• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Aqueous absorbent composition. The invention relates to an absorbent composition for capturing CO2or 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:ES2673740A1
    申请号:ES201601110
    申请日:2016-12-23
    公开日:2018-06-25
    发明作者:Fernando VEGA BORRERO；Benito Navarrete Rubia；José Antonio CAMINO FERNÁNDEZ；Mercedes CANO PALACIO；Vicente Jesús CORTÉS GALEANO；Sara CAMINO PEÑUELA；Jaime GARRIDO LÓPEZ
    申请人:Universidad de Sevilla；
    IPC主号:
    专利说明:

    The present invention relates to an aqueous absorbent composition and its use in a process of separating CO2 from a gas stream by regenerative chemical absorption. based on the optimization of the cyclic capacity of the absorbent. Therefore, the present invention is framed in the area of environmental technology and chemical processes. In particular, it is included in the sector of CO2 capture from stationary emission sources in industrial combustion facilities, but it is applicable to other industrial processes where a separation of CO2 and / or acid gases from any compound process stream is required by a mixture of gases. STATE OF THE TECHNIQUE
    The process of separation of acid gases from a gas stream by regenerative chemical absorption has been used since the 30s of the last century in numerous industrial processes, such as the treatment of synthesis gas. In recent years, these processes have aroused great interest at the industrial level thanks to the possibility of being used within CO2 capture and storage technologies (W01995 / 021683 A1).
    The general scheme of the CO2 separation process by chemical absorption was patented by R. R. Bottoms (U81783901A). Said invention describes a system composed of an absorber, in which the gases to be treated are contacted, in countercurrent, with an absorbent solution that separates the acid gases (C02, H2S and 802) from the main stream by dissolution and chemical reaction. , and a regenerator, where the operating conditions are opposed to the absorber, the acidic compound being separated from the absorbent, this being available for reincorporation into the absorption process. Numerous absorbents have been proposed to be used in this process, the majority being amino-based compounds: monoethanolamine (MEA), triethanolamine (TEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA) and diglylamine (DGA) were the first compounds used in aqueous solution to separate acid gases selectively in process streams. These compounds had to be diluted in aqueous solution because they generate important corrosion problems. From the 50s, various chemical companies such as DOW, BASF or UOP developed proprietary formulations in industrial property of absorbent mixtures which included, in addition to common absorbents, corrosion inhibitors, defoamers, buffers and promoters, which boosted the operational capacities of these units thanks to a significant increase in absorbent concentrations in the aqueous solution. The main problems associated with the use of chemical absorbents for CO2 separation are 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 that it suffers due to oxidative and thermal mechanisms that occurs during the process of CO2 absorption and regeneration of the absorbent.
    The application of CO2 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 are intended to optimize the performance of traditional absorbents in terms of load capacity (mol of CO2 per mol of absorbent), degradation resistance, low volatility, rapid kinetics and low enthalpy of CO2 solubility and can operate optimized For each case.
    The application of chemical absorption in CO2 capture processes has resulted in new absorbent formulations 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 such as the use of sterically hindered amino acids that facilitate the release of absorbed CO2 by the formation of weakened bonds 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 based on 2-amino-2-methyl-1-propanol, 2-methylaminoethanol, 2-ethylaminoethanol and 2-piperidine ethanol as hindered amine (US6036931A). Other innovative absorbents are the so-called ionic liquids, the amino acid salts with high melting points, high viscosity and low kinetics, still being studied on a laboratory scale (Galán Sánchez, LM, G Meindersma, A Dehaan. 2007, Chemical Engineering Research and Design 85: 31-39).
    The use of piperazine mixtures (PZ) and derivatives with different types of low absorption kinetics absorbents has also been proposed. The use of PZ as an absorbent (CA2651265A1) has been proposed primarily as a promoter of slow kinetic absorbent mixtures 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% w / w, while solving the problems associated with problems of solubility piperacin in aqueous solution.
    On the other hand, numerous configurations of the basic process have been developed over the last years with the aim of optimizing the overall CO2 separation process and, in particular, significantly reducing the energy consumption mainly associated 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 outlet of the regenerator so that the total energy supply 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.
    The appearance of new configurations of the process of separation of CO2 and / or acid gases requires the use of specifically designed absorbents that allowIn this way, significant reductions of 2 can be obtained. DESCRIPTION OF THE INVENTION
    The present invention provides a new absorbent composition formulated to capture CO2 and / or an acid gas from a gaseous stream by regenerative chemical absorption, and in particular by regenerative chemical absorption operated in an alternative configuration to the traditional CO2 separation system of a stream of gases by chemical absorption, based on the optimization of the cyclic capacity of operation of the absorbent used through a particular arrangement of the currents involved in the process of absorption-desorption of CO2 and a very exhaustive control of the operating conditions of the currents of input to the regenerator, mainly in terms of temperature and distribution of feed flows to the equipment. This procedure is protected by the Spanish patent application P201600519 (see example 1 and FIGs 1 to 3), which can comprise the following steps:
    a) absorption of CO2 from a gaseous stream to be treated at a temperature preferably below 60 ° C and a pressure in the range of 1 to 1.5 bar, by contacting an absorber of said stream with a absorbent solution to which the CO2 is to be retained;
    b) recirculation of up to 75% of the current comprising the CO2-rich absorbent solution from stage a) to the lower bed of the absorption system. The operation under these conditions allows optimally adjusting the range of cyclic working capacity of the absorbent during the operation;
    c) desorption of the CO2 in a current regenerator comprising the absorbent solution rich in CO2 from stage a) not recirculated to stage b) at a temperature between 80 ° C and 120 ° C, a pressure between 1 , 5 AND 5 bar and a steam flow rate of between 10 and 90% by volume with respect to the desorbed CO2 flow, where said current is divided into at least two streams by a heat exchanger train, prior to the entrance of the regenerator;
    d) recovery of the absorbent solution resulting from stage c) to the absorber of stage a).
