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    • 专利摘要:
    Aqueous composition for the separation of CO2 , and/or acid gases. The invention relates to an absorbent composition for capturing CO2 or any other acid gas from a gaseous stream by chemical regenerative absorption based on an optimized adjustment of the cyclic working capacity of the absorbent. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2697300A1
    申请号:ES201730955
    申请日:2017-07-21
    公开日:2019-01-22
    发明作者:Borrero Fernando Vega；Rubia Benito Navarrete；Fernandez Jose Antonio Camino；Palacio Mercedes Cano；Galeano Vicente Jesus Cortes；Penuela Sara Camino；Lopez Jaime Garrido
    申请人:Universidad de Sevilla；
    IPC主号:
    专利说明:

    [0001]
    [0002] Aqueous composition for the separation of CO2 and / or acid gases
    [0003]
    [0004] The present invention relates to an aqueous composition and its use in the separation of CO2 and / or acid gases by means of a CO2 separation system according to a regenerative chemical absorption process based on an optimized adjustment of the cyclic working capacity of the absorbent and optimized control of the operating conditions of the regenerator inlet currents, mainly in terms of temperature and distribution of feed flows to the equipment. Therefore, the present invention is framed in the area of environmental technology and chemical processes. In particular, it is included in the sector of capture of CO 2 and / or acid gases from stationary emission sources from industrial combustion plants, but it is applicable to other industrial processes where CO 2 separation is required and / or acid gases of any process stream composed of a mixture of gases.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007]
    [0008] The process of separation of acid gases from a gaseous current by chemical regenerative absorption has been used since the 1930s in numerous industrial processes, such as the synthesis gas treatment. In recent years, these processes have aroused great interest at the industrial level thanks to the possibility of being employed within the CO2 capture and storage technologies (WO1995 / 021683 A1).
    [0009]
    [0010] The general scheme of the process of separation of CO 2 by chemical absorption was patented by RR Bottoms (US1783901A). Said invention describes a system composed of an absorber, in which the gases to be treated are brought into contact, in countercurrent, with an absorbent solution that separates the acid gases (CO 2 , H 2 S and SO 2 ) from the main stream through dissolution and chemical reaction, and a regenerator, where the operating conditions are opposite to the absorber, separating the acidic compound from the absorbent, making it available for its reincorporation to the absorption process. Numerous absorbents have been proposed to be used in this process, the majority being amine-based compounds: monoethanolamine (MEA), triethanolamine (TEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA) and diglycolamine (DGA) were the first compounds used in aqueous solution to selectively separate acid gases in process streams. These compounds had to be diluted in aqueous solution because they generate important corrosion problems. From the 1950s, various chemical companies such as DOW, BASF or UOP developed proprietary proprietary formulations of absorbent mixtures that included, in addition to the common absorbents, corrosion inhibitors, defoamers, buffers and promoters, which They boosted the operative capacities of these units thanks to a significant increase in the concentrations of absorbent in the aqueous solution. The main problems associated with the use of chemical absorbents for the separation of CO 2 consist of the high energy consumption associated with the regeneration of the absorbent, the emissions of absorbent and derivatives, due to its high volatility and / or drag of the gas phase, and in the degradation suffered by the same due to oxidative and thermal mechanisms that occurs during the process of CO2 absorption and regeneration of the absorbent.
    [0011]
    [0012] The application of CO 2 chemical absorption processes to separate it from combustion gases from the combustion of fossil fuels and / or industrial processes requires the development of absorbent mixtures specifically formulated to operate in these operating conditions. These absorbent mixtures aim to optimize the performance of traditional absorbers in terms of load capacity (mol of CO2 per mole of absorbent), resistance to degradation, low volatility, fast kinetics and low enthalpy of CO 2 solubility and can operate optimized for each case.
    [0013]
    [0014] The application of chemical absorption in processes of capture of CO 2 has led to new formulations of absorbers based on mixtures of primary / secondary amines with tertiary amines or salts such as potassium carbonate, so that they have an intermediate functionality between their components, as well as the use of sterically hindered amines that facilitate the release of the absorbed CO2 through the formation of bonds weakened by the presence of large functional groups in the vicinity of the amino groups. The use of amines with steric hindrance was initially proposed by Sartori et. to the. (US4112050A). There are numerous patents that are based on 2-amino-2-methyl-1-propanol, 2-methylaminoethanol, 2-ethylaminoethanol and 2-piperidine ethanol as hindered amine (US6036931A). Other innovative absorbers are the so-called ionic liquids, the salts of amino acids with high melting points, high viscosity and low kinetics, still under study at laboratory scale (Galán Sánchez, LM, G Meindersma, A Dehaan, 2007, Chemical Engineering Research and Design 85: 31-39).
