to as IV distillation column (21), in a low-boiling fraction (22) comprising alcohol, a sidestream fraction (23) comprising water and methacrylic acid, and a fraction of base (24) comprising water, the organic and/or inorganic acid and the alkali metal salts thereof. The innovation in this document is, in particular, the side chain removed separately (23).
    [0020] The process for sintering MMA comprising the two reaction stages mentioned above (A) and (B) can be read, in particular, in documents US 5,969,178, US 7,012039 and WO 2014/170223. The first stage of the process for sintering metacrolein is freely chosen according to the invention. The process according to the invention is applicable to a first-stage synthesis either based on tert-butanol or isobutylene or on propanal and formaldehyde. It is preferred when the oxidative esterification is carried out in the liquid phase at a pressure of 0.2 MPa to 10 MPa (2 to 100 bar), preferably at a pressure in the range of 0.2 MPa to 5 MPa (2 to 50 bar ), and a temperature in the range of 10 °C to 200 °C with a heterogeneous catalyst. The heterogeneous catalyst generally comprises compatible gold-containing nanoparticles having a particle size less than 20 nm, preferably between 0.2 and 20 nm. Reaction stage (A) may comprise an optional and less preferred distillation column II for removing low boiling points such as remaining propionaldehyde and/or high boiling points such as dimeric methacrolein.
    [0021] This distillation stage is preferably an IV distillation column (21) which is integrated in the following configuration. The crude product from the oxidizing esterification is initially free of methacrolein and partially of alcohol, eg methanol in a distillation column III (15). This produces a stream comprising an alkyl methacrylate, preferably MMA, water, an alkali metal methacrylate and/or methacrylic acid and methanol. This stream is then separated into an extraction phase (20) and/or a phase separation (19) present without an extraction or arranged upstream of said extraction into a light phase comprising an alkyl methacrylate, preferably , MMA and methacrylic acid and a heavy phase comprising water, methanol and the alkali metal methacrylate. This heavy phase is then passed into the IV distillation column (21) and the withdrawn side stream from the IV distillation column (21) is returned to the extraction (20). In this process mode, the addition of strong acid (eg as (17)) is also affected in this document, for example, upstream of the feed in phase separation (19) or in extraction (20).
    [0022] It is preferred when the feed of strong acid (for example, 17) is affected between the distillation column III (15) and the extraction (20), in the extraction itself (20), in the heavy phase withdrawn from the extraction (20 ) and/or in the IV distillation column (21). It is particularly preferred when the stream from the distillation column III comprising the alkyl methacrylate is admixed with the strong acid.
    [0023] In the case where the strong acid feed is already at least partially affected upstream of the extraction (20), the distillation column stream III (15) also already comprises proportions of that acid and corresponding alkali metal salts of the acid . In that case, methacrylic acid is present as the free acid.
    [0024] A feature of the present invention which is essential according to the invention is the IV distillation column (21), particularly preferably comprising sidestream withdrawal. In particular, this means that aspects described hereinafter and not specifically directed to the preferred modality having a distillation column III (15) and an extraction (20) are not limited to these modalities. In addition, the IV distillation column (21) can also be called a desorption column.
    [0025] This preferred procedure is, furthermore, preferably characterized in that the feed in the extraction, the extraction itself, the heavy phase removed from the extraction and/or the IV distillation column (21) is mixed by addition with the strong acid, preferably exclusively inorganic. It is particularly preferred when the strong acid feed in the heavy phase of the extraction is affected directly upstream of the IV distillation column.
    [0026] In a further advantageous optional variant of the invention, the stream from the distillation column III (15) comprising the alkyl methacrylate is passed into a phase separator (19) from which an organic phase is passed in the extraction ( 20) and an aqueous phase is passed through the IV distillation column (21).
    [0027] In a further advantageous optional variant of the invention, the stream from the distillation column III (15) comprising the alkyl methacrylate is passed into a mixer (16) in which the strong acid and optionally water are sent and mixed with the stream comprising alkyl methacrylate and that this mixture is subsequently passed through the phase separator (19) or directly into the extraction (20). Addition mixing with the strong acid also causes an acetal cleavage. Acetals can be present in the mixture as an impurity. Such acetal cleavage is described, for example, in JP11-302224A.