    In a preferred embodiment, the CO2 is absorbed from the stream to be treated in step a) of the process of the invention in the absorber unit from the gas phase to the liquid phase, where it is dissolved and chemically bonded with the absorbent
    or absorbent solution. Absorbents that operate only with physical, and non-chemical, absorption mechanisms can also be used.
    From this basic configuration, the procedure first proposes the incorporation of a recirculation line aimed at the absorber that constitutes a derivation of the output of the absorbent solution rich in CO2, which is partially redirected to the absorber in order to optimize the capacity of CO2 absorption of the absorbent 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 areas located at different heights, stratifying the feed to the regenerator, which causes a decrease in the temperature profile of the regenerator.
    This chemical absorption process allows an efficient operation of the regenerator at a lower thermal level than those proposed in traditional modes of operation 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 CO2 in the regenerated absorbent and, in this way, move the cyclic capacity of operation to areas where the energy consumption associated with CO2 desorption is lower. Likewise, the decrease obtained in the temperature profile of the regenerator reduces the degradation rate of the absorbent associated with thermal mechanisms.
    The mixture of absorbents aims 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 of absorbent solution is required and lower energy consumption in the global capture process.
    The absorbent composition of the present invention is characterized by a high loading capacity and flexibility of operation that maximizes the performance of the absorption-desorption process with a significant reduction in energy consumption compared to the same operation of the CO2 capture unit using monoethanolamine 30% w / w as absorbent (reference absorbent).
    Therefore, a first aspect of the present invention relates to an aqueous acid gas absorbent composition comprising:
    i. a saturated heterocyclic amine, which acts as a promoter or as an absorber of high kinetics and with a high loading capacity;
    ii. an amine with steric hindrance, which reduces the heat of absorption of the overall acid gases of the system;
    10 iii. an organic diamine, which adjusts the kinetics and loading capacity of the absorbent composition, and
    iv. Water.
    By "saturated heterocyclic amine" is meant that organic compound that
    15 comprises at least one heterocyclic ring consisting of 3 to 10 carbon atoms, which is saturated or partially saturated, and which contains at least one N atom forming part of the ring. These amino compounds are amines without steric hindrance. Preferably the heterocyclic amine is saturated. In a preferred embodiment the saturated heterocyclic amine is of the general formula (1):
    (one)
    where: X is selected from NR2 and CR3R4; preferably X is NR2 and more preferably X is NH; R1 and R2 are each independently selected from hydrogen, (C1-CS) alkyl, optionally substituted by an amino terminal group (-NH2); R3 and R4 are each independently selected from hydrogen and (C1-CS) alkyl, preferably selected from hydrogen and methyl; and 30 n is O or 1, formed a ring of five or six members respectively, preferably n is 1.
    The term "alkyl" refers, in the present invention, to saturated, linear or branched hydrocarbon chains having 1 to 5 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl , tert-butyl, sec-butyl or n-pentyl. Preferably the alkyl group has between 1 and 4 carbon atoms.
    In a preferred embodiment, the saturated heterocyclic amine is 1- (2-amino alkyl (C, Cs)) -piperazine, more preferably 1- (2-amino ethyl) -piperazine.
    In another preferred embodiment, the saturated heterocyclic amine has a loading capacity expressed in moles of CO2 per mole of absorbent close to or greater than 1 and is at a concentration of at least 1% w / w in solution, more preferably at a concentration of between 5% w / w and 50% w / w solution.
    By "amines with impediment be rich" are defined the compounds that structurally contain at least one primary amine attached to a tertiary carbon atom or a secondary amine attached to a secondary or tertiary carbon atom and at least one water solubilization group . Water solubilization groups are groups that help or allow the dissolution of the compound in water and can be selected from carboxylic acid (COOH), sulfonic acid (S03H), hydroxyl (OH), sulfinic acid (S02H), sulfate (- OS03H), among other groups. In a preferred embodiment the amine with aesthetic impairment is an alkanolamine, as for example but not limited to 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1-butanol, 3 amino-3- methyl- 1-butanol, 3-amino-3-methyl-2-butanol, 2-ethanol piperidine, 2-methanol piperidine, among others.
    In a preferred embodiment, the hindered amine is rich is amino-2-methyl-1propane!
    In another preferred embodiment, the steric hindered amine is in a concentration of at least 1% w / w, being limited by the maximum solubility in aqueous solution and the viscosity of the absorbent system, more preferably between 5% w / w And 50% w / w solution.
    By "organic diamine" is meant in the present invention two groups of primary amines (-NH2) linked by a linear or cyclic chain of saturated or unsaturated hydrocarbons. Where the linear chain may be branched and contain from 2 to 20 carbon atoms, preferably from 6 to 12, and the cyclic chain from 4 to 18 carbon atoms, preferably from 5 to 15, and may be optionally substituted. Non-limiting examples are 1,2-diaminoethane, 1,1-dimethylletylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, diaminocyclohexane, o-phenylenediamine, isophorondiamine, among others.
    In a preferred embodiment the diamine is selected from a compound of formula (11)
    Where: R is an alkylene group, branched or not, Cr C2o, preferably C6-C12,
    or R is an optionally substituted cycloalkyl group, preferably C4-C18 cycloalkyl, more preferably CS-C1S.
    In a preferred embodiment, the diamine is isophorondiamine or any of its derivatives, more preferably the diamine is isophorondiamine.