    [0015]
    [0016] The use of mixtures of piperazine (PZ) and derivatives with different types of absorbers with low absorption kinetics has also been proposed. The use of PZ as an absorbent (CA2651265A1) has been proposed mainly as a promoter of mixtures of slow kinetic absorbents such as piperazine and monodiethanolamine (MDEA) (US2009 / 0211446A1), piperazine and potassium carbonate (US4581209A), piperazine and alcohols (US8388855B2). All of them showed excellent results compared to MEA 30% p / p, solving in turn the problems associated with solubility problems piperazine in aqueous solution.
    [0017]
    [0018] On the other hand, numerous configurations of the basic process have been developed over the last few years in order to optimize the overall CO 2 separation process and, in particular, to significantly reduce the energy consumption associated mainly with the regeneration of the absorbent. Different variants have been proposed on the traditional arrangement of the absorber, (US8192530B2) and modifications on the regenerator, such as, for example, energy use of the sensible heat of the regenerator output current (US4798910A), preheating of the condensates at the regenerator inlet (W02007 / 107004A1), partial evaporation of the poor amine at the exit of the regenerator so that the total energy contribution to the reboiler of the regeneration unit is minimized (W02008 / 063079A2), pressurization of the upper section of the regenerator to decrease the ratio water / C02 in the stripping current of the regeneration unit (W02008 / 063082A2). Many of them have led to significant energy reductions in the regeneration of the absorbent compared to the traditional arrangement.
    [0019]
    [0020] The appearance of new configurations of the separation process of C02 and / or acid gases requires the use of specifically designed absorbents that allow a wide range of operation and a maximization of the performance of each of the new technologies. In this way, significant reductions in energy consumption of the global CO2 capture process.
    [0021]
    [0022] Therefore, it would be desirable to have an absorbent system capable of separating CO2 and / or acid gases from a gas stream that minimizes the energy requirements of the absorbent regeneration process.
    [0023]
    [0024] DESCRIPTION OF THE INVENTION
    [0025]
    [0026] In a first aspect, the present invention relates to an aqueous composition absorbing CO 2 and / or acid gases comprising:
    [0027] i. a cyclic structure diamine of formula (I):
    [0028]
    [0029]
    [0030]
    [0031] where:
    [0032] R1 is a C1-4 alkyl group substituted by a -NH2 group; Y
    [0033] R 2 is H or a C 1-4 alkyl group optionally substituted by an -NH 2 group; ii. an amine of formula (II):
    [0034]
    [0035]
    [0036]
    [0037] where:
    [0038] n represents 0 to 10;
    [0039]
    [0040] iii. a primary amine of linear or branched structure, a secondary amine of linear, branched or cyclic structure; or a cyclic amine of formula (III):
    [0041]
    [0042] where:
    [0043] X represents H, -NR3 or -CR4R5; Y
    [0044] each R3, R4 and R5 independently represent H or C1-4alkyl; Y
    [0045]
    [0046] iv. Water.
    [0047]
    [0048] Component (i) of the defined composition acts as a support for CO 2 loading capacity.
    [0049]
    [0050] The component (ii) of the defined composition that reduces the overall CO2 absorption heat of the system and, therefore, decreases the heat necessary for the regeneration of the absorbent.
    [0051]
    [0052] Component (iii) of the defined composition is a promoter that increases the kinetics of the CO2 absorption process.
    [0053]
    [0054] In another embodiment the invention relates to the composition defined above wherein R2 is H or a C1-4 alkyl group, and preferably wherein R2 is H.
    [0055]
    [0056] In another embodiment the invention relates to the composition defined above, wherein (i) is 1- (2-aminoethyl) -piperazine.
    [0057]
    [0058] In another embodiment the invention relates to the composition defined above, wherein (ii) is methyldiethanolamine.
    [0059]
    [0060] In another embodiment the invention relates to the composition defined above, wherein (iii) is a cyclic amine of formula (III).
    [0061]
    [0062] In another embodiment the invention relates to the composition defined above, wherein (iii) is a cyclic amine of formula (III) wherein:
    [0063] X represents -NR3 or -CR4R5; Y
    [0064] each R3, R4 and R5 independently represent H or C1-4alkyl.