    [0028] A great advantage of this procedure is that in the IV distillation column (21) the alkali metal methacrylate is practically completely converted to methacrylic acid in the presence of strong acid and, in particular, inorganic acid and passed again in the extraction ( 20) by means of the side chain (23). Said methacrylic acid is then discharged from the system at that point as a constituent of the low boiling fraction along with MMA and can be isolated. In this way, this process allows for a completely higher yield of desired C4 products. Otherwise, methacrylic acid, in particular in the form of an alkali metal salt, would be withdrawn from the IV distillation column (21) in the aqueous phase and sent, for example, for disposal (24).
    [0029] It is particularly preferred to feed all or at least most of the inorganic acid into the heavy phase of the extraction directly upstream of the IV distillation column (21). This modality has the great advantage of having only this feed, the column of the IV distillation column (21) and the conduit for removing the bottom fraction (24) of this column, as well as the downstream components of said conduit need to be manufactured in from a particularly corrosion resistant material or with a corrosion resistant coating. An example of such corrosion resistant material is zirconium. This modality is comparatively less dependent on extraction (20) and distillation column III (15) and a simpler material can be employed, which in turn saves on capital costs.
    [0030] It is also preferred when strong acid is added to the respective stream, in particular, downstream of the distillation column III (15) or in the extraction (20), only in a sufficient amount to ensure that the pH in the extraction is always > 3.
    [0031] In addition to the preferred configuration described, other constructions comprising the inventive IV distillation column (21) with, preferably, the present side stream withdrawal, are also conceivable according to the invention. Thus, an installation in which distillation column III (15) is absent is conceivable. A simple phase separation, for example in the form of a centrifuge, would also be conceivable in place of extraction. It is also possible to connect a plurality of distillation stages, phase separators and/or centrifuges in series to withdraw the individual fractions.
    [0032] However, it is possible in a particular modality to feed small amounts of the strong acid in the respective stream downstream of the distillation column III (15) or in the extraction (20). So, it is necessary, if the intention is still to use the same materials for distillation column III (15) and extraction (20), to choose the amount of inorganic acid feed so that the relevant stream is adjusted to a non-pH. less than 3. The advantage of this variant is that a portion of the alkali metal methacrylate is already converted to the free acid upstream of or in the raw MMA feed in the extraction (20) and can already be withdrawn from the system upstream of the conduit in the column IV distillation (21).
    [0033] In particular, the cited alkali metal salt is sodium sulfate, the alkali metal methacrylate is sodium methacrylate and the inorganic acid is sulfuric acid. However, it is also conceivable to employ other alkali metals, for example potassium. It is also very preferable that all the stages mentioned, and thus the entire particular process, be carried out continuously regardless of the exact configuration.
    [0034] The processes for additional processing of chains removed from the described procedure are described below:
    [0035] The light phase which, in the preferred embodiment, is removed from extraction can, for example, be processed through at least two, preferably at least three, additional distillation stages. For this purpose, raw MMA initially has high-boiling constituents removed from it in a V distillation column (25) and then has low-boiling constituents removed from it in a VI distillation column (26) . This can optionally be followed by a final purification on a VII distillation column (27), eg for reformulated removal of additional low boiling constituents. Purified alkyl methacrylate, in particular MMA (28) is thus generated, for example, as an overhead stream from a third stage of distillation, while methacrylic acid can be isolated as the bottom of the first (29) and /or third distillation column and can optionally be sent to an additional distillation stage. Alternatively, one or more or all of these distillation stages may, in particular for purifying methacrylic acid, be replaced by a crystallization. Regardless of the procedure, a fraction predominantly composed of methacrylic acid (29) and a fraction predominantly composed of MMA (28) are obtained.
    [0036] The fraction predominantly composed of methacrylic acid (29) can then be esterified with an alcohol to produce an alkyl methacrylate. In particular, methacrylic acid can be esterified with methanol to produce MMA. This is preferably done in a separate reactor (30) and not when returning to reactor II (10). The reason why this occurs is that either an excessively high acid content in the reactor for oxidative esterification would damage the catalyst employed therein or that - in particular - a pH of about 7 is established therein by addition of an alkali metal hydroxide , for example, sodium hydroxide, which would again convert the methacrylic acid into an alkali metal salt and thus prevent an esterification.