    By "isoforondamine derivatives" are understood the compounds of formula (lilac) or (IIlb):
    (lilac) (IIlb) where: R1 is hydrogen or a (C1-C4) alkyl group; preferably it is hydrogen or methyl; R2 and R3, each independently selected from hydrogen or
    a (C1-C4) alkyl group, preferably they are hydrogen;
    each R4 is a (C1-C4) alkyl group; preferably a methyl;
    n is between 1 and 8, preferably 1, 2 or 3; more preferably 1 and 30 m is between 1 and 9, preferably 2 or 3, more preferably 2
    In a preferred embodiment, the diamine has a loading capacity expressed in moles of CO2 per mole of absorbent greater than 1 and is in a concentration of up to 5% plp in solution.
    In a more preferred embodiment, the composition of the invention comprises 1- (2-amino ethyl) -piperazine, 2-amino-2-methyl-1-propanol and isophorondiamine. More preferably, the composition of the invention comprises 1- (2-amino ethyl) -piperazine in 20% plp, 2-amino-2-methyl-1-propanol in 15% plp and isophorondiamine in 1.5% plp , in aqueous solution.
    In another even more preferred embodiment, the absorbent composition of the invention further comprises additives selected from promoters for the adjustment of the kinetics of the absorption process, of adjuvant agents, anti-foaming agents, corrosion inhibitors, oxidative degradation inhibitors or Any of your combinations. Examples of these additives can be selected, without being limited to arsenious anhydride, selenium or tellurium acids, protids, amino acids, such as glycine, vanadium oxides or chromates, among others. All these additives can be found in the composition in amounts suitable for proper functionality and operability of the absorbent in a CO2 separation process by chemical absorption described in the present invention, amounts known to one skilled in the art.
    The process of separation of acid gases, in particular of CO2, by chemical absorption is based on an optimization of the cyclic load capacity in operation of the absorbent, understood as the difference between the CO2 load of the rich absorbent composition at the exit of the absorber and poor absorbent composition at the outlet of the regenerator, so that the energy requirements in the reboi / er associated with the regeneration process of the absorbent are minimized.
    The displacement of the cyclic charge capacity of CO2 in operation of the absorbent allows an operation in a region of lower enthalpy of CO2 solubility, whereby a decrease in energy consumption in the regenerator is obtained compared to a conventional operation. The optimization of the cyclic load capacity is done by adjusting the degree of regeneration required by the absorbent. This adjustment is achieved by introducing the stream of absorbent composition rich in CO2 obtained at the outlet of the absorber at different heights of the regenerator and / or by adjusting the temperature of the streams of absorbent composition rich in CO2 at the inlet of the regenerator.
    This configuration of the CO2 regenerative absorption process concludes with the reintroduction of the CO2-poor current at the outlet of the regenerator in the absorber, to again produce the absorption of CO2 and / or acid gases, these being retained within the absorber. To produce an increase in the CO2 load of the absorbent during the absorption process, part of the charged CO2 current at the outlet of the absorber is partially recirculated after pre-cooling. This results in an increase in the overall CO2 load of the absorbent at the outlet of the absorber. The operation under these conditions allows optimally adjusting the range of cyclic working capacity of the absorbent during the operation. In this way, this procedure has significantly reduced the specific consumption associated with the regeneration of the absorbent compared to a conventional configuration of the absorption system.
    Therefore, another aspect of the present invention relates to a process for separating acid gases from a gas stream based on chemical absorption, which comprises the following steps:
    a) absorption of acid gases from the gaseous stream to be treated at a temperature between 40 ° C and 60 ° C and a pressure in a range between 1 and 1.5 bar, by bringing an absorber of said current into contact with an 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 current comprising the absorbent solution rich in acid gas from step (a); c) desorption of the acid gas in a current regenerator comprising the absorbent solution rich in acid gas, preferably CO2, from step (a) not recirculated to step (b) at a temperature 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 desorbed acid gas, where said stream is divided into at least two streams by a train of heat exchangers, prior to the regenerator input; and d) recovery of the absorbent solution resulting from step (c) to the absorber of step (a).
    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 is dissolved and chemically bonded to the absorbent.
    In a preferred embodiment of the process of the invention the recirculated flow rate of stage (b) reaches between 25% and 75% of the total acid-rich solution from stage (a).
    In a preferred embodiment of the process of the invention the recirculation of the current from stage (b) takes place in the lower bed of the absorber of stage (a).
    In a preferred embodiment of the process of the invention the currents from stage (c) are introduced into areas located at different heights of the regenerator of stage (d).
    In a preferred embodiment of the process of the invention, prior to step (c), a train of heat exchangers is incorporated, through which the current comprising the absorbent solution rich in acid gas, preferably CO2, from the stage ( a) not recirculated to step (b). This train of exchangers apart from thermally conditioning the CO2-rich absorbent solution divides it into at least two streams that are introduced into the regenerator in areas located at different heights, stratifying the feed to the regenerator, which causes a decrease in the temperature profile of the regenerator.
    The absorbent composition of the present invention is suited to 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:
    a) High CO2 loading capacity, expressed as moles of CO2 per mole
    of absorbent in aqueous solution: This characteristic infers a better
    adaptation to the operating conditions imposed by the procedure
    described
    b) High kinetic ratios of CO2 absorption, expressed as mass flow of CO2 per unit of time, which leads to a reduction in the volume of absorbent required to achieve a given CO2 separation performance and, therefore, to a decrease in the investment, by reducing the size of the equipment and lines of the CO2 separation unit.
    c) Both characteristics described above entail a lower requirement of the operating L / G ratio to achieve a given CO2 separation performance. This implies a lower circulation of liquid absorbent solution and, therefore, a lower consumption in impulse of the absorbent.
    d) The use of the absorbent composition described in this invention in the process of the invention makes it possible to significantly reduce the energy consumption associated with the regeneration of the absorbent.
    Another aspect of the present invention relates to the use of the composition of the invention for the absorption of acid gases.
