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    purification process of co ~ 2 ~ alkanolamine. a co-2 ~ amine purification process uses an absorbent mixture consisting of a co-2 ~ alkanolamine sorbent, in combination with a non-nucleophilic base. alkanolamine has oxygen and nitrogen sites capable of nucleophilic attack on the co ~ 2 ~ carbon atom. nucleophilic addition is promoted in the presence of the relatively stronger non-nucleophilic base, acting as a proton acceptor. the non-nucleophilic-based promoter, which can also act as a solvent for alkanolamine, can promote the reaction with the co ~ 2 ~ in each of the hydroxyl and amine reactive group (s) of the alkanolamines. in the case of primary amino alkanolamines, the co ~ 2 ~ can be absorbed by a double carboxylation reaction in which two moles of co ~ 2 ~ are absorbed by the reacting primary amine groups.
    公开号:BR112013004225B1
    申请号:R112013004225
    申请日:2011-09-09
    公开日:2020-01-21
    发明作者:C Calabro David；S Baugh Lisa；Siskin Michael；Kortunov Pavel
    申请人:Exxonmobil Res And Engeneering Company；
    IPC主号:
    专利说明:

    “ALCAN 0 LAM I DE CO2 PURIFICATION PROCESS”
    FIELD OF THE INVENTION [0001] This invention relates to the removal of carbon dioxide and other acidic gases from a gas stream containing one or more of these gases. In particular, the invention relates to a method for separating an acidic gas, e.g. carbon dioxide, of a gas mixture employing one or more alkanolamines as a sorbent.
    BACKGROUND OF THE INVENTION [0002] The removal of carbon dioxide from mixed gas streams is of great industrial importance and commercial value. Carbon dioxide is a ubiquitous and inescapable by-product of hydrocarbon combustion, and there is growing concern about its accumulation in the atmosphere and its potential role in a perceived global climate change. Laws and regulations triggered by environmental factors can therefore be expected soon to require their capture and kidnapping. Although existing CO2 capture methods have been adequately satisfactory for the scale at which they have so far been used, future uses on a much larger scale, required for significant reductions in atmospheric CO2 emissions by major stationary combustion sources, such as forces driven by fossil fuels, make it necessary to improve the processes used to remove CO2 from gas mixtures. According to data developed by the Intergovernmental Panel on Climate Change, power generation produces approximately 78% of global CO2 emissions, with other industries such as cement production (7%), refineries (6%), iron and steel manufacturing (5%), petrochemicals (3%), oil and gas processing (0.4%) and the biomass industry (bioethanol and bioenergy) (1%) composing the mass of the total, illustrating the very large differences in scale between the generation of force on the one hand and all other uses on the other. To this must be added the individual problem of the pure volumes of gas that will need to be treated: the flue gases mainly consist of nitrogen in the combustion air, with CO2, nitrogen oxides and other emissions, such as sulfur oxides,
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    2/34 composing relatively smaller proportions of gases that require treatment: typically, flue gases from fossil fuel power stations typically contain about 7 to 15 percent by volume of CO2, depending on the fuel, with natural gas supplying the lowest amounts and the highest anthracites.
    [0003] Cyclic CO2 absorption technologies, such as pressure swing absorption (PSA) and temperature swing absorption (TSA), using liquid absorbents, are well-established. Mostly used absorbents include liquid solvents, as in amine purification processes, although solid sorbents are also used in PSA and TSA processes. Liquid amine absorbers, including alkanolamines, dissolved in water, are probably the most common absorbers. The amine purification is based on the chemical reaction of CO2 with amines, to generate carbonate / bicarbonate and carbamate salts: aqueous amine solutions chemically trap CO2 by forming one or more ammonium salts (carbamate / bicarbonate / carbonate), which are thermally unstable, allowing the regeneration of free amines at moderately high temperatures. Commercially, amine purification typically involves contacting the CO2 and / or gas stream containing H2S with an aqueous solution of one or more simple amines (eg, monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA) or triethanolamine (TEA)). MEA's low molecular weight makes it economically attractive because sorption occurs on a molecular basis, while amine is sold on a weight basis. The cyclic sorption process requires high gas-liquid exchange rates, the transfer of large liquid inventories between the absorption and regeneration steps, and high energy requirements for the regeneration of amine solutions. It is challenged by the corrosive nature of the amine solutions containing the sorbed CO2. Without further improvement, these difficulties would limit the economic viability of the aqueous amine purification process in very large scale applications.
    [0004] Cyclic absorption processes using aqueous sorbents require a large temperature differential in the gas stream between the parts
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    3/34 absorption and desorption (regeneration) of the cycle. In conventional aqueous amine purification methods, relatively low temperatures, e.g. less than 50 ° C, are required for CO2 absorption with an increase to a temperature above about 100 ° C, e.g. 120 ° C, required for desorption. The heat required to maintain the thermal differential is a major factor in the cost of the process and, with the need to regenerate the solution at temperatures above 100 ° C, the high latent heat of water vaporization (2260 kJ / Kg at 100 ° C ) obviously makes a significant contribution to total energy consumption. In addition, low molecular weight amines, commonly used in the liquid process, suffer significant loss of amine due to vaporization in the temperature oscillation process. If CO2 capture is to be conducted on a larger scale, suitable for use in power stations, more effective and economical separation techniques need to be developed.
    [0005] Another area in which more efficient CO2 separation processes are used is in the enhanced oil recovery (EOR), in which CO2 is reinjected into the gaseous or liquid hydrocarbon deposits, to maintain the reservoir pressure. With the advanced age of many producing reservoirs worldwide and the ever-increasing challenge of meeting demand, the expanded use of EOR methods is becoming much more widespread. Typically, the carbon dioxide source for EOR is the production hydrocarbon stream itself, which can contain anywhere from less than 5% to more than 80% CO2. Other options are to capture CO2 from flue gases from various combustion sources and capture pre-combustion of displaced CO2 produced in fuel gasification processes.
    [0006] Various commercial CO2 capture processes have been brought to the market. The Fluorine Daniel Econamine ™ Process (originally developed by Dow Chemical and Union Carbide), which uses MEA to recover CO2 from flue gases, mainly for EOR applications, has numerous operational plants. The Benfield ™ Process, using hot potassium carbonate, is used in many ammonia, hydrogen, ethylene oxide and natural gas plants with
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    4/34 over 675 UOP licensed worldwide units and has been proposed to treat flue gas, despite its minimum CO2 partial pressure requirement of 210 345 kPag (30-50 psig). A significant disadvantage of the Benfield Process is its use in a high temperature reduction step (175 ° C) approximately 75 100 ° C above the temperature of the absorption step. The Catacarb ™ process, also employing hot potassium carbonate, also uses high temperature reduction, resulting in high energy consumption.
    [0007] Processes using sterically hindered amines as alternatives to MEA, DEA and TEA have also been successful, including the ExxonMobil Flexsorb ™ Process and the KS ™ Process by Mitsubhishi Heavy Industries and Kansai Electric Power Co.
    [0008] Processes employing solid absorbents are also known, and while they can avoid many of the limitations of amine purification, solid sorbents are generally challenged by poor mass and heat transfer properties, while solid physical sorbents resent lack of sufficiently selective CO2 absorption under the wet conditions present in most commercial flue gas processes.