    [0065]
    [0066] In another embodiment the invention relates to the composition defined above, wherein (iii) is a cyclic amine of formula (III) wherein:
    [0067] X represents -NR3; Y
    [0068] R3 represents H or C1-4alkyl.
    [0069]
    [0070] In another embodiment the invention relates to the composition defined above, wherein (iii) is a cyclic amine of formula (III) wherein:
    [0071] X represents -CR4R5; Y
    [0072] each R 4 and R 5 independently represent H or C 1-4 alkyl.
    [0073]
    [0074] In another embodiment the invention relates to the composition defined above, wherein (iii) is a cyclic amine of formula (III) wherein:
    [0075] X represents H; Y
    [0076] each R3, R4 and R5 independently represent H or C1-4alkyl.
    [0077]
    [0078] In another embodiment the invention relates to the composition defined above, wherein (iii) is piperidine or monomethylamine.
    [0079]
    [0080] In another embodiment, the invention relates to the composition defined above, wherein:
    [0081] (i) is a compound of formula (I), and preferably 1- (2-aminoethyl) -piperazine; (ii) is an amine of formula (II), and preferably methyldiethanolamine; Y
    [0082] (iii) is a primary amine of linear or branched structure, a secondary amine of linear, branched or cyclic structure or a cyclic amine of formula (III), and preferably piperidine or monomethylamine.
    [0083]
    [0084] In another embodiment the invention relates to the composition defined above, wherein (i) it is at a concentration of at least 5% w / w in solution, preferably in a concentration of between 10% w / w and 50% p / p in solution, and more preferably in a concentration of 25% w / w in solution.
    [0085]
    [0086] In another embodiment the invention relates to the composition defined above, where (ii) is at a concentration of at least 1% w / w in solution, preferably in a concentration of between 3% w / w and 30% w / w in solution, and more preferably in a concentration of 5% w / w in solution. % p / p in solution.
    [0087]
    [0088] In another embodiment the invention relates to the composition defined above, wherein (iii) is at a concentration of at least 0.01% w / w in solution, preferably at a concentration of between 1% w / w and 15%. % w / w in solution, and more preferably in a concentration of 5% w / w in solution.
    [0089]
    [0090] In another embodiment, the invention relates to the composition defined above, wherein:
    [0091] (i) is a compound of formula (I), and preferably 1- (2-aminoethyl) -piperazine, wherein (i) is at a concentration of at least 5% w / w in solution, preferably at a concentration of between 10% w / w and 50% w / w in solution, and more preferably at a concentration of 25% w / w in solution;
    [0092] (ii) is a compound of formula (II), and preferably methyldiethanolamine, where (ii) is at a concentration of at least 1% w / w in solution, preferably at a concentration of between 3% w / w and 30% w / w in solution, and more preferably in a concentration of 5% w / w in solution; and (iii) is a primary amine of linear or branched structure, a secondary amine of linear, branched or cyclic structure or a cyclic amine of formula (III), and preferably monomethylamine or piperidine, where (iii) is in a concentration of at least 0.01% w / w in solution, preferably in a concentration of between 1% w / w and 15% w / w in solution, and more preferably in a concentration of 5% w / w in solution.
    [0093]
    [0094] In another embodiment the invention relates to the composition defined above, which further comprises one or more adjuvants, anti-foaming agents, corrosion inhibitors, inhibitors of oxidative degradation and mixtures thereof.
    [0095]
    [0096] The amount present in the composition of the invention of the adjuvants, anti-foaming agents, corrosion inhibitors and inhibitors of oxidative degradation will be suitable for a person skilled in the art for a correct functionality and operability of the absorbent in a separation process of CO2 and / or acid gases by chemical absorption based on an optimized adjustment of the cyclic working capacity of the absorbent and an optimized control of the operating conditions of the regenerator inlet currents, mainly in terms of temperature and distribution of feed flows to the equipment.
    [0097]
    [0098] Examples of these additives may be selected, without being limited to arsenious anhydride, selenium or tellurium acids, protides, amino acids, such as glycine, vanadium oxides or chromates, among others. All these additives can be found in the composition in amounts suitable for a correct functionality and operability of the absorbent in a process of separation of CO2 by the chemical absorption described in the present invention, amounts known to a person skilled in the art.