    By "acid gas" we mean in the present invention any of the following: CO2, H2S and S02, or mixtures thereof, preferably the acid gas to be separated in the process of the present invention is CO2.
    The application of this CO2 capture procedure can be for gases or gaseous streams from stationary sources of combustion, such as electrical production systems, cement, oil refineries or 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 separation of CO2 into a gas stream under these conditions is highly favored when CO2 has a high concentration of CO2.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived 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.
    DESCRIPTION OF THE FIGURES
    FIG. 1: Shows a scheme of a CO2 absorption-desorption system through a process of optimization of the cyclic capacity of the absorbent to operate.
    FIG. 2: Shows a detail of the heat exchanger train.
    FIG. 3: It shows a graph in which the enthalpy of CO2 solubility is represented as a function of the absorbent load expressed in moles of CO2 per mole of absorbent (generic absorbent). The cyclic capacity of operation for a conventional configuration and an optimization configuration of the cyclic capacity of operation of the absorbent are generically indicated.
    FIG. 4: Evolution of the CO2 absorption ratios obtained in laboratory tests The CO2 absorption ratio is represented 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 performed with the new absorbent mixture are represented,
    using 60% v / v CO2 (- ••) and 15% v / v CO2 (••••••••) in the gas phase. In the case of MEA, the absorption ratios obtained for 60% v / v CO2 (
    - ) and 15% v / v CO2 () in the gas phase.
    FIG. 5: CO2 capture performance obtained for each UG ratio using the new absorbent mixture (.) And the reference absorbent (...) using a current of 40% v / v CO2 in a CO2 chemical absorption unit operating through a process for optimizing the cyclic capacity of the absorbent to operate. The CO2 capture performance, defined as the difference in mass flow of CO2 in the gas phase between the output and the input of the CO2 absorption unit, is represented. The percentage capture efficiency is expressed based on the mass flow of CO2 at the input of the absorption unit. This parameter has been represented as a function of the UG ratio of each test, expressed as mass flow of absorbent in liquid phase (kg / h) versus mass flow of gas to be treated (kg / h). The essays
    performed using the new absorbent mixture are represented by (.), while tests performed using MEA are represented by (&).
    FIG. 6: Specific consumption of the regeneration of the absorbent obtained for
    each UG ratio using the new absorbent mixture (.) and the reference absorbent (&) using a current of 40% v / v CO2 in a CO2 chemical absorption unit operating through a process of optimization of the cyclic capacity of operation of the absorbent. The specific consumption associated with the regeneration of the absorbent, expressed in energy units per unit mass of CO2 (GJ / t CO2) is represented. This parameter has been represented as a function of the LlG ratio of each test, expressed as mass flow rate of liquid phase absorbent (kg / h) versus mass flow of gas to be treated (kg / h). Tests performed using the new absorbent mixture are represented by (.), While tests performed using MEA are represented by (&).
    EXAMPLES
    The invention will now be illustrated by tests carried out by the inventors, which shows the effectiveness of the absorbent composition of the invention and more specifically the improvements in the performance of the separation process by means of an optimization process of the cyclic capacity of operation of the absorbent (Spanish patent application P201600519), associated with the use of this composition, in combination with a unit of chemical absorption of CO2. .
    Example 1: Preferred embodiment of the optimization system of the cyclic capacity of the absorbent.
    Specifically in FIG 1, the CO2 absorption-desorption system has been represented, which includes the elements described below:
    1.-Gas stream to be treated 2.-Absorber 3.-Clean gas 4.-Absorbent solution rich in CO2 5.-First discharge pump 6.-Absorbent solution rich in CO2 7.-Rich absorbent solution in recirculated CO2 8.A.-First heat exchanger 8.8.-Second heat exchanger 9.-Train of exchangers 10.-Primary current 11.-Heat exchanger for energy use of the gas stream at the outlet of the regenerator 12 .-Main input current to the regenerator of CO2-rich absorbent solution
    13.-Secondary current 14.-Alternative input currents to the CO2-rich absorbent solution regenerator 15.-Regenerator 16.-Regenerator output gas current
    17.-Condensate separator 18.-High CO2 concentration gas stream 19.-Condensate stream 20.-Boiler 21.-Poor regenerated absorbent solution 22.-Second discharge pump 23.-Solution inlet stream regenerated absorbent
    As can be seen in FIG 1, the system incorporates an absorber (2) comprising a filler column that can be both structured and unstructured, and a lower bed, where the gas stream to be treated (1) arrives that will enter in contact in the absorber (2) with an absorbent liquid that is used to retain the CO2 of the gas to be treated (1). The absorber (2) incorporates a CO2-rich outlet absorbent solution outlet (4), an input for the regenerated absorbent solution inlet stream (23), a recycled CO2-rich absorbent solution stream (7) and a exit through which the clean gas is evacuated
    (3) CO2 free.
    The input stream of regenerated absorbent solution (23) from the regenerator (15) is at a temperature that has been adjusted to values close to that of the gas stream to be treated (1) by using a second heat exchanger. heat (88).
    On the other hand, the absorber (2) incorporates an inlet of a recirculation line of recirculated CO2-rich absorbent solution (7), which is redirected to the lower bed of the absorber (2) in order to increase its load, with intermediation of a first heat exchanger (8A) that cools its temperature.
    In a preferred embodiment, the design of the absorber (2) requires an increase in the section in the lower bed with respect to the rest of the column, as shown in FIG. one.
    It is also observed in FIG. 1 that the CO2-rich exit absorbent solution (4) is extracted from the absorber (2) from the bottom thereof and driven by a first drive pump (5) that drives the CO2-rich exit absorbent solution (4) to then separate into the recirculated CO2 rich absorbent solution (7) and a CO2 rich absorbent solution (6), which is previously introduced into the heat exchanger train (9).