    [0037] In contrast, the low boiling fractions from the III distillation column (15) which comprise the methcrolein remaining in the crude product from the oxidizing esterification and a fraction of the unconverted methanol can preferably be passed back into the reactor to oxidizing esterification (10) in the second reaction stage. The same also applies to the low boiling fraction (22) of the IV distillation column (21) which predominantly comprises the remaining methanol. It is also preferably passed back into the reactor of the second reaction stage (10).
    [0038] In particular, the low boiling fraction of the IV distillation column comprises more than 60% by weight, preferably more than 65% by weight of alcohol and less than 20% by weight, preferably less than 10% by weight of water. The bottom fraction in particular comprises more than 60% by weight, preferably more than 80% by weight of water, and preferably the present sidestream fraction of distillation column IV comprises in particular more than 80% by weight, preferably more than 95% by weight of water and less than 5% by weight, preferably less than 1% by weight of alcohol.
    [0039] The heavy phase also called the bottom fraction (24) of the second IV distillation column (21) can finally be sent for disposal (24), for example, to a biological procedure or an oxidizing incineration.
    [0040] It is particularly preferred when the side stream (23) of the column of the IV distillation column (21) is withdrawn at a point in that column at which the alcohol content and preferably the methanol content is less than 1% by weight. The column preferably comprises perforated trays so that the side stream (23) is withdrawn in liquid form and does not need to be further condensed. However, when withdrawn in liquid form, the side stream (23) could contain a fraction of the strong acid, in particular sulfuric acid, which would thus be passed back on in the extraction (20). In the case where these quantities are only small and a pH above 3 is thus achieved in the extraction, this does not pose a major problem. However, the side stream (23) must be removed so that the acid content is higher, the extraction (20) must also be constructed from a suitable corrosion resistant material.
    [0041] Alternatively and particularly preferably, the lower part of the IV distillation column (21) comprises a partition wall. In this modality, the column feed in the IV distillation column (21) is supplied at the upper end of the partition wall and the extraction side is positioned at a point on the other side of the partition wall so that at said point the concentration of strong acid is less than 0.1% by weight, while the alcohol content is less than 1% by weight. In that case, the side stream can preferably be withdrawn in liquid form at the upper edge of that side of the dividing wall. This variant additionally has the great advantage that, in particular, the water on the withdrawal side of the dividing wall hardly contains any sulfur compounds and that a longer residence time for the reaction of the alkyl methacrylate with the sulfuric acid is achieved in the other side of the dividing wall. Then, it is also possible to build the conduit to transfer the side stream back to the extraction (20) from less corrosion resistant material. Distillation columns comprising a dividing wall can be read, for example, in N. Asprion, G. Kaibel, Chem. Eng. and Process., 49 (2010), 139 to 146 or in I. Dejanovic et al., Chem. Eng. and Process., 49 (2010), 559 to 580.
    [0042] It is particularly preferable to additionally install a heat exchanger in the installation whereby the side stream fraction (23) of the IV distillation column (21) is cooled before introduction into the extraction (20) and the heavy phase of the extraction (20) is simultaneously heated prior to introduction into the IV distillation column (21).
    [0043] Regardless of the specific modalities of the process according to the invention, said process has the great advantage compared to processes known from the prior art, which varies only in the particular extent thereof, which, in particular, the local concentrations of the Strong acid, in particular sulfuric acid, can be locally controlled and kept low, in particular in the III distillation stage (15), in the additional phase separator (19) and in the extraction (20), as well as in the ducts and optional additional component parts located between them. This not only has the advantage that few corrosion resistant materials can be employed, but in particular also that the alkyl methacrylate, the raw materials employed in this way and remnants and the by-products formed are exposed to this acid to a lesser extent. , if they are exposed. This would result in the formation of additional by-products coupled with reduced yield and eventual discoloration of the final product. A simultaneous advantage is that, in general, less acid needs to be used.