    [0009] In designing a practical CO2 capture process, numerous problems need to be considered, including:
    (i) The efficiency of the capture process in terms of the relative amount of absorbent required, (ii) The efficiency of the capture process in terms of the energy required for absorption / desorption, and (iii) Corrosion factors.
    [0010] These problems are, of course, directly affected by the chemistry of the sorption process. The efficiency of the chemisorption processes, such as conventional amine purification processes, is partly dependent on the ability of the absorbent medium to react with CO2. In conventional aqueous amine systems, the process by which CO2 is absorbed by the amines is believed to be processed by the CO2 gas dissolving in water to form
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    5/34
    H2CO3, which is neutralized by the amine to form an ammonium bicarbonate. Depending on the pH, the ammonium bicarbonate can then react with a second mole of amine to form an ammonium carbonate. Primary and secondary amines can also react directly with CO2 to form an ammonium carbamate, which is itself stable in the presence of water and can be present as a significant reaction product, especially at high amine concentrations. Further reaction of the carbamate with water can result in a final bicarbonate product with a C02: amine ratio of 1: 1, or a carbonate product with a C02: amine ratio of 1: 2 (depending on the pH of the solution) . Thus, conventional amine processes are limited to a sorption efficiency that, in principle, has a maximum C02: amine ratio of 1: 1. Further improvements in the capture ratio and thus in the efficiencies and scalability of related processes are desirable.
    SUMMARY OF THE INVENTION [0011] We have now discovered that it is possible to increase the CO2 absorption efficiencies in an alkanolamine purification process, using alkanolamine sorbents in combination with a strong, non-nucleophilic base as a second reaction component. Analysis showed that the pathway to increased CO2 absorption can be processed by nucleophilic addition of CO2 to both the hydroxyl oxygen atoms and the alkanolamine amine nitrogen. The reaction products of the chemical reaction between CO2 and the alkanolamine / base combination can be decomposed by heat treatment and / or by reducing the partial pressure of CO2, to release CO2 and to regenerate the sorbent for acid gas purification operations .
    [0012] According to the present invention, a CO2 amine purification process can use a combination of one or more CO2 sorbent (s) of alkanolamine with a second non-nucleophilic base which is more strongly basic in terms of pKa , than alkanolamine (s). The secondary base can act to promote the reaction between CO2 and alkanolamine, preferably in the locations of both hydroxyl oxygen and nitrogen amine available in alkanolamine.
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    In principle, the process has the capacity to absorb CO2 in each amine site, as well as in each oxygen of the alkanolamine, so that the alkanolamine can work with a high sorption efficiency.
    [0013] The process can normally be operated in a cyclic manner with a liquid absorber comprising the alkanolamine and secondary-based promoter circulating between a sorption zone, typically a sorption tower, and a regeneration zone, and a regeneration zone, repeating, typically in the form of a tower. The process may include:
    (i) contacting the gas stream in a sorption zone with an absorbent liquid comprising at least one alkanolamine CO2 sorbent and a non-nucleophilic base having a higher pKa than that of alkanolamine to sorb CO2 by chemisorption, (ii ) pass the absorbent liquid containing the absorbed CO2 into a desorption zone, to release CO2 from the absorbent liquid containing CO2 and regenerate the absorbent liquid by treating the absorbent containing the absorbed CO2 under sufficient conditions to cause desorption of at least part of the CO2 of the absorbent, and (iii) return the absorbent liquid from which the CO2 was released to the sorption zone.
    BRIEF DESCRIPTION OF THE DRAWINGS [0014] Figure 1 is a simplified schematic of a cyclic separation unit, to separate CO2 from a flue gas stream.
    [0015] Figure 2 shows the spectra 13 c and 1 H NMR of ~ 1: 3 TEA: TMG (triethanolamine: tetramethylguanidine) in DMSO-solution before and after carbonation with CO2.
    [0016] Figure 2A shows keys for the structures associated with the correspondingly numbered spectral lines of Figure 2 (top section).
    [0017] Figure 2B shows keys for the structures associated with the correspondingly numbered spectral lines of Figure 2 (base section).
    [0018] Figure 3 shows the 13 c and 1 H NMR spectra of ~ 1: 3 DEA: TMG
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    7/34 (diethanolamine: tetramethylguanidine) in DMSO-solution before and after carbonation-0 and carxoxylation-N with CO2.
    [0019] Figure 3A shows keys for the structures associated with the correspondingly numbered spectral lines of Figure 3 (top section).
    [0020] Figure 3B shows keys for the structures associated with the correspondingly numbered spectral lines (base section).
    [0021] Figure 4 shows the 13 and 1 H NMR spectra of ~ 1: 3 MEA: TMG (monoethanolamine: tetramethylguanidine) in DMSO-solution before and after carbonation-0 and carboxylation-N with CO2.
    [0022] Figure 4A shows keys for the structures associated with the correspondingly numbered spectral lines of Figure 4 (top section).
    [0023] Figure 4B shows keys for the structures associated with the correspondingly numbered spectral lines of Figure 4 (base section).
    [0024] Figure 5 shows a graph of vapor-liquid balance for the DMAE: TMG (dimethylaminoetanoktetramethylguanidine) system with CO2.
    DETAILED DESCRIPTION OF THE INVENTION [0025] The separation process of the present invention involves removing CO2 and / or other acidic gases, such as H2S, from a gas stream containing one or more of these gases, using a liquid sorbent medium comprising a combination of hair least two bases of different relative basicities. One basic component can comprise one or more alkalonamines and the second basic component can comprise one or more relatively stronger non-nuclear nitrogenous bases. The strongest base component can itself be effective in absorbing CO2 and can therefore be considered as a cosorbent as well as a promoter for the amine component. One way of carrying out the sorption process may be to operate with a liquid sorption medium, comprising the amine and the secondary base with or without a solvent. In this variant, sorption is generally carried out in a sorption zone, typically a sorption tower in a cyclically operational unit, to produce a stream of effluent gas, which has a reduced concentration of the component
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    8/34 absorbed relative to the gas mixture entering. The sorbent component is normally desorbed and the sorbent medium regenerated by changing the conditions in order to favor desorption, usually by increasing the temperature of the sorbent medium, decreasing the pressure or by reducing the gas, typically with an inert gas ( non-reactive) or a stream of natural gas in a regeneration tower. Under the selected desorption conditions, the sorbent component is purged of the selective absorbent and sent for use and / or sequestration.
    [0026] Cyclic Sorption Unit [0027] Figure 1 shows a simplified schematic of a continuous cyclic gas separation unit, which can be used to separate CO2 from flue gas streams, natural gas streams and other streams, employing the basic absorbent medium. The hot combustion gas stream enters the unit via line 10, entering the foot of the absorber tower 11 and passing through the cooling section 12, where its temperature is reduced by direct or indirect cooling. Cooling is also effective in reducing the water content, if desired, of the gas stream. If the cooling step is not necessary, the gas can be passed directly to the sorption section 13.