    The above-mentioned CO2-rich absorbent solution (6) reaches the heat exchanger train (9), where the temperature of this current is optimally adjusted before being divided and directed towards the regenerator (15), as well as arrives a poor regenerated absorbent solution (21) from the regenerator (15), and the regenerated absorbent solution inlet stream (23) directed to the absorber (2) leaves the heat exchanger train (9), as well as exits, consequence of the said division of the absorbent solution rich in CO2 (6), a primary current (10) and a secondary current (13).
    In FIG. 2 the train of heat exchangers (9) comprising the following elements is observed:
    6.-CO2-rich absorbent solution 9.-Exchangers train 10.-Primary current 13.-Secondary current 13.A.-Alternative for extracting the first secondary current exchanger entering the CO2-rich absorbent solution regenerator 13.8.-Alternative of extraction of the second secondary current exchanger of entry to the regenerator of CO2-rich absorbent solution 13.C.-Alternative of extraction of successive secondary exchangers of input current to the regenerator of CO2-rich absorbent solution 21. -Poor solution of regenerated absorbent 21.A.-Alternative supply of regenerated absorbent solution to successive exchangers in the exchange train
    21 .8. -Alternative of regenerated absorbent solution feed to the second exchanger in the exchanger train 21 .C.-Alternative alternative of regenerated absorbent solution to the first exchanger in the exchange train
    23.-Input current to the regenerated solution absorber 24.-First internal exchanger of the exchange train 25.-Second internal exchanger of the exchange train 26.-Successive exchangers of the exchange train
    The exchanger train (9) shown in FIG. 2 comprises a series of N internal heat exchangers (24, 25, 26), preferably from 2 to 4 heat exchangers, where the CO2-rich absorbent solution (6) is heated to different levels by using the solution poor regenerated absorbent (21) from the bottom of the regenerator (15). The stream of CO2-rich absorbent solution (6) is divided into two main streams. The primary current (10) is heated by the use of all internal heat exchangers (24, 25, 26), while the secondary current (13) can be extracted at the output of each of the internal exchangers, resulting in at internal currents (13A, 138, 13C). The poor solution stream of regenerated absorbent
    (21) can in turn be divided into different subcurrents, called (21A, 21 B, 21C), to achieve an even more precise adjustment of the thermal level of the primary current of rich solution (10) and, therefore, of the profile of regenerator temperatures (1 5).
    The distribution of the CO2-rich absorbent solution (6) between the primary current (10) and the secondary current (11) is preferably set in the range of 0.25 to 0.75. The primary current (10) is then preheated in a second indirect contact exchanger (11) using the regenerator output current (16), at a temperature greater than 100 ° C, resulting in a main input current to the regenerator (12).
    The absorber current (2) reaches different heights and temperatures at the regenerator (15), so that the degree of regeneration of the absorbent is optimally adjusted.
    The main input current to the regenerator (12) is introduced in the upper part of the regenerator (15). On the other hand, the secondary current (13) is introduced at a temperature lower than that set for the primary current (10) in an intermediate bed of the regenerator (15), achieving a temperature profile that optimizes the energy requirements of the overall process of capture. The secondary current (13) can in turn be divided into another additional current (14) to be fed at different heights of the regenerator (15).
    This configuration allows to obtain a partial regeneration of the absorbent, displacing the cyclic capacity of the same towards areas of lower energy requirement of the CO2 desorption. The energy necessary for regeneration of the absorbent to occur is supplied to the regenerator (15) by means of a boiler (20) preferably using steam as a working fluid.
    On the other hand, the output current (16) from the top of the regenerator, composed mainly of CO2 and water vapor, is introduced into a separator (17), where the high concentration of CO2 saturated in water is obtained
    (18) and a condensate stream (19), which is subsequently recirculated to the regenerator (15).
    Finally, the poor regenerated absorbent solution (21) is extracted from the lower part of the regenerator (15) and driven by a second pump (22) to the train of exchangers (9) prior to its return to the absorption system (23) .
    The regenerator (15) preferably works in a pressure range of between 1.5 and 5 bar, and at a maximum temperature of less than 120 · C, more preferably, in a temperature range of between 100 ° C and 120 ° C , so that less degradation of the absorbent is guaranteed.
    Particularly, a process of CO2 separation of a synthetic gas stream was carried out in a laboratory-scale unit based on two operating configurations that correspond on the one hand to a conventional configuration and on the other to a configuration according to the system described.
    In this way, a synthetic gas flow rate of 7 L / min has been used, with a composition of 60% v / v CO2, saturated in water vapor and completed with N2. Monoethanolamine in 30% w / w aqueous solution has been used as an absorbent, as it is a reference absorbent. The total amount of absorbent used in the system is 2 L. The CO2 absorption is carried out at a pressure of 1 atm and a temperature of 50 · C in a column 3 cm in diameter and 2 m high using as an absorption bed 6 mm Raschig ceramic rings. The regeneration of the abscess is carried out at a pressure of 2 bar on a column 3 cm in diameter and 1 m high using 6 mm 316L stainless steel Raschig rings.
    The conventional configuration has consisted of having a recirculation rate in the absorber of O (7), a single internal heat exchanger (24) composes the train of exchangers (9) and the feeding to the regenerator (15) is carried out by means of the use of a single primary current (10) introduced by the top of the regenerator (15). The absorbent flow rate was set at 7.01 kg / h, which corresponds to an L / G ratio equal to 12, the absorber inlet temperature being 49 · C.