    [0044] An even greater advantage of the present invention is that the bottom fraction (24) comprises less acid, product, reactants and by-products. Recycling the removed alkyl methacrylate and methacrylic acid products resulted in a significant improvement in the overall process C4 yield. Removal of reactants, in particular alcohol, and optional recycling in reactor II (10) further improves the efficiency of the process. In particular, however, the watery bottom fraction (24) is less contaminated with all of these cited constituents which primarily simplifies the disposal of that fraction and, furthermore, also results in a reduced environmental burden even for proper disposal. In particular, this bottom stream (24) from the IV distillation column (21) can be sent to a further separation stage to recover water and methacrylic acid and to concentrate the salt-containing residue stream. Such a separation stage can be, for example, an extraction column, a membrane separation stage or a combination of several such elements. An extraction column in this document is kept markedly hotter and thus faster than the IV distillation column (21). Such an additional procedure serves, in particular, to effect the recovery and recycling of methacrylic acid and water from the then concentrated salt-containing waste stream.
    [0045] In a particularly preferred variant, the undercurrent is worked so that the salt concentration is close to the concentration of a saturated solution after the concentration operation. This advantageously also minimizes the amount of methacrylic acid in the waste stream. It is also possible to generate two waste streams by means of an appropriate arrangement of different membrane separation stages, for example. One of these two streams is then highly concentrated in terms of by-product and salt content, while the other is predominantly water. This has the advantage that the second low concentration waste stream can be sent, for example, for biological disposal. The highly concentrated current is usually sent to a thermal oxidizer. List of Reference Numbers (1) metacrolein synthesis and isolation ((1) to (8), (33) to (35)) (1) reactor I for metacrolein synthesis (2) formaldehyde feed (3) propionaldehyde (4) base feed I (5) acid feed I (6) distillation column I, catalyst removal (7) optional catalyst fraction return to reactor I (8) MAL phase separation, methacrolein isolation (33) return MAL-containing aqueous phase to distillation column I (6) (34) metacrolein synthesis residue stream (35) stream to transfer metacrolein from MAL synthesis (A) to oxidative esterification (B); optionally but non-preferably comprising a distillation column II (8) oxidizing esterification of methcrolein to produce an alkyl methacrylate and recycling of methcrolein ((9) to (15)) (9) methcrolein stream feed in reactor II (10) reactor II for oxidative esterification of methacrolein (11) alcohol feed (generally methanol feed) (12) air/oxygen feed (13) base feed II (14) recycle stream comprising methcrolein and alcohol (15) distillation column III to separate methcrolein and partially alcohol from crude alkyl methacrylate (C) inventive preferential separation of reactor effluent from reactor II ((16) to (24)) (16) optional mixer (17) acid feed II (18) optional water feed (19) phase separation (20) extraction (21) inventive distillation stage (distillation column IV) (22) low boiling fraction comprising alcohol for return to reactor II (23 ) side stream fraction comprising water and methacrylic acid to return to the extraction stage (20), mixer (16) or phase separation (19). (24) bottom fraction comprising water, acid II and the alkali metal salts thereof for disposal or further procedure (D) preferential procedure of crude alkyl methacrylate (eg crude MMA) ((25) to (32) ) (25) distillation column V for removal of high boiling points (26) distillation column VI for removal of lowered boilers (27) distillation column VII for final purification of alkyl methacrylate (28) methacrylate product stream of alkyl (29) methacrylic acid containing stream from distillation column V (25) (30) optional esterification of methacrylic acid to produce alkyl methacrylate which includes separation of an alkyl methacrylate containing phase from a residue phase (31) isolation optional pure methacrylic acid as second product (32) Esterification residue stream (30)
    权利要求:
    Claims (14)
    [0001]
    1. Process to produce MMA in which, in a first reaction stage in reactor I, methacrolein is produced and, in a second reaction stage in reactor II, said methacrolein is oxidatively esterified with an alcohol to produce an alkyl methacrylate, characterized in that a low boiling fraction comprising mainly alcohol is obtained from a mixture comprising water, alcohol, at least one alkali metal salt, methacrylic acid and a strong acid in a IV distillation column, and this alcohol is used again to produce alkyl methacrylates.