    [0028] In the sorption section 13, the gas passes in countercurrent contact with a downward current of the liquid sorbent medium. CO2, along with any other gases that are receptive to absorption in the solution, is absorbed and the “rich” solution 14 containing the sorbed CO2 is removed with a separating tray (not shown) at the bottom end of the sorption section. The rich solution 14 then passes through the heat exchanger 15 to the desorption / regeneration tower 20, in which the CO2 and other gases are desorbed; in this case, by an increase in temperature with agitation being provided by the stream of desorbed CO2 or purge gas. The rich solution enters the tower and at an appropriate level for its composition and passes downwards when dissolved gases are removed. Heat for the regeneration tower is supplied by the annealing boiler 21, which circulates a stream of solution taken from the base of the regeneration tower via line 22. A stream of poor regenerated solution with a lower
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    9/34 CO2 equilibrium level is taken from the annealing boiler on line 23, to pass through the other side of the heat exchanger 15 before re-entering the absorber tower 11 for passage through the gas stream. The gas stream purged from dissolved CO2 passes out of the absorber tower 11 through line 16 and the desorbed CO2 and other acid gases removed from the original gas stream are removed in concentrated form through line 24 and taken for sequestration or end use, P. in the industry or in enhanced oil recovery.
    [0029] Conventional equipment can be used to perform the various functions of the cyclic purification process, such as monitoring and automatic regulation of gas flows, so that they can be fully automated to operate continuously in an efficient manner.
    [0030] Gas Stream [0031] Gas streams particularly receptive to treatment by the present sorption process are combustion gases from the combustion of carbonaceous fuels and natural gas from underground sources. The flue gas can originate from the combustion of fossil fuels such as natural gas, lignite coals, sub-bituminous coals, and anthracite coals. Its CO2 content can typically vary from about 6 to about 15 weight percent, depending on the fuel, with the highest levels coming from anthracite combustion and the lowest levels of natural gas. Streams of natural gas containing carbon dioxide may contain, in addition to methane and carbon dioxide, one or more other gases, such as ethane, n-butane, i-butane, hydrogen, carbon monoxide, ethylene, ethine, propene , nitrogen, oxygen, helium, carbonyl sulfide, hydrogen sulfide and the like, as well as, in some cases, mercury contaminants if they have not been removed by another pretreatment. Other streams that can be treated by the present separation process include single and single displaced, produced in fuel gasification processes and gas streams from petrochemical plants, the composition of which will naturally depend on the process from which they are derived. Water is likely to be present in both flue gases and natural gas from the combustion of hydrocarbon or contact fuels
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    10/34 with soil water. Although the present process can accept water in the incoming gas stream, as described below, removal of substantial amounts may be desirable, for example, by treatment with a drying agent or by cooling to condense and thereby reduce the content of Water.
    [0032] Absorption Process [0033] The efficiency of CO2 sorption is directly affected by the chemistry of the process. In conventional aqueous alkanolamine systems, the process by which CO2 is absorbed by the amines is triggered by acid-base chemistry taking place at the alkanolamine amine sites. Hydroxyl groups are generally considered inert and do not play a direct role in sorption, except possibly to improve the solubility of alkanolamine and CO2 adduct in water. The essential details of the sorption sequence at the amine sites undergo nucleophilic attack from a Lewis base (nitrogen amine) in a Lewis acid (CO2) and subsequent transfer of protons from a Bronsted acid (the resulting zuitehon / carbamic acid described below) to a Bronsted base (a second mol of the amine), forming an ammonium carbamate product. In the absence of a sufficiently nucleophilic amine or in the case of a tertiary amine without a transferable proton, the oxygen in the water acts as the nucleophile forming a Bronsted acid, H2CO3 (CO2 gas phase dissolution in water), which is neutralized by the alkanolamine acting as a Bronsted base to form an ammonium bicarbonate. At high pH, ammonium bicarbonate can then react with a second mole of amine to form ammonium carbonate. In all cases, the chemistry proceeds via a nucleophilic attack (primary or secondary amine nitrogen, or oxygen from water) on carbon CO2, followed by transfer of protons to an amine acceptor. The ammonium carbamate product, which initially forms with the primary and secondary amine groups, is itself stable in the presence of water and can be present as a significant reaction product, especially in a high concentration of alkanolamine. However, the subsequent reaction of the carbamate with water can result in a final bicarbonate product. The conventional aqueous process is based on the rapid formation
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    11/34 carbamate with very small amounts of bicarbonate.
    [0034] In non-aqueous systems, the primary and secondary amines react as described above, to produce ammonium carbamate products; tertiary amines are not reactive. As shown below, the initial nucleophilic attack forms a zuiterion intermediate that is unstable and rapidly decomposes via internal proton transfer in carbamic acid. Carbamic acids are Bronsted acids that can react with a second amine group to form an ammonium carbamate. Both zuiterionic and carbamic acids are unstable and it is not known which form of equilibrium undergoes the most reaction, although it is postulated that it is the carbamic acid that can be deprotonated by a second equivalent amine to produce the ammonium carbamate salt with the total stoichiometric requirement of two amines per mole of carbon dioxide absorbed (0.5: 1 CO2: amine group). This pathway is also found in aqueous systems in early reaction stages, although there is a different balance of carbamate-carbamic acid in non-aqueous systems. Finally, in aqueous systems there is the possibility of further reaction with water to form bicarbonate and carbonate, as described above.
    ooo free amine zuiterion carbamic acid ammonium carbamate [0035] This chemistry requires the amine to function both as an effective nucleophile (Lewis base) in its attack on CO2 and as a proton acceptor (Bronsted base) in its reaction with carbamic acid to form ammonium carbamate. These two types of basicity are, however, different in that Lewis acid-base reactions involve electron transfer, whereas Bronsted acid-base reactions involve proton transfer. A strong Bronsted base may not necessarily be a strong Lewis base and vice versa. Both the internal proton transfer, to form carbamic acid, and the subsequent acid-base reaction, to form the carbamate product, would be
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    Expected to be fast.
    [0036] CO2 Chimisorção Alcanolamina Promoted by Base [0037] The present invention uses a new approach to significantly increase the CO2 absorption efficiency of alkanolamines. In the presence of a strong non-nucleophilic Bronsted base (proton acceptor), both protonated nucleophilic sites (O-H and N-H) are activated for reaction with CO2 to form alkylcarbonate products such as carbamate, respectively. In addition, the strong alkanolamine / Bronsted base combination is capable of promoting the formation of dicarbamate species in primary amine sites, as shown in exemplary mode by the following equations:
    O

    [0038] In all of the above reactions, all available O-H bonds are carbonated by CO2 to form alkylcarbonate anions, which are balanced in charge by the protonated form of the strong non-nucleophilic Bronsted base. Similarly, all N-H bonds undergo carboxylation to form carbamate anions, which are also balanced in charge by the protonated form of the strong non-nucleophilic Bronsted base. Thus, in each case, total carbonation at the O-H sites and total carboxylation at the N-H sites are made possible by the strong acceptance of protons from the Bronsted base. This complete use of alkanolamine nucleophilic sites increases their total CO2 sorption capacity beyond that achieved in the prior art. As indicated by the third equation above, a reaction of two moles of CO2 at each nucleophilic primary amine site is possible in the presence of the secondary base, thus making the use of alkanolamines with primary amino groups, such as ethanolamine, attractive.