    The configuration of the invention has employed a partial recirculation of the stream of recirculated CO2-rich absorbent solution (7), a train of exchangers (9) composed of internal heat exchangers (24, 25), and the current has been distributed Input to the regenerator in two currents: a primary current (10) in the upper part of the regenerator (15) and a secondary current (13) in the intermediate zone of the regenerator (15). This secondary current (13) was extracted at the exit of the first internal heat exchanger (24) of the exchanger train (9). The absorbent flow rate was set at 8.18 kg / h, which corresponds to an L / G ratio equal to 14, with the inlet temperature of the gas entering the absorber 4TC.
    The most relevant operating conditions and results obtained are summarized in Table 1. The operation by the method of the invention allowed to increase the cyclic capacity of the absorbent and the CO2 separation performance during the separation operation thanks to a greater load of the absorbent Rich in the absorption stage. This load increase is mainly due to the recirculation of part of the recycled CO2-rich absorbent solution (7). The stratification of the feed in the regenerator (15) caused a decrease in the temperature profile in the regenerator (15) and, therefore, a more loaded poor solution
    in CO2. This shift in the cyclic capacity of the absorbent operation allowed the use of the new configuration to achieve a 11% reduction in the specific energy consumption associated with the regeneration of the absorbent, producing a net benefit with respect to the traditional configuration of this type of processes In addition, the lower thermal level obtained in the regenerator favors the reduction of the degradation of the absorbent associated with thermal mechanisms.
    Table 1 System Configuration
    Conventional Units FIG. 1
    Operational Parameters Example 2: Different tests were performed in a laboratory assembly operating in semi-continuous regime to produce saturation of a known amount of the absorbent mixture proposed in this invention. For this, 250 mL of solution was available
    Absorber LlG Ratio Recirculation Ratekg / kg%12 -14 20
    Bottom temperature ·C120118
    Regenerate or Feeding Primary flow rate Temperaturekg / hC7.01 1125.73 108
    Food Flowkg / h-2.45
    secondary school Temperatures·C-100
    Cast by train (21 C / 21 B) -100/080/20
    Results
    Poor absorbent load mol CO2 / mol absorbent0.150.19
    Rich absorbent load mol CO2 / mol absorbent0.340.41
    Cyclic capacity mol CO2 / mol absorbent0.190.22
    CO2 capture performance %9698
    Specific consumption of captured CO2 GJ / t CO24.554.05
    5 absorber in a reactor where 2 L1min of a gas stream of known composition has been introduced until saturation. The test temperature was set at 50 · C. Once the test was finished, the loading of the absorbent mixture in equilibrium, expressed in moles of CO2 per mole of absorbent, was determined using an inorganic carbon analyzer. Table 2 shows the results obtained for the
    10 tests performed using absorbent mixture 1: comprising 1- (2-amino ethyl) piperazine in 20% w / w, 2-amino-2-methyl-1-propanol in 15% w / w and isophorondiamine in one 1.5% w / w in aqueous solution and its comparison with the reference absorbent (30% w / w aqueous MEA solution).
    15 Table 2. Summary absorbent load in equilibrium at different concentrations of CO2 in gas phase 15% v / v test 40% v / v test Absorbent
    CO2 CO2
    Absorbent mixture 1 0.889 0.955 MEA 30% w / w 0.535 0.584
    The absorbent mixture 1 achieves up to 65% more CO2 loading capacity compared to the reference absorbent. In turn, the absorbent mixture
    20 has a high loading capacity, very close to 1 mole of CO2 per mole of absorbent in solution. In this way, the new absorbent mixture has a greater flexibility of operation and adaptation to the optimization system of the cyclic capacity of the absorbent (example 1).
    Example 3: From the tests described in example 2, it was possible to determine the absorption ratios measured in the gas phase for each of the tests performed. Figure 4 summarizes the results obtained in these tests, representing the evolution of the CO2 absorption ratios obtained in the laboratory tests.
    The absorption rates increase significantly with an increase in the concentration of CO2 in the gas phase. In addition, the absorbent mixture 1 has
    higher absorption rates of e02 than those obtained with the reference absorbent (30% w / w aqueous solution of MEA) for the same concentration of e02 in the gas phase, demonstrating a better kinetic behavior for an operation based on the system of optimization of the cyclic capacity of absorbent operation (example 1).
    Example 4: A process of separating e02 from a synthetic gas stream was carried out in a laboratory-scale unit based on an operation according to the optimization system of the cyclic capacity of the absorbent (example 1), using the absorbent mixture 1 and MEA 30% w / w as reference absorbent. In the exemplary embodiment, a synthetic gas flow rate of 7 L / min was used, with a composition of 40% v / v eo2, saturated in water and balanced with N2. The total amount of absorbent used in the system was 2 L. The absorption of e02 was performed at 1 atm and 500 e on a column 3 cm in diameter and 2 m high using 6 mm Raschig ceramic rings.
    The regeneration of the absorbent took place at 2 bar in a column 3 cm in diameter and 1 m high using a filling of 6 mm 316L stainless steel Raschig rings. The average operating temperature in the regeneration unit was 118 ° e for the MEA tests 30% w / w and 11 Te for the absorbent mixture tests, operating according to the procedure for optimizing the cyclic capacity of the absorbent operation . The L / G ratio varied for each absorbent to reach a capture yield of 100%. Figure 5 shows the capture yields of e02 obtained as a function of the L / G ratio used in each test.
    The tests carried out demonstrate the greater absorption capacity and flexibility of operation of the absorbent mixture 1 with respect to the reference absorbent. The L / G ratios obtained are lower than those required by the reference absorbent for a defined e02 capture performance. In particular, the new absorbent system requires an L / G ratio of 7.3 while MEA 30% w / w requires an L / G ratio of 10 in the case of obtaining an e02 capture yield of 90% using a gas stream with a concentration of 40% v / v eo2.