    [0099]
    [0100] Another aspect of the invention relates to the use of the composition defined above for the absorption of acid gases, and preferably where the acid gases comprise CO 2 .
    [0101]
    [0102] Another aspect of the invention relates to the use of the composition defined above for the absorption of acid gases by a system of separation of CO 2 by chemical absorption based on an optimized adjustment of the cyclic working capacity of the absorbent and an optimized control of the operating conditions of the inlet streams to the regenerator, mainly in terms of temperature and distribution of feed flows to the equipment, and preferably where the acid gases comprise CO 2 .
    [0103]
    [0104] Throughout the invention, the term "primary amine" refers to a compound comprising the -NH3 group where one of the hydrogen atoms of the group is substituted by another group, such as, for example, C1-4 alkyl (primary alkanolamine) The primary amines of the invention may be linear or branched Examples include, among others, monoethanolamine, methylamine, ethylamine, 2-methylpropylamine, propylamine and butylamine.
    [0105]
    [0106] "Secondary amine" refers to a compound comprising the group -NH3 where two of the hydrogen atoms in the group are substituted by another group, such as, for example, C1-4 alkyl (secondary alkanolamine) The secondary amines of the invention may be linear, branched or cyclical Examples include, among others diethanolamine, dimethylamine, diglyclamine, diethylamine, methylethylamine, 1-butyl-1- (2-methylpropyl) amine, piperidine, piperazine and 1- (2-aminoethyl) piperazine.
    [0107]
    [0108] "Tertiary amine" refers to a compound comprising the group -NH3 where the three hydrogen atoms of the group are substituted by another group, such as, for example, C1-4 alkyl (tertiary alkanolamine) The tertiary amines of the invention may be linear, branched or cyclic Examples include triethanolamine, methyldiethanolamine
    [0109]
    [0110] "Polyamine" refers to a compound that contains 2 or more -NH3 groups where one of the hydrogen atoms of the group is substituted by another group, such as, for example, C 1-4 alkyl The polyamines of this invention may be linear , branched or cyclic Examples include isophoronediamine and tetramethylethylenediamine.
    [0111]
    [0112] "Alkaline salt", define and incorporate as an example potassium carbonate, calcium carbonate, sodium carbonate.
    [0113]
    [0114] "C1-4 alkyl" means as a group or part of a group, means a straight or branched chain alkyl group containing from 1 to 4 carbon atoms and includes the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec groups -butyl and tert-butyl.
    [0115]
    [0116] By "acid gas" we refer in the present invention to any of the following: CO2, H2S and SO2, or their mixtures, preferably the acid gas to be separated in the process of the present invention is CO2.
    [0117]
    [0118] The application of this CO2 capture procedure can be for gases or gaseous streams coming from stationary sources of combustion, such as electricity production systems, cement plants, oil refineries or iron and steel, and can also be extended to a gas stream from any industrial process where the separation of CO2 and / or acid gases is required, such as the production of synthesis gas. The process of separating CO 2 in a gas stream under these conditions is highly favored when CO2 has a high concentration of CO2.
    [0119]
    [0120] Thus, the present invention provides a new absorbent composition formulated to capture CO2 and / or an acid gas from a gaseous stream by chemical regenerative absorption, and in particular by regenerative chemical absorption operated in an alternative configuration to the traditional system of separation of CO 2 from a gas stream by chemical absorption, based in the optimization of the cyclic capacity of operation of the absorbent used by a particular disposition of the currents involved in the process of absorption-desorption of CO2 and a very exhaustive control of the operation conditions of the input currents to the regenerator, mainly in terms of temperature and distribution of flow rates to the equipment. This method of separating CO 2 and / or acid gases based on the regenerative chemical absorption is described in the Spanish patent application P201600519 "Procedure and CO2 separation system based on chemical absorption" (see example 1 and FIGs 1 to 3) , which may comprise the following stages:
    [0121]
    [0122] a) absorption of CO 2 from a gaseous stream to be treated at a temperature preferably lower than 60 ° C and a pressure comprised in a range of between 1 and 1.5 bar, by contacting an absorber of said stream with an absorbent solution to which CO2 is to be retained;
    [0123]
    [0124] b) recirculation of up to 75% of the stream comprising the CO2-rich absorbent solution from stage a) to the lower bed of the absorption system. The operation under these conditions allows to optimally adjust the range of cyclic working capacity of the absorbent during the operation;
    [0125]
    [0126] c) desorption of the CO 2 in a regenerator of the stream comprising the absorbent solution rich in CO2 from stage a) not recirculated to stage b) at a temperature of between 80 ° C and 120 ° C, a pressure of between 1.5 and 5 bar and a steam flow rate of between 10 and 90% by volume with respect to the flow of CO 2 desorbed, where said stream is divided into at least two streams by means of a train of heat exchangers, prior to the regenerator input;
    [0127]
    [0128] d) recovery of the absorbent solution resulting from step c) to the absorber of stage a).