    [0039] Using alkanolamines, such as monoethanolamine (MEA), diethanolamine (DEA) and triethanolamine (TEA), as shown above, the possibility
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    13/34 to form reaction products with stoichiometry 3: 1 CO2: alkanolamine is created, which is at least three times higher on a molar basis than the CO2 load achieved in current commercial reactors (1: 2 CO2: alkanolamine in the case of MEA). This approach can be extended to other alkanolamines, including N-methyl diethanolamine (CH3N (C2H4OH) 2, (MDEA)), hydroxyethyl ethylenediamine and others. If the structure has more than potentially nucleophilic sites, the potential for even higher CO2 stoichiometry: alkanolamine may exist, although possibly not fully realized in practice. The temperature stability of these reaction products (eg, absorption / desorption temperature) is generally less than the stability of regular and mixed carbamates and can be fine-tuned by varying the electronic effects and thus the nucleophilicity of the alcohol group and the non-nucleophilic nitrogenous base. The reduction of regeneration energy can be considered a benefit of these alkanolamine / base mixtures.
    [0040] Although alkanolamines alone are highly effective in the CO2 capture process, they are unable to undergo carbonation-0 at hydroxyl sites. The use of the strong, secondary, non-nucleophilic Bronsted base effectively promotes the oxygen carbonation reaction and can also act as a solvent in the sorbent medium.
    [0041] As shown in the equations above, a mechanism is postulated involving the reaction of a CO2 molecule, in each of the alkanolamine oxygen, in addition to reaction at primary and secondary amine sites. The nucleophilic group (s) attack the C = O group of CO2 to form a kind of intermediate alkylcarbonic acid, while nucleophilic attack on CO2 by the primary and secondary amine sites can occur in a similar way to form a kind of carbamic acid / intermediate zuitehon, which is in rapid internal balance with itself. The secondary non-nucleophilic base promotes the total formation of the alkylcarbonate in the oxygen and carbamate species in the nitrogens, by a mechanism that is hypothesized as deprotonation of the intermediate species with the secondary base acting in the role of a Bronsted base.
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    14/34 protons).
    [0042] Another advantage of this invention is that the resulting carbamate / alkylcarbonate products are expected to be less stable than regular carbamates, since the carbonate groups can first decompose at a lower temperature. This can allow decomposition of reaction products and CO2 regeneration at lower temperatures, saving energy for regeneration. The stability of carbamate / alkylcarbonate products can be tuned by varying the nucleophilicity of the alcohol group and the basicity of the secondary base. Adapting to the energetics and kinetics of an acid gas purification process, it is possible to use various strong alkanolamine / non-nucleophilic combinations (eg, guanidines, biguanidines, triazabicyclodecenes, amidines, imidazolines, pyrimidines) .
    [0043] Alcanolamines [0044] The nucleophilic function (Lewis base) for the initial reaction with CO2 is provided in the present process by an alkanolamine, that is, compounds containing one or more hydroxyl groups and one or more primary, secondary amino groups or tertiary. Substituting groups for the nitrogen (s) may include groups other than hydroxyalkyl, for example, alkyl, aryl, substituted alkyl or substituted aralkyl. The alkanolamines that are therefore considered include compounds such as monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEA), diglycolamine (DGA), 2-amino-2-methyl-1-propanol (AMP ), 2- (2-aminoethylamino) ethanol (AEE - HOC2H4NHC2H4NH2, also known as hydroxyethylethylenediamine, HEEDA), 2-amino-2-hydroxymethyl-1,3-propanediol (Tris), diisopropanolamine (DIPA) and tertiary ethoxyethanol (butyl) EETB).
    [0045] Secondary Base [0046] In addition to alkanolamine, the sorbent medium also contains one or more non-nucleophilic compounds, more strongly basic, which provide the Bronsted base function in the reaction to form carbamate and alkylcarbonate salts. This class of bases is represented generically by non-nucleophilic nitrogenous bases, having a pK a (as measured or predicted at 25 ° C in solution
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    15/34 aqueous or as a measure in another solvent and converted to an aqueous value) higher than that of the amine functionality of alkanolamine. The secondary backing will typically have a pKa value of at least 9.0, although higher values of 11.0 or at least 10.0, preferably at least 12.0, and most preferably at least 13.0 are favored by excellent promotion of the O-carbonation reaction. A useful way to make an adequate prediction of the base pKa value can be provided by the ACD / PhysChem Suite (a set of software tools for predicting basic physicochemical properties including pKa), available from Advanced Chemistry Development, Inc., 110 Yonge Street , Toronto, Ontario, Canada M5C 1Q4. Exemplary pKa values for a limited number of compounds (in dimethylsulfoxide) can be found in Bordwell's online pKa database, http://www.chem.wise.edu/areas/reich/pkatabel/index.htm.
    [0047] The strong base must be quite basic to influence the balance towards carbamate and alkylcarbonate products effectively, but on the other hand, not so strong that it stabilizes these products to the point that the reaction sequence becomes irreversible and the CO2 desorption becomes difficult or unworkable, p. eg due to an uneconomically high temperature requirement. Bases that are not acceptable are those that precipitate from the sorbent solution, or species that may influence the CO2 reaction chemistry (eg, hydroxide bases that form water in protonation). The base should preferably also not have the propensity to act as a competitor nucleophile in relation to CO2 under the conditions of the sorption process, although some degree of nucleophilicity can be tolerated.
    [0048] Nitrogenous non-nucleophilic bases, which can be used to promote carbonation-0 reactions and N-carboxylation include cyclic, multicyclic and acyclic structures such as imines, imines and heterocyclic amines, amidines (carboxamidines), such such as dimethylamidine, guanidines, thazabicyclodecenes, imidazolines and pyrimidines, including N, N-di (lower alkyl) carboxamidines, where the lower alkyl is preferably C1-C6 alkyl, Nmethyltetrahydropihmidine (MTHP), 1,8-diazabicycles [5.4.0 ] -undecene-7-ene (DBU),
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    1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene (MTBD), 1,5- diazabicycle [4.3.0] non-5-ene (DBN), substituted guanidines of formula (R 1 R 2 N) (R 3 R 4 N) C = NR 5 , where R 1 , R 2 , R 3 and R 4 are preferably lower alkyl (Ci-Ce) and R 5 is preferably H or lower alkyl (Ci-Ce), such as 1,1,3,3tetramethylguanidine and biguanidines. Other substituent groups for these compounds, such as alkyl, cycloalkyl, aryl, upper alkenyl and substituted alkyl and other structures, can also be used.