    Example 5:From the tests described in the previous example, the consumptions have been obtainedspecific associated to the regeneration of the absorbent for each test performed,modifying the LlG ratio. Figure 6 represents the evolution of this parameter for
    5 each test performed, using the two absorbers indicated above.
    As demonstrated from the results indicated in Figure 6 and in table 3 (summary), the absorbent mixture 1 provides a lower energy consumption of the regeneration of the absorbent in an operation to optimize the cyclic capacity
    10 of absorbent operation. The absorbent mixture proposed in this invention manages to reduce energy consumption up to 24% compared to the reference absorbent.
    Table 3. Summary of energy consumption and capture yields associated with
    15 obtained in an operation to optimize the cyclic capacity of the absorbent (see example 1). Consumption
    Performance Absorbent Specific UG Ratio (GJ / t Capture (%)
    CO2)
    Absorbent mixture 1 8 4.59 93.1 MEA 30% w / w 12 6.03 91.8
    权利要求:
    Claims (19)
    [1]
    1. Aqueous absorbent composition comprising:
    i. a saturated heterocyclic amine of general formula (1):
    (1) where: X is selected from NR2 and CR3R4;
    10 R, and R2 are each independently selected from hydrogen,
    alkyl (C, -Cs), optionally substituted by an amine group;
    R3 and R4 are each independently selected from hydrogen
    and alkyl (C, -Cs); Y
    n is O or 1;
    fifteen ii.an amine with a disability is rich,
    iii. aorganic diamine thatbeselect from isoforondamineor their
    derivatives selected from a compound of formula (lilac) or (1IIb):
    twenty
    (lilac) (1IIb)
    where: R, is hydrogen or a (C, -C4) alkyl group,
    R2 YR3, beselect eachonefromwayindependent between
    hydrogen or a (C, -C4) alkyl group,
    25 each R4 is a (C, -C4) alkyl group,
    n is between 1 and 8, Y
    m is between 1 and 9, Y
    iv. Water.
    [2]
    2. Composition according to claim 1, wherein the saturated heterocyclic amine is in a concentration of at least 1% w / w in solution, preferably in a concentration of between 5% w / w and 50% w / w in solution.
    [3]
    3. Compound according to any one of claims 1 or 2, wherein the saturated heterocyclic amine is 1- (2-amino ethyl) -piperazine.
    [4]
    Four. Composition according to any one of claims 1 to 3, wherein the steric hindered amine is in a concentration of at least 1% w / w in solution, preferably between 5% w / w and 50% w / w in solution.
    [5]
    5. Composition according to any one of claims 1 to 4, wherein the steric hindered amine is amino-2-methyl-1-propanol.
    [6]
    6. Composition according to any one of claims 1 to 5, wherein the diamine is in a concentration of up to 5% w / w in solution.
    [7]
    7. Composition according to any one of claims 1 to 6, wherein the diamine is isophorondiamine.
    [8]
    8. Composition according to any one of claims 1 to 7, wherein the composition comprises 1- (2-amino ethyl) -piperazine, 2-amino-2-methyl-1-propanol and isophorondiamine.
    [9]
    9. Composition according to any one of claims 1 to 8, wherein the composition comprises 1- (2-amino ethyl) -piperacin in 20% w / w, 2-amino-2-methyl-1-propanol in 15% w / w And isoforondiamine in 1.5% w / w, in aqueous solution.
    [10]
    10. Composition according to any one of claims 1 to 9, wherein it further comprises promoters for the adjustment of the kinetics of the absorption process, of adjuvant agents, anti-foaming agents, corrosion inhibitors and oxidative degradation inhibitors.
    [11 ]
    eleven . Method of separation of acid gases from a gas stream based on chemical absorption, comprising the following steps:
    a) absorption of acid gases from the gaseous stream to be treated at a temperature between 400 and 600 e and a pressure in a range of 1 to 1.5 bar, by contacting an absorber of said stream with a solution absorbent in which the acid gases are to be retained, where the absorbent solution is a composition described in any of the
    claims 1 to 10;
    b) recirculation to the absorber of up to 75% of the current comprising the
    absorbent solution rich in acid gas from step (a);
    c) desorption of the acid gas in a current regenerator comprising the
    absorbent solution rich in e02 from step (a) not recirculated to the
    step (b) at a temperature between 800 and 120oe, a pressure between 1.5 and 5
    bar and a steam flow rate of between 10 and 90% by volume with respect to
    desorbed acid gas flow, where said current is divided into at least two
    currents through a train of heat exchangers, prior to
    regenerator input; Y
    d) recovery of the absorbent solution resulting from step (c) to the absorber
    of stage (a).
    [12]
    12. Process according to claim 11 wherein the acid gas of the gas stream to be treated in step (a) is transferred to the liquid phase where it is dissolved and chemically bonded to the absorbent.
    [13]
    13. Process according to any of claims 11 or 12, wherein the recirculated flow rate of stage (b) reaches between 25% and 75% of the total acid-rich solution from step (a).
    [14]
    14. Method according to any of claims 11 to 13, wherein the recirculation of the current from stage (b) takes place in the lower bed of the absorber of stage (a).
    [15]
    fifteen. Method according to any of claims 11 to 14, wherein the currents from stage (c) are introduced into areas located at different heights of the regenerator of stage (d).
    [16]
    16. Process according to any of claims 11 to 15, wherein prior to step (c), the absorbent solution rich in acid gas from step (a) does not
    recirculated to stage (b) is passed through a train of heat exchangers, which
    divide that stream into at least two streams that are introduced into the
    stage regenerator (c) in areas located at different heights.
    Method according to any one of claims 11 to 16, wherein the acid gas comprises CO2.