    [0129]
    [0130] From this basic configuration, the procedure first proposes the incorporation of a recirculation line directed to the absorber that constitutes a derivation of the exit of the absorbent solution rich in CO2, which is partially recycled to the absorber in order to optimize the CO2 absorption capacity of the absorber used. Secondly, the procedure incorporates a particular train of heat exchangers that, apart from thermally conditioning the CO2-rich solution, divides it into at least two streams that are introduced into the regenerator in zones located at different heights, stratifying the feed to the regenerator. which causes a decrease in the regenerator's temperature profile.
    [0131]
    [0132] This chemical absorption process allows an efficient operation of the regenerator at a thermal level lower than those proposed in traditional operating modes and, therefore, significantly reduces the specific consumption associated with the regeneration of the absorbent. With this, it is possible to work with a greater load or concentration of CO 2 in the regenerated absorbent and, in this way, displace the cyclic capacity of operation of the same towards areas where the energy consumption associated with the desorption of CO 2 is lower. Likewise, the decrease obtained in the regenerator's temperature profile reduces the degradation speed of the absorbent associated with thermal mechanisms.
    [0133]
    [0134] The purpose of the mixture of absorbents is to optimize the performance of this configuration due to a greater load capacity thereof, so that a better adjustment of the operating conditions is possible and, therefore, a lower flow rate of absorbent solution is required. lower energy consumption in the overall capture process.
    [0135]
    [0136] The absorbent composition of the present invention is characterized by a high load capacity and operating flexibility that maximizes the performance of the absorption-desorption process with a significant reduction in energy consumption compared to the same operation of the CO 2 capture unit using 30% w / w monoethanolamine as an absorbent (MEA 30% w / w, reference absorber).
    [0137]
    [0138] The process of separating acid gases, in particular CO2, by chemical absorption is based on an optimization of the cyclic load capacity in absorbent operation, understood as the difference between the CO2 load of the rich absorbent composition at the exit of the absorber and the poor absorbent composition at the regenerator outlet, so as to minimize the energy requirements in the reboiler associated with the process of regeneration of the absorbent.
    [0139]
    [0140] The displacement of the cyclic load capacity of CO 2 in operation of the absorber allows an operation in a region of lower enthalpy of CO 2 solubility, therefore, a reduction of the energy consumption in the regenerator is obtained in comparison with a conventional operation . The optimization of the cyclic load capacity is carried out by adjusting the degree of regeneration required by the absorbent. This adjustment is achieved by introducing the current of CO 2 -rich absorbent composition obtained at the outlet of the absorber at different heights of the regenerator and / or by adjusting the temperature of the CO2-rich absorbent composition streams to the regenerator inlet.
    [0141]
    [0142] This configuration of the process of regenerative absorption of CO 2 concludes with the re-introduction of the CO2-poor current at the regenerator outlet in the absorber, to once again produce the absorption of CO2 and / or acid gases, these being retained within the absorbent. To produce an increase in the CO2 load of the absorber during the absorption process, part of the CO 2 charged stream at the absorber outlet is partially recirculated after previous cooling. This results in an increase in the overall CO 2 load of the absorber at the outlet of the absorber. The operation under these conditions allows to optimally adjust the range of cyclic working capacity of the absorbent during the operation. In this way, this method has made it possible to significantly reduce the specific consumption associated with the regeneration of the absorbent compared to a conventional configuration of the absorption system.