    [0049] The reaction of CO2 with reactive hydroxyl oxygen and the NH sites of nitrogens of the amino group is, as shown by the equations above, stoichiometric with one mole of the secondary base required to form the carbamate or alkylcarbonate entity at each of the hydroxyl or reactive amine of alkanolamine. The secondary base, therefore, will preferably be used on an equivalent 1: 1 nucleophilic base (nucleol base relative to the sum of each reactive hydroxyl group (nucleophilic) and each proton of the nucleophilic amine group (s) of the alkanolamine). Thus, for example, in the case of monoethanolamine with a reactive hydroxyl oxygen and two protons in the primary amino group, capable of participating in the nucleophilic reactions with CO2, at least threeols of the secondary base must be used per mol of ethanolamine. Similarly, a minimum ratio of 3: 1 is appropriate for thethanolamine (three reactive oxygen, one non-nuclear amino nitrogen). Diethanolamine with its two hydroxyl oxygen and an amino nucleophilic nitrogen must use a minimum molar ratio for the secondary base of 3: 1. With N-methyldiethanolamine, there are no non-nucleophilic amino nitrogen at the tertiary amine site, but two potentially reactive hydroxyl oxygen and, in this case, a molar ratio of at least 2: 1 is appropriate. The secondary base can, however, be used in excess if it is capable of reacting with only CO2 or desired for its use as a solvent. Although it is in principle possible to use less than one molar equivalent of non-nucleophilic base per amine site to generate the final carbamate product, since the intermediate products present in the carbamic acid of the carbamic acid / carbamate balance are neutral and thus , do not require a counterion for the formation of the final carbamate,
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    17/34 it was found that the formation of the carbonated-0 species increases and approaches 100% with higher secondary base ratios for alkanolamine, typically in the range of 3: 1 or 4: 1. Generally, therefore, the relative amount of the secondary base will be more than the minimum of 1 molar equivalent of strong base per reactive alkanolamine site, e.g. eg, 2: 1 or higher, if the full potential of chemanolization of alkanolamine is to be obtained. Due to tolerance, the relative proportions of the hydroxyl and nucleophilic amine sites should be made in establishing the secondary base ratio for alkanolamine. [0050] Solvent [0051] The amine / base mixture can be used as the pure liquid sorbent material, as long as it remains sufficiently liquid to be pumped and handled in the unit; with a molar excess of the non-nuclear secondary base normally being used in order to promote the carbonation / carboxylation reaction at each of the alkanolamine nucleophilic sites, the secondary base normally functioning as a solvent or co-solvent for alkanolamine. The existence of multiple potential reaction sites in alkanolamine, however, will create the potential for the production of CO2 sorption products in the form of gels with relatively high molecular weights and viscosities; Strong intermolecular interactions can also increase the viscosity of the sorbent medium. It may therefore be desirable to use a solvent to control the viscosity of the sorbent medium, so that it can readily circulate in the unit: the concentration of the alkanolamine / base in the solvent can be adjusted to maintain the desired viscosity of the solution as needed, particularly for the rich solution containing the sorbed CO2.
    [0052] The beneficial aspects of this invention can be obtained in both aqueous and non-aqueous solvents, however, more polar, non-aqueous aprotic solvents may be preferred in some embodiments. Polar solvents may be able to solvate the reaction products better when compared to solvents of lower polarity and thus minimize the tendency to form dimers in solution. A polar solvent can also increase absorption
    Petition 870190062486, of 07/04/2019, p. 21/42
    18/34 physics of CO2 in solution, thereby facilitating the increased load and capacity of the absorbent. These benefits are fully expected in water, with the added benefit of enabling the formation of bicarbonate with tertiary alkanolamines. Thus, an aqueous solution of a 1: 3 molar ratio of TEA and the strong non-nucleophilic base has the potential to capture four moles of CO2, three via carbonation-0 to form an equilibrium load balance of alkylcarbonate anions for three moles of base strong protonate, and a quarter mol per bicarbonate anion charge balanced by the protonated tertiary amine site. The bicarbonate formed at the tertiary amine site is less stable and, therefore, preferred over that which would be expected to form directly with the strong non-nucleophilic base in water. In addition, the use of aqueous alkanolamine solutions allows the present process to be readily adapted to application in existing commercial aqueous amine purification units.
    [0053] Polar non-aqueous solvents would be expected to be less corrosive, enabling the use of cheaper metallurgies, p. carbon steel, with little concern about corrosion at higher loads.
    [0054] A solvent such as toluene, with a relatively low dipole moment, can be found to be effective, although in general higher values for the dipole moment (Debye) of at least 2 and preferably at least 3 are preferred. Polar solvents, such as DMSO (dimethyl sulfoxide), DMF (N, Ndimethylformamide), NMP (N-methyl-2-pyrrolidone), HMPA (hexamethylphosphoramide), THF (tetrahydrofuran) and the like are preferred.
    [0055] Preferred solvents preferably have a boiling point of at least 65 ° C and, preferably, 70 ° C or higher, in order to reduce solvent losses in the process and higher boiling points are desirable, depending on the conditions regeneration that are to be used. The use of solvents with a higher boiling point will conserve valuable energy that would otherwise be consumed in vaporizing the solvent.
    [0056] Solvents that have been found effective in various extensions include toluene, sulfolane (tetramethylene sulfone) and dimethyl sulfoxide (DMSO). Other solvents
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    19/34 of suitable boiling point and dipole moment would include acetonitrile, N, Ndimethylformamide (DMF), tetrahydrofuran (THF), N-methyl2-pyrrolidone (NMP), propylene carbonate, dimethyl ethers of ethylene and propylene glycols, ketones such as methyl ethyl ketone (MEK), esters such as ethyl acetate and amyl acetate, and hydrocarbons such as 1,2-dichlorobenzene (ODCB). The dipole moments (D) and boiling points for selected solvents are:
    Dipole Moment (D) Boiling point(° C) Toluene 0.36 110.6 Sulfolane 4.35 285 DMSO 3.96 189 DMF 3.82 153 MEK 2.78 80 Acetonitrile 3.92 81 THF 1.63 66 ODCB 2.50 180.5
    [0057] Another possibility is the use of an ionic liquid as the solvent as an amine solvent in the associated CO2 sorption processes. Ionic liquids can themselves act as useful chemo-solvents for CO2 under the conditions contemplated for use in the present process and can therefore be useful in this role of adjunct. Many of them are non-flammable, non-explosive and have high thermal stability. They can also be recyclable, which can be useful in reducing environmental concerns through their use.
    [0058] A class of ionic liquids, which has been found to be useful as amine solvents and CO2 qumissorventes are the salts of imidazolium, benzimidazolium, imidazolidinium (4,5-dihydro-1 H-imidazolium) and thiazolium. Preferred anions to form salts with these cations are those in which the counter-ion conjugate acid has a pK a as measured or predicted at 25 ° C in aqueous solution (or as measured in another solvent and converted to an aqueous value, referred to as equivalent scale
    Petition 870190062486, of 07/04/2019, p. 23/42
    20/34 aqueous) of at least 0 and more preferably at least 2.0 or even as high as 4.0 or more. The anion of the liquid ionic salt will affect its ability to act as an agent for the capture of CO2, with more basic anions such as acetate and thiocyanate increasing the chemisorption and less basic anions, such as chloride, being less effective. The imidazolium salts, which have been found to work well as amine solvents and chemo-solvents for CO2 are the 1,3-dialkyl substituted imidazolium salts, with preference for the acetate salts as exemplified by 1-ethyl-3-methyl imidazókio acetate and 1-butyl-3-methyl imidazolium acetate, however other salts can be considered, such as those with halide, thiocyanate or lower alkyl chain carboxylate anions.