    [18]
    18. Use of the composition according to any of claims 1 to 10, for the
    acid gas absorption. 10
    [19]
    19. Use according to the preceding claim, wherein the acid gas comprises CO2.
    ~
    I I I
    • I
    ~:
    iD .. t,
    , '"'
    II ~
    FIG2
    120 ~ -----------------------,
    20 ~~~~ - + ~~~~ + - ~~~~~~~~ - ~~~
    [0]
    0.00 0.20 0.40 0.60 0.80 1.00
    Load I (rml CO / mol absorbent) FIG 3
    ...... •. New Absorbent System 15% v / v C02 -. • New Absorbent System 60% v / v C02
    - MEA 15% v / v C02 --MEA60% v / vC02
    3.5
    and
    ~ 3.0 _ E 2.5
    N
    or
    u 2.0
    Qj
    '1: 1
    c: 1.5
    or()
    'or
    5 1.0
    11 .Q
    «0,5
    Qj
    '1: 1
    or
    -
    0.0 or 10,000 $ -15,000 20,000 • 25,000 30,000
    to:
    100.0
    90.0
    ) / !. 80.0
    N
    OR
    OR
    10 70.0
    ... .. "Q.
    U lO 60.0
    OR
    ..
    ., e 50.0
    AND
    :
    c: 40.0
    .,
    a: 30.0
    20.0
    TIME (5)
    FIG. 4
    - + - Absorbent Blend - * - "MEA
    O 2 4 6 8 10 12 14L / G ratio
    FIG. 5
    ... Absorbent Blend ........ MEA
    _ 10.00
    N
    OR
     OR ... .
    .......
    ..... 8.00
    ~ ~
    or
    ... •
    ! E •. ~
    ... 6.00
    Q)
    ..Q.
    IU
    or
    E 4.00
    ~
    ..
    C:
    or
    or
    2.00
    ° 2 4 6 8 10 12
    l / G
    FIG. 6
    类似技术:
    公开号 | 公开日 | 专利标题
    ES2394100T3|2013-01-17|Process for the recovery of carbon dioxide
    ES2754801T3|2020-04-20|CO2 washing process with an alkanolamine
    US8388855B2|2013-03-05|Polyamine/alkali salt blends for carbon dioxide removal from gas streams
    ES2521624T3|2014-11-13|Alkylamino alkyloxy | monoalkyl ether for acid gas washing process
    JP5713997B2|2015-05-07|Acid gas absorbent, acid gas removal device, and acid gas removal method
    KR20100092050A|2010-08-19|System and method for regeneration of an absorbent solution
    JP5452222B2|2014-03-26|Method for efficiently recovering carbon dioxide in gas
    Vega et al.2018|Solvents for carbon dioxide capture
    JP5506486B2|2014-05-28|Aqueous solution that effectively absorbs and recovers carbon dioxide contained in gas
    ES2368091T3|2011-11-14|ELIMINATION OF CARBON DIOXIDE FROM COMBUSTION GASES.
    JP5557426B2|2014-07-23|Aqueous solution and method for efficiently absorbing and recovering carbon dioxide in gas
    JP2006240966A|2006-09-14|Method for recovering carbon dioxide in exhaust gas by absorption and releasing
    JP2014004533A|2014-01-16|Acid gas absorbent, acid gas removing method and acid gas removing device
    AU2018271225B2|2020-09-03|Acid gas absorbent, acid gas removal method, and acid gas removal device
    JP2008013400A|2008-01-24|Method for recovering carbon dioxide in waste gas by absorption and releasing
    JP2012139622A|2012-07-26|Solid absorber for separating/recovering carbon dioxide and method for recovering carbon dioxide
    JP2018122278A|2018-08-09|Acidic gas absorbent, acidic gas removal method and acidic gas removal device
    WO2015167729A1|2015-11-05|Carbon dioxide scrubbing process
    ES2673740B2|2018-10-31|Aqueous absorbent composition
    JP2008168184A|2008-07-24|Composition for absorbing and dissociating carbon dioxide in exhaust gas to recover it and carbon dioxide recovering method using it
    JP2014097498A|2014-05-29|Acid gas absorbent, acid gas removal device and acid gas removal method
    ES2697300B2|2019-05-24|AQUEOUS COMPOSITION FOR THE SEPARATION OF CO2 AND / OR ACID GASES
    JP6445874B2|2018-12-26|Acid gas absorbent, acid gas removal method, and acid gas removal apparatus
    ES2842276T3|2021-07-13|Procedure for the removal of acid gases from gas mixtures using an aqueous solution of 2-dimethylamino-2-hydroxymethyl-1,3-propanediol
    ES2650963B2|2018-05-08|CO2 separation procedure and system based on chemical absorption
    同族专利:
    公开号 | 公开日
    ES2673740B2|2018-10-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20110100217A1|2009-10-30|2011-05-05|General Electric Company|Spray process for the recovery of co2 from a gas stream and a related apparatus|
    WO2013075697A1|2011-11-25|2013-05-30|Buettner Hermann|Use of cyclic amines for reversible absorption of co2|
    FR3001157A1|2013-01-24|2014-07-25|IFP Energies Nouvelles|ABSORBENT SOLUTION BASED ON A TERTIARY OR CONTAINED AMINE AND A PARTICULAR ACTIVATOR AND METHOD FOR REMOVING ACIDIC COMPOUNDS FROM A GASEOUS EFFLUENT|
    法律状态:
    2018-06-25| BA2A| Patent application published|Ref document number: 2673740 Country of ref document: ES Kind code of ref document: A1 Effective date: 20180625 |
    2018-10-31| FG2A| Definitive protection|Ref document number: 2673740 Country of ref document: ES Kind code of ref document: B2 Effective date: 20181031 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201601110A|ES2673740B2|2016-12-23|2016-12-23|Aqueous absorbent composition|ES201601110A| ES2673740B2|2016-12-23|2016-12-23|Aqueous absorbent composition|
    [返回顶部]