    [0143]
    [0144] Therefore another aspect of the present invention relates to a process for separating acid gases from a gas stream based on chemical absorption, comprising the following steps:
    [0145] a) absorption of acid gases from the gaseous stream to be treated at a temperature of between 40 ° C and 60 ° C and a pressure in a range of between 1 and 1.5 bar, by putting it in contact with an absorber of said gas current with a absorbent solution in which the acid gases are to be retained, where the absorbent solution is an absorbent composition of the present invention; b) recirculation to the absorber of up to 75% of the stream comprising the absorbent solution rich in acid gas from step (a);
    [0146] c) desorption of the acid gas in a regenerator of the stream comprising the absorbent solution rich in acid gas, preferably CO2, coming from step (a) not recirculated to stage (b) at a temperature of between 80 ° C and 120 ° C, a pressure of between 1.5 and 5 bar and a steam carry-over flow of between 10 and 90% by volume with respect to the flow rate of desorbed acid gas, where said stream is divided into at least two streams by a train of heat exchangers, prior to the entrance of the regenerator; Y
    [0147] d) recovering the absorbent solution resulting from step (c) to the absorber of step (a).
    [0148]
    [0149] In a preferred embodiment of the process of the invention, the acid gas of the gas stream to be treated in step (a) is transferred to the liquid phase where it dissolves and chemically bonds to the absorbent.
    [0150]
    [0151] In a preferred embodiment of the process of the invention, the recirculated flow of stage (b) reaches between 25% and 75% of the total solution rich in acid gas from stage (a).
    [0152]
    [0153] In a preferred embodiment of the method of the invention, the recirculation of the stream from stage (b) takes place in the lower bed of the absorber of stage (a).
    [0154]
    [0155] In a preferred embodiment of the method of the invention, the streams from step (c) are introduced into zones located at different heights of the regenerator of step (d).
    [0156]
    [0157] In a preferred embodiment of the method of the invention, prior to step (c) a train of heat exchangers is incorporated, through which the stream comprising the absorbent solution rich in acid gas, preferably CO 2 , from the stage is introduced. (a) not recirculated to stage (b). This train of exchangers apart from thermally conditioning the absorbent solution rich in CO2 divides it into less two streams that are introduced in the regenerator in zones located at different heights, stratifying the feed to the regenerator, which causes a decrease in the regenerator's temperature profile.
    [0158]
    [0159] The absorbent composition of the present invention is suitable for this process of separating CO2 and / or acid gases from a gas stream. The improvement of the performance of the process from the use of the absorbent composition described in this invention is based on the following characteristics, which have been corroborated in the examples:
    [0160] a) High load capacity of CO 2 , expressed as moles of CO 2 per mole of absorbent in aqueous solution: This characteristic infers a better adaptation to the operating conditions imposed by the described procedure.
    [0161] b) High kinetic ratios of CO2 absorption, expressed as mass flow of CO 2 per unit of time, which leads to a reduction in the flow rate of absorber required to reach a given CO 2 separation yield and, therefore, to a decrease in investment, due to reduction in the size of equipment and lines of the CO2 separation unit.
    [0162] c) Both characteristics described above entail a lower requirement of the L / G ratio in operation to achieve a given CO 2 separation performance. This implies a lower circulation of liquid absorbent solution and, therefore, a lower consumption in the absorption of the absorbent.
    [0163] d) The use of the absorbent composition described in this invention in the method of the invention makes it possible to significantly reduce the energy consumption associated with the regeneration of the absorbent.
    [0164]
    [0165] Throughout the description and the claims the word "comprises" and its variants do not intend to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will emerge partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0166]
    [0167] BRIEF DESCRIPTION OF THE FIGURES
    [0168] FIG. 1. Evolution of the CO2 absorption ratios obtained in laboratory tests
    [0169] The CO2 absorption rate is plotted as a function of the experimental time after the execution of each test, expressed as mL of CO2 absorbed per minute (mL CO2 / min). The tests carried out with the new absorbent system are represented, using 60% v / v CO2 (yellow) and 15% v / v CO2 (blue) in the gas phase. In the case of MEA, the absorption ratios obtained for 60% v / v CO2 (red) and 15% v / v CO2 (green) in the gas phase have been represented.
    [0170]
    [0171] FIG. 2. CO2 capture performance obtained for each L / G ratio using the new absorbent system (■) and the reference absorber (A)
    [0172] The CO 2 capture performance is represented, defined as the difference in mass flow of CO2 in the gas phase between the outlet and the inlet of the CO2 absorption unit. The percentage yield of capture is expressed based on the mass flow of CO2 at the entrance of the absorption unit. This parameter has been represented according to the L / G ratio of each test, expressed as mass flow rate of absorber in liquid phase (kg / h) versus mass flow of gas to be treated (kg / h). The tests performed using the new absorbent system are represented by (■), while the tests performed using MEA are represented by (A).