    [0059] Once the absorbent medium has been formulated with a combination of amine / base and the solvent, optionally with ingredients such as antioxidants, corrosion inhibitors and the like, it can be used, for example, in an absorption unit, such as illustrated in general lines in Figure 1. [0060] The concentration of alkanolamine, secondary non-nucleophilic nitrogenous base and solvent can vary over a wide range, usually from 5 or 10% to 90% w for alkanolamine / solvent base. Since the sorption temperature and the pK a of alkanolamine and the strong base can play the reaction equilibrium game, the optimum concentration can be determined empirically taking this into account together with the sorbent viscosity and other factors. In general, the total concentration of alkanolamine / base in the solvent will preferably be about 10% to about 50% w, or even less, for example, 10 to 30% w.
    [0061] The formation of precipitates is considered to be generally undesirable, since if precipitates are formed, the concentration of the active alkanolamine sorbent decreases and the amount of amine available for CO2 capture decreases correspondingly, even though the characteristic electronegative oxygen alkanolamines tend to make the CO2 reaction products more soluble.
    [0062] Solid Phase Operation
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    21/34 [0063] Although the present process may be suitable for operation in the liquid phase, the same chemistry can alternatively be conducted in the pores or on the surface of a solid porous support. This may involve impregnating a solution of the alkanolamine and strong non-nucleophilic base onto a porous support, or chemically grafting one or both of the alkanolamine and strong base onto the surface of the support by chemical reaction between the support material and the alkanolamine and / or base. Alternatively, an amine and / or base precursor can be used or a reactive compound containing the alkanolamine / base groups required to participate in the carbonation / carboxylation reactions. Common support materials may include coal (activated charcoal), as well as porous solid oxides of metals and metalloids and mixed oxides, including but not limited to alumina, silica, silica-alumina, magnesia and zeolites. Porous solid polymeric materials are also suitable, as long as they are resistant to the environment in which the sorption reaction is conducted. Discounting the presence of significant solvent effects in obtaining CO2 absorption in the liquid phase, the same chemistry will be applicable with alkanolamine and strong non-nucleophilic base in the solid support in the presence of CO2. Regeneration, in this case, would be achieved by operating in a temperature oscillation sorption mode, heating the solid containing the sorbed CO2 to decompose the CCte / mixed base reaction products on the support surface, to release the sorbed CO2. Heating can conveniently be carried out by passing a heated gas stream through the solid sorbent bed, usually in countercurrent to the direction of the initial gas stream; the purge gas can be supplied using an air stream from the purified gas stream. In this way, energy savings can be achieved by avoiding the need to heat large volumes of solution.
    [0064] As the components of the gas stream have relatively small molecular dimensions, the minimum pore size of the support is not itself a severely limiting factor, however, when basic nitrogenous compounds are impregnated, the inputs to the pore systems of small and intermediate pore size zeolites can become clogged by the
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    22/34 bulky component (s) of alkanolamine / base and, for this reason, are not preferred, especially with bases of relatively larger molecular dimensions. In order to minimize diffusion limitations, especially with bulky alkanolamine and / or base components, preferred porous solid support materials have relatively large pore sizes, with mesoporous and macropose materials being more suitable. Large pore zeolites may be suitable, depending on the dimensions of the amine and the secondary base. Amorphous pore solids, with a range of different pore sizes, are likely to be suitable, since at least some of the pores will have openings large enough to accept the basic component (s) and then leave sufficient access to the components of the gas stream. Supports containing highly acidic reaction sites, as with the most highly active zeolites, are more likely to be more susceptible to fouling reactions in the reaction with the nitrogen compound than less acidic species, and are therefore less likely to be preferred.
    [0065] A preferred class of solid oxide support consists of mesoporous and macroporous materials (as defined by IUPAC), for example, the M41S series silica compounds, including MCM-41 (hexagonal) and other mesoporous materials, such as SBA-15.
    [0066] Absorption / Desorption Conditions [0067] For absorption, the temperature is typically in the range of about 20 ° C to about 90 ° C, preferably from about 30 ° C to about 70 ° C. Although some mixed-base systems (alkanolamine plus secondary base) may have the ability to effectively absorb CO2 at temperatures above 50 ° C and even as high as about 90 ° C (with a preferred maximum of about 70 ° C), the stability of the alkanolamine / mixed base reaction products may allow operation of the sorption part of the cycle at relatively low temperatures, close to the environment or just above the environment, typically 15 to 70 ° C and, preferably, 20 to 50 ° Ç.
    [0068] The pressure during the sorption step is typically in the range of about
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    23/34
    0.1 bar to about 20 bar and in some cases from 0.1 to about 10 bar. The partial pressure of carbon dioxide in the gas mixture will vary according to the composition of the gas and the operating pressure, but will typically be from about 0.1 to about 20 bar, preferably from about 0.1 to about 10 bar. The low flue gas pressure, typically around 1 bar with partial CO2 pressure corresponding to about 0.1 bar, may impose a limitation on CO2 recovery, however the cost of compression is relatively high and compression is usually will not be favored with the present sorption process. The pressure when treating flue gas entering the combustion source at a low pressure is unlikely to exceed 1 bar. Natural gas is commonly at a higher pressure and can enter the treatment process at a pressure typically in the range of about 1 to about 150 bar, with the actual value selected being dependent on the pipe specifications and the extent to which it is desired to eliminate recompression after treatment. All references to pressure values in units of bars here are in absolute pressures, unless otherwise specifically stated.
    [0069] The gas mixture can be contacted countercurrent or concurrently with the absorbent material at an hourly space gas velocity (GHSV) of about 50 (S.T.P.) / Hour to about 50,000 (S.T.P.) / Hour.
    [0070] CO2 can in favorable cases be effectively desorbed by a reduction in the partial pressure of CO2. This can be accomplished by reduction with an inert (non-reactive) gas, such as nitrogen or a stream of natural gas; reducing temperatures at or near the sorption temperature is a preferred option for process savings, e.g. at a temperature of no more than 10, 20 or 30 ° C above the sorption temperature. Another option is to desorb the CO2 with pure co24 (previously isolated) at 1 atm or higher at high temperatures, typically above 100 to 120 ° C. The water removed from the amine / base solution at desorption temperatures above 100 ° C can be separated from CO2 in another separation step downstream by pressure oscillation operation, preferably at an elevated temperature above the ambient. Systems
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    24/34 heat exchangers staged with vapor-liquid separators, where water is removed first, followed by CO2 as a pressurized gas stream, can be used as an alternative. Selective CO2 capture from chains containing wet CO2, such as flue gas or wet natural gas, can be achieved. [0071] The stability of the reaction products can be such that isothermal (or almost isothermal) sorption / desorption is made possible by reducing the partial pressure of CO2 in the desorption step, p. eg by reduction with a non-reactive gas for example, at a temperature preferably not more than 30 ° C higher than the sorption temperature and, when a particularly favorable amine / base combination is used, it may be possible to obtain a sorption / desorption temperature differential of no more than 10 or 20 ° C. Typically, however, desorption is favored by an increase in the temperature of the solution, with desorption being faster with greater temperature differentials. In situations where a non-aqueous solvent is used, but water is present in the stream to be processed, regeneration may need to be carried out at a temperature sufficient to remove water and prevent build-up in the purification circuit. In such a situation, CO2 can be removed at pressures below atmospheric pressure, but above 100 ° C. For example, the regeneration temperature can be around 90 ° C, but to remove any water from the sorbent, temperatures in the range of 100 to 120 ° C may be required. Although this is less energetically favorable than desorption at temperatures below 100 ° C, it compares favorably to significantly higher temperatures of 140 to 175 ° C and higher used in conventional aqueous systems, where the additional energy required for desorption has imposed substantial operating costs.