    [0002]
    2. Process according to claim 1, characterized in that the crude alkyl methacrylate from the oxidative esterification is free of methcrolein and partially of alcohol in a distillation column III, in which a stream comprising alkyl methacrylate , water, an alkali metal methacrylate and/or methacrylic acid and alcohol is obtained, mixed by addition with a strong acid and separated into a phase separation and/or an extraction into a light phase comprising alkyl methacrylate and methacrylic acid and a heavy phase comprising water, alcohol, at least one alkali metal salt and methacrylic acid which is passed directly or indirectly to the distillation column IV.
    [0003]
    3. Process according to claim 1 or 2, characterized in that a mixture comprising water, alcohol, at least one alkali metal salt, a strong acid and methacrylic acid is separated in an IV distillation column in a low boiling fraction comprising alcohol, a sidestream fraction comprising water and methacrylic acid, and a bottom fraction comprising water, the strong acid and the alkali metal salts thereof.
    [0004]
    4. Process according to any one of claims 1 to 3, characterized in that the stream from the distillation column III comprising the alkyl methacrylate is mixed by addition with the strong acid and passed a phase separation from from which an organic phase is passed in the extraction and an aqueous phase is passed through the distillation column IV.
    [0005]
    5. Process according to any one of claims 2 to 4, characterized in that the stream from the distillation column III comprising the alkyl methacrylate is passed through a mixer in which the strong acid and, optionally, water are sent and mixed with the stream comprising alkyl methacrylate and that this mixture is subsequently passed through the phase separator and/or extraction.
    [0006]
    6. Process according to any one of claims 2 to 5, characterized in that the feed of strong acid in the heavy phase of extraction is affected directly upstream of the IV distillation column.
    [0007]
    7. Process according to any one of claims 1 to 6, characterized in that the alkali metal salt is sodium sulfate, alkali metal methacrylate is sodium methacrylate, inorganic acid is sulfuric acid, alcohol is methanol and the alkyl methacrylate is MMA.
    [0008]
    8. Process according to any one of claims 2 to 7, characterized in that the light extraction phase is fed into at least two additional distillation stages and/or a crystallization and that a fraction predominantly composed of methacrylic acid and a fraction composed predominantly of MMA are thus obtained.
    [0009]
    9. Process according to claim 8, characterized in that the fraction predominantly composed of methacrylic acid is esterified with an alcohol to produce an alkyl methacrylate.
    [0010]
    10. Process according to any one of claims 2 to 9, characterized in that the strong acid is added to the respective stream downstream of the distillation column III or in the extraction only in an amount sufficient to ensure that the pH in the extraction always be > 3.
    [0011]
    11. Process according to any one of claims 2 to 10, characterized in that the low boiling fractions of the III distillation column and/or the IV distillation column are passed in reactor II.
    [0012]
    12. Process according to any one of claims 1 to 11, characterized in that the low boiling fraction of the IV distillation column comprises more than 60% by weight of alcohol and less than 20% by weight of water , the bottom fraction comprises more than 60% by weight of water and the sidestream fraction of the IV distillation column comprises more than 80% by weight of water and less than 5% by weight of alcohol.
    [0013]
    13. Process according to any one of claims 1 to 12, characterized in that the lower part of the IV distillation column comprises a partition wall, in which the column feed is supplied at the upper end of the partition wall and in which the lateral extraction is taken out in liquid form at a point on the other side of the dividing wall where the concentration of strong acid is less than 0.1% by weight, while the alcohol content is less than 1% by weight.
    [0014]
    14. Process according to any one of claims 1 to 13, characterized in that the bottom stream of the IV distillation column is sent to an additional separation stage to recover water and methacrylic acid and to concentrate the residue stream which contains salt.