    [0173]
    [0174] FIG. 3. Specific consumption of the regeneration of the absorbent obtained for each L / G ratio using the new system to bsorbent (■) and the abs orbent of reference (A)
    [0175] The specific consumption associated with the regeneration of the absorber is represented, expressed in energy units per unit mass of CO2 (GJ / t CO2). This parameter has been represented according to the L / G ratio of each test, expressed as mass flow rate of absorber in liquid phase (kg / h) versus mass flow of gas to be treated (kg / h). The tests performed using the new absorbent system are represented by (■), while the tests performed using MEA are represented by (A).
    [0176]
    [0177] EXAMPLES
    [0178]
    [0179] The invention will now be illustrated by means of tests carried out by the inventors, which highlights the effectiveness of the product of the invention.
    [0180]
    [0181] Example 1:
    [0182] Different tests have been carried out in a laboratory assembly operating in a semi-continuous regime to produce the saturation of a known amount of absorbent solution. To this end, 250 mL of absorbent solution has been placed in a reactor where 2 L / min of a gas stream of known composition to saturation has been introduced. The test temperature has been set at 50 ° C. Once the test is finished, the load of the absorbent in equilibrium, expressed in moles of CO 2 per mole of absorbent, has been determined using an inorganic carbon analyzer. Table 1 shows the results obtained for the tests carried out using the absorbent system described in this invention and its comparison with the reference absorber (aqueous solution of MEA at 30% w / w).
    [0183]
    [0184] Table 1. Summary of absorber load in equilibrium at different concentrations of CO 2 in gas phase
    [0185]
    [0186]
    [0187]
    [0188]
    [0189] The new absorbent system allows up to 70% more CO2 loading capacity compared to the reference absorber. In this way, the new absorbent system presents a greater flexibility of operation and adaptation to the new CO 2 separation system based on an optimized adjustment of the cyclic working capacity of the absorbent and an optimized control of the operating conditions of the waste streams. entrance to the regenerator.
    [0190]
    [0191] Example 2:
    [0192]
    [0193] From the tests described in example 1, it was possible to determine the absorption ratios measured in gas phase for each of the tests carried out. Figure 1 summarizes the results obtained in these trials, representing the evolution of the CO2 absorption ratios obtained in laboratory tests.
    [0194]
    [0195] The absorption ratios increase significantly with an increase in the concentration of CO2 in the gas phase. In addition, the new absorbent system has higher CO2 absorption ratios than those obtained with the reference absorber (aqueous solution of MEA at 30% w / w) for the same concentration of CO2 in the gas phase, demonstrating a better kinetic behavior in operation according to the new CO2 separation system based on an optimized adjustment of the cyclic working capacity of the absorbent and an optimized control of the operating conditions of the regenerator inlet currents.
    [0196]
    [0197] Example 3:
    [0198]
    [0199] A process for separating CO2 from a synthetic gas stream in a laboratory-scale unit has been carried out based on an operation according to the new CO 2 separation system based on an optimized adjustment of the cyclical working capacity of the absorber and an optimized control of the operating conditions of the inlet streams to the regenerator, using the new absorbent system proposed in this invention and MEA 30% p / p as a reference absorber. In the exemplary embodiment, a synthetic gas flow rate of 7 L / min was used, with a composition of 60% v / v CO2, saturated in water and balanced with N2. The total amount of absorber used in the system was 2 L. The absorption of CO 2 was carried out at 1 atm and 50 ° C in a column of 3 cm in diameter and 2 m in height using 6 mm Raschig ceramic rings.
    [0200]
    [0201] The regeneration of the absorbent took place at a pressure of 2 bar in a column of 3 cm in diameter and 1 m in height using a Raschig ring filling of 316L stainless steel of 6 mm. The average operating temperature in the regeneration unit was 118 ° C for the MEA tests 30% p / p and 117 ° C for the tests of the proposed new absorbent system, operating according to the new CO 2 separation system. The L / G ratio has been varied for each absorber until reaching a capture efficiency of 100%. Figure 2 shows the CO2 capture yields obtained according to the L / G ratio used in each test.
    [0202]
    [0203] The tests carried out demonstrate the greater absorption capacity and flexibility of operation of the new absorbent system operating according to the new CO2 separation system with respect to the reference absorber. The L / G ratios obtained are lower than those required by the reference absorber for a defined CO2 capture performance. In particular, the new absorbent system requires an L / G ratio of 8 while MEA 30% p / p requires an L / G ratio of 13 in the case of obtaining a CO2 capture efficiency of 90%.