    [0072] When these factors are considered, the temperature selected for desorption will typically be in the range of about 70 to about 120 ° C, preferably from about 70 or 90 to about 100 ° C and, more preferably, no more than about 90 ° C.
    [0073] The alkanolamine / mixed base sorbent system is not limited to removal
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    25/34 CO2, however, in view of the basic nature of amines, it is capable of removing other acid gases such as those typically found in flue gas and natural wellhead gas.
    [0074] The Examples below illustrate the promotion of the carbonation-0 reaction in alkanolamines by the secondary non-nucleophilic base component. Table 1 provides detailed information on the production of carbonation-0 and total CO2 load in a molar base of several alkanolamines in different molar ratios, with a secondary base (1,1,3,3-tetramethylguanidine, TMG). For alkanolamines with primary and / or secondary amines (MEA, DEA, HEDA), the total production of Ncarboxylation per molecule is also shown. As comparative examples, TaBELA 1 includes CO2 absorption data for single component alkanolamines (without a secondary base) in non-aqueous and aqueous solution.
    [0075] EXAMPLES [0076] Example 1. Absorption of carbonative CO2-0 with TEA / TMG sorbent system [0077] A solution of approximately 30% by weight of a molar mixture ~ 1: 3 of thethanolamine (TEA) and tetramethylguanidine (TMG ) was prepared in deDMSO in a ~ 5 mm NMR tube, equipped with a plastic cap. The NMR tube was placed inside a narrow hole Bruker Avance III 400 MHz NMR spectrometer with a QNP probe.
    [0078] After initial speciation and quantification of the prepared solution (Figure 2, top), CO2 was bubbled through (~ 1 atm, or partial pressure of ~ 100 kpa at ~ 5 cc / min, measured by a Brooks 5896 flow controller) through the room temperature solution outside the NMR spectrometer for approximately 5 hours. As illustrated in Figure 2, the initial spectra of the starting materials appeared to change with the addition of CO2. The peaks 13 and NMR at ~ 156.55 ppm (Figure 2, base) appeared to represent a carbonation of alcohol groups of TEA (e.g., -OCOO). At the same time, the C = N guanidinium resonance appeared to change to ~ 162.05 ppm and the structural peaks of the TEA appeared to split into ~ 62.42 / ~ 59.80 ppm and ~ 55.09 / ~ 57.79 ppm, respectively, with a molar ratio of ~ 80.6%:
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    26/34 ~ 19.4%. The peak 1 H NMR at ~ 8.36 ppm was attributed to the counter-ion -NH2- of the product (insertion in Figure 2, base). According to the structural peak division and integration of the reaction product peak (~ 156.55 ppm) versus the structural peaks, ~ 80.65 of the alcohol groups were carboxylated to provide a total CO2 charge of ~ 2.42 CO2 molecules per TEA molecule, or ~ 71.4 wt% TEA. The keys for the structures in Figure 2 (top) and Figure 2 (bottom) are shown in Figures 2A and 2B, respectively.
    [0079] The CO2-saturated TEA: TMG mixture was then exposed to a -5 cc / min N2 purge at room temperature in order to examine the stability of the reaction products. After ~ 2 hours under slow flow of N2, 13 c and 1 H NMR spectroscopy (not shown) confirmed that ~ 13.3% of the alcohol groups remained 0carbonated, to provide a total charge of ~ 0.40 CO2 by TEA. The TEA: CO2: TMG reaction products therefore appeared to be stable and to decompose at temperatures slightly above ambient. After ~ 8 hours under a slow flow of N2, ~ 96.7% of the alcohol groups appeared to be free of carbonation, which is believed to confirm almost complete desorption of CO2 at room temperature.
    [0080] A similar procedure was performed using a ~ 1: 4 mixture of TEA and TMG in DMSO-de. Peak 13 ca ~ 156.49 ppm is believed to represent carbonation of the alcohol groups of TEA (not shown). At the same time, the C = N guanidinium resonance appeared to change to ~ 162.40 ppm, apparently confirming the TMG reaction, and the structural TEA peaks appeared to split into ~ 62.41 / ~ 59.80 ppm and ~ 55 , 12 / -57.81 ppm, respectively, with a molar ratio of ~ 90.8%: ~ 9.2%. The 1 H NMR peak at ~ 8.50 ppm was attributed to the product's -NH2 4 · counterion (not shown). According to the integration of the peak of the reaction product (~ 156.49 ppm) through the divided structural peaks, ~ 90.8% of the alcohol groups were O-carboxylated to provide a total CO2 load of ~ 2.72 molecules of CO2 per TEA molecule, or -80.3% w of TEA.
    [0081] The TEA: TMG mixture saturated with CO2 was then exposed to an N2 plug at room temperature in order to examine the stability of the reaction products. After ~ 13 hours under N2 flow, only ~ 7.5% of the alcohol groups
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    27/34 remained O-carbonated, to provide a total charge of ~ 0.23 CO2 per TEA.
    [0082] Comparative Example C1. CO2 absorption with / TEA in aqueous / non-aqueous solutions [0083] A procedure similar to that described in Example 1 was performed using a ~ 15% wt solution of TEA in DMSO-de. After treatment by CO2 ~ 3 hours, both spectra 13 and M # 1 (not shown) did not seem to change, which indicated the lack of a chemical reaction between CO2 and TEA under non-aqueous conditions. A new resonance of 13 ca ~ 125.18 ppm is believed to reflect fisisorvide CO2 (presumably through hydrogen bonding interactions between -OH groups of TEA and O = C = O) with a charge of about 0.13 CO2 per TEA in average, or -3.8% w of TEA. This was about 21 times less than the CO2 load of TEA in TMG solution.
    [0084] A procedure similar to that described in Example 1 was performed using a ~ 15% wt solution of TEA in H2O. After CO2 Treatment for -2 hours, a new resonance was detected at 13 ~ C 160.28 ppm (not shown), which is believed to correspond to bicarbonate formation of the tertiary nitrogen of TEA (p. G., HCOO). Product peak integration at ~ 160.28 ppm versus structural peaks at ~ 55.55 and ~ 55.28 ppm provided an estimated total CO2 load of about 0.86 CO2 by TEA on average, or ~ 25.4% p of TEA. This was about 3 times less than the CO2 load of TEA in TMG solution.
    [0085] Example 2. Absorption of carbonative CO2-0 with DEA / TMG sorbent system [0086] A solution of approximately 30% w of a molar mixture of ~ 1: 3 of diethanolamine (DEA) and tetramethylguanidine (TMG) was prepared in de-DMSO in a ~ 5 mm NMR tube, equipped with a plastic cap and capillary immersion tube. After speciation and quantification of the prepared solution (Figure 3, top), CO2 was bubbled through the room temperature solution outside the NMR spectrometer for approximately 2 hours. The keys for the structures in Figure 3 (top) are shown in Figure 3A. As illustrated in Figure 3, the initial spectra
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    28/34 of the starting materials appeared to change with the addition of CO2.