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    US4280009A|1981-07-21|Continuous production of 2-ethyl-hexyl acrylate free from dioctylether
    EP2643288B1|2016-04-06|Acrylate production process
    BRPI0620615A2|2011-11-16|Method and apparatus for producing purified methyl isobutyl ketone
    BR112017001772B1|2021-01-05|improved manufacturing process for alkyl | acrylates
    CN103483147B|2016-05-04|Improved Butanol Recycling method and apparatus
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    BR112018011104B1|2021-03-23|PROCESS TO PURIFY METHYL METHACRYLATE
    CZ363896A3|1997-07-16|Process for preparing alkyl acrylates
    BR112018005075B1|2021-06-29|PROCESS TO PREPARE AT LEAST ONE ALKYL METACRYLATE AND METACRYLIC ACID
    JP2001181233A|2001-07-03|Method for producing |acrylic ester
    BR112020026544A2|2021-03-23|PROCESS TO PREPARE MMA IN HIGH PERFORMANCE
    JP2002363150A|2002-12-18|Method and apparatus for separating acetic acid and dimethylformamide by distillation
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3819685A|1971-12-06|1974-06-25|Standard Oil Co|Preparation of esters from unsaturated aldehydes and alcohols|
    DE3411384A1|1984-03-28|1985-10-10|Basf Ag, 6700 Ludwigshafen|METHOD FOR THE EXTRACTION OF WATER-FREE OR MOSTLY WATER-FREE FORMIC ACID BY HYDROLYSIS OF METHYLFORMIAT|
    JPH0769948A|1993-09-02|1995-03-14|Kuraray Co Ltd|Recovery of methanol|
    JP3950505B2|1996-12-13|2007-08-01|旭化成ケミカルズ株式会社|How to recover lead|
    SG71815A1|1997-07-08|2000-04-18|Asahi Chemical Ind|Method of producing methyl methacrylate|
    JP3532763B2|1998-04-22|2004-05-31|旭化成ケミカルズ株式会社|Purification method of methyl methacrylate|
    JP2001288147A|2000-04-11|2001-10-16|Mitsubishi Rayon Co Ltd|Method for producing methyl methacrylate|
    JP3672818B2|2000-12-26|2005-07-20|三菱レイヨン株式会社| acrylic acid ester purification method|
    US7012039B2|2001-12-21|2006-03-14|Asahi Kasei Chemicals Corporation|Oxide catalyst composition|
    JP3819419B2|2006-04-21|2006-09-06|旭化成ケミカルズ株式会社|Method for recovering methacrolein and methanol|
    CN103833551A|2012-11-27|2014-06-04|华东理工大学工程设计研究院有限公司|Separation equipment and separation method of methyl methacrylate |
    MY176555A|2013-04-19|2020-08-16|Roehm Gmbh|Method for producing methylmethacrylate|TW201722903A|2015-12-18|2017-07-01|陶氏全球科技責任有限公司|Process for purification of methyl methacrylate|
    TW201739730A|2015-12-18|2017-11-16|陶氏全球科技責任有限公司|Process for purification of methyl methacrylate|
    SG11202000829RA|2017-08-04|2020-02-27|Roehm Gmbh|Concrete flow improvers and water reducers|
    EP3450422A1|2017-08-29|2019-03-06|Evonik Röhm GmbH|Method for producing optical moulding compositions|
    EP3549961A1|2018-04-03|2019-10-09|Evonik Röhm GmbH|Concrete flow improver and water reducing agent|
    CN111233667A|2018-11-29|2020-06-05|中国科学院大连化学物理研究所|Improved method for preparing methyl methacrylate|
    EP3786148A1|2019-08-28|2021-03-03|Röhm GmbH|Simplified processing of the reactor output from an oxidative esterification|
    EP3798206A1|2019-09-25|2021-03-31|Röhm GmbH|Method for producing alkyl methacrylates with improved water and acid guidance|
    EP3798202A1|2019-09-25|2021-03-31|Röhm GmbH|Method for purifying methyl methacrylate from low boiling point components|
    EP3945088A1|2020-07-30|2022-02-02|Röhm GmbH|Process for minimising the loss of activity in reaction steps carried out in circulation|
    法律状态:
    2019-12-03| B25D| Requested change of name of applicant approved|Owner name: ROEHM GMBH (DE) |
    2019-12-17| B25G| Requested change of headquarter approved|Owner name: ROEHM GMBH (DE) |
    2020-03-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-08-18| B25G| Requested change of headquarter approved|Owner name: ROEHM GMBH (DE) |
    2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-29| 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 14/09/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP15185434.6|2015-09-16|
    EP15185434|2015-09-16|
    PCT/EP2016/071608|WO2017046110A1|2015-09-16|2016-09-14|Extractive workup of a sodium-salt-containing mma-methanol mixture|
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