    [0204]
    [0205] Example 4:
    [0206]
    [0207] From the tests described in the previous example, the specific consumptions associated with the regeneration of the absorbent have been obtained for each test carried out, modifying the L / G ratio. Figure 3 represents the evolution of this parameter for each test carried out, using the two absorbers indicated above.
    [0208]
    [0209] As shown by the results indicated in Figure 3 and Table 2 (summary), the new absorbent system provides a lower energy consumption of the regeneration of the absorbent in an operation according to the new CO2 separation system. The new absorbent system manages to reduce energy consumption up to 22% compared to the reference absorber.
    [0210]
    [0211] Table 2. Summary of energy consumption and capture yields associated to it obtained in an operation according to the new CO 2 separation system:
    [0212]
    [0213]
    权利要求:
    Claims (19)
    [1]
    1. Aqueous absorbent composition of CO2 and / or acid gases comprising:
    i. a cyclic structure diamine of formula (I):

    [2]
    2. The composition according to claim 1, wherein the component (i) is a diamine of cyclic structure of formula (I) wherein R2 is H or a C1-4 alkyl group.
    [3]
    3. The composition according to any of claims 1 or 2, wherein (i) is 1- (2-aminoethyl) -piperazine.
    [4]
    4. The composition according to claim 3, wherein (ii) is methyldiethanolamine.
    [5]
    The composition according to any of claims 1 to 4, wherein (iii) is monomethylamine.
    [6]
    6. The composition according to any of claims 1 to 4, wherein (iii) is a compound of formula (III).
    [7]
    The composition according to claim 6, wherein (iii) is piperidine
    [8]
    The composition according to any of claims 1 to 7, wherein (i) is in a concentration of at least 5% w / w in solution.
    [9]
    9. The composition according to claim 8, wherein (i) is in a concentration of between 10% w / w and 50% w / w in solution.
    [10]
    The composition according to any of claims 8 or 9, wherein (i) is in a concentration of 25% w / w in solution.
    [11]
    11. The composition according to any of claims 1 to 10, wherein (ii) is in a concentration of at least 1% w / w in solution.
    [12]
    12. The composition according to claim 11, wherein (ii) is in a concentration of between 3% w / w and 30% w / w in solution.
    [13]
    The composition according to any of claims 11 or 12, wherein (ii) is in a concentration of 5% w / w in solution.
    [14]
    The composition according to any of claims 1 to 13, wherein (iii) is in a concentration of at least 0.01% w / w in solution.
    [15]
    15. The composition according to claim 14, wherein (iii) is in a concentration of between 1% w / w and 15% w / w in solution.
    [16]
    16. The composition according to any of claims 14 or 15, wherein (iii) is in a concentration of 5% w / w in solution.
    [17]
    17. The composition according to any of claims 1 to 16, further comprising one or more adjuvants, anti-foaming agents, corrosion inhibitors, inhibitors of oxidative degradation and mixtures thereof.
    [18]
    18. Use of the composition according to any of claims 1 to 17, for the absorption of acid gases by a system of CO2 separation by chemical absorption based on an optimized adjustment of the cyclic working capacity of the absorbent and an optimized control of the operating conditions of the inlet currents to the regenerator, mainly in terms of temperature and distribution of feed flows to the equipment.
    [19]
    19. The use according to claim 18, wherein the acid gases comprise CO2.
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    同族专利:
    公开号 | 公开日
    EP3656459A1|2020-05-27|
    WO2019016418A1|2019-01-24|
    ES2697300B2|2019-05-24|
    EP3656459A4|2021-04-21|
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    ES201730955A|ES2697300B2|2017-07-21|2017-07-21|AQUEOUS COMPOSITION FOR THE SEPARATION OF CO2 AND / OR ACID GASES|ES201730955A| ES2697300B2|2017-07-21|2017-07-21|AQUEOUS COMPOSITION FOR THE SEPARATION OF CO2 AND / OR ACID GASES|
    EP18835901.2A| EP3656459A4|2017-07-21|2018-07-20|Aqueous composition for the separation of co2 and/or acid gases|
    PCT/ES2018/000061| WO2019016418A1|2017-07-21|2018-07-20|Aqueous composition for the separation of co2 and/or acid gases|
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