    [0087] Peaks 13 and NMR at -161.78 (overlap with C = N guanidinium resonance), ~ 159.01 and ~ 156.71 ppm are believed to represent CO2 reaction products with DEA in the presence of TMG of strong base (Figure 3, base). The first peak at -161.78 ppm was assigned as a mixed carbamate formed on the secondary DEA amine (eg, -N-COO) with a CO2 charge of about 0.91 CO2 molecules per DEA. Two other peaks at ~ 156.71 and ~ 159.01 ppm seemed to show carbonation-0 (eg, -O-COO) of DEA alcohol groups with a CO2 charge of ~ 1.59 CO2 molecules per DEA (or ~ 0.79 CO2 molecules per single alcohol group). The 1 H NMR peak at ~ 8.89 ppm (insertion in Fig. 3 base) was attributed to all -NH2 4 · counterions of the products that are in equilibrium with residual -OH and -NH groups. In the DEA: TMG mixture, the total CO2 charge was ~ 2.50 CO2 molecules per DEA, or ~ 104.7 wt% DEA. The keys for the structures in Figure 3 (base) are shown in Figure 3B.
    [0088] The DEA: TMG saturated-CO2 mixture was then exposed to an N2 plug of ~ 5 cc / min at room temperature in order to examine the stability of the reaction products. After ~ 2 hours under N2 flow spectroscopy 13 C and 1 H - NMR (not shown) seem to confirm that ~ 6.3% of alcohol-carbonate groups remained 0 to provide a total load of 0.13 ~ CO2 DEA. The DEA carbonated-0 reaction products were therefore not found to be stable and appeared to be decomposable at temperatures slightly above ambient. At the same time, decomposition of the mixed carbamate from the secondary DEA amine (eg, -N-COO ') was not observed. The CO2 load in this type of product remained around 0.99 CO2 per DEA molecule, providing around 1.12 CO2 per DEA in both products.
    [0089] A similar procedure was performed using a ~ 1: 2 mixture of DEA and TMG in DMSO-de. Peaks 13 and NMR at ~ 162.41 (overlapping with C = N guanidinium resonance), ~ 158.97 and ~ 156.73 ppm were attributed to the formation of mixed carbamate in the secondary DEA amine (eg, -N-COO ') and carbonationO (eg, -O-COO') of the DEA alcohol groups, respectively. The 1 H NMR peak at
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    29/34 ~ 8.59 ppm (not shown) was assigned to all of the -NH2 + counterions of the products, which were believed to be in equilibrium with residual -OH and -NH groups. The total CO2 load of the combination of carbonation products N and O was calculated to be -2.08 CO2 per DEA, or -87.2% w of DEA.
    [0090] Comparative Example C2. CO2 absorption with DEA in simple non-aqueous solution [0091] A procedure similar to that described in Example 2 was performed using -15% wt DEA in DMSO-de solution. After CO2 treatment for -4 hours, a new 13 c NMR resonance was detected at -161.56 ppm (not shown). Detailed analysis of the 13 c and 1 H NMR spectra seemed to confirm the formation of carbamate / carbamic acid in the secondary amine group of DEA. The alcohol groups appeared to remain inactive due to the low basicity of the secondary amine. The total CO2 load at room temperature was about 0.61 CO2 per DEA, or -25.6% wt DEA. This was about 4 times less than the CO2 load of DEA with TMG in solution.
    [0092] Example 3. Absorption of O-Carbonative / N-Carboxylative CO2 with MEA / TMG sorbent system [0093] A solution of approximately 50% w of a -1: 3 molar mixture of monoethanolamine (MEA) and tetramethylguanidine (TMG) was prepared in de-DMSO in a -5 mm NMR tube equipped with a plastic cap and capillary immersion tube. After initial speciation and quantification of the prepared solution (Figure 4, top), CO2 was bubbled through the solution at room temperature for approximately 1 hour. As illustrated in Figure 4, the initial spectra of the starting materials appeared to change with the addition of CO2. The keys for the structures in Figure 4 (top) are shown in Figure 4A.
    [0094] Peaks 13 and NMR at -156.96 and -156.80 ppm, attributed to carbonation-0 products (eg, -O-COO ') of the alcohol group of MEA molecules in the presence of base TMG strong (Figure 4, base). Peaks at -162.67 and -157.93 ppm were attributed to the formation of mixed carbamate (eg, -N-COO) and formation of mixed dicarbamate (eg, OOC-N-C00 '), respectively , in the primary amine of
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    30/34
    MEA. The integration of the product peaks versus structural peaks at ~ 64.32 and ~ 62.38 ppm suggested complete carbonation-0 of all MEA molecules. At the same time, ~ 36.8% of MEA molecules appeared to form a single N-carbamate in the primary amine of MEA and the remaining ~ 63.2% formed a dicarbamate in the primary amine (see keys for the structures shown in Figure 4 (base ) in Figure 4B). The total CO2 load (including both carbonation-0 and N-carboxylation products) was about 2.63 CO2 molecules per MEA molecule, or ~ 189.7% wt MEA.
    [0095] A similar procedure was performed using a ~ 1: 2 mixture of MEA and TMG in DMSO-de. Peaks 13 and NMR at ~ 156.84 and ~ 156.70 ppm were attributed to carbonation-0 products (eg, -O-COO) of the alcohol group of MEA molecules in the presence of strong base TMG (not shown) ). Peaks at ~ 162.12 and ~ 157.89 ppm were attributed to the formation of mixed carbamate (eg, -N-COO) and the formation of mixed dicarbamate (eg, OOC-N-COO '), respectively , in the primary amine of MEA. The integration of the product peaks versus structural peaks at ~ 64.08 and ~ 62.31 ppm suggested carbonation-0 of ~ 74% of the MEA molecules. At the same time, carbonated-0 and MEA-free molecules appeared to react with CO2 through the carboxylation of primary amines, forming a single N-carbamate and a TMG dicarbamate (see keys for structures indicated in Figure 4 (base) in Figure 4B) . The total CO2 load (including both carbonation-0 and carboxylation-N products) was calculated to be about 1.92 CO2 molecules per molecule of MEA, or ~ 138.5 wt% MEA.
    [0096] A similar procedure was performed using a ~ 1: 1 mixture of MEA and TMG in DMSO-de. Peak 13 c NMR at ~ 156.97 ppm was attributed to carbonation-0 products (eg, -O-COO ') of the alcohol group of the MEA molecules, in the presence of strong base TMG (not shown). Peaks at ~ 161.25 and ~ 157.92 ppm appeared to indicate mixed carbamate formation (eg, -N-COO ') and mixed dicarbamate formation (eg, OOC-N-COO'), respectively , in the primary amine of MEA. The integration of the product peaks versus structural peaks at ~ 63.86 and ~ 62.42 ppm suggested carboxylation-0 of ~ 39% of the MEA molecules. At the same time,
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    31/34 carbonated-0 molecules and free MEA molecules appeared to react with CO2 through primary amine carboxylation, forming a single N-carbamate and TMG dicarbamate (see keys for structures shown in Figure 4 (base) in Figure 4B) . The total CO2 load (including both carbonation-0 and carboxylation-N products) was calculated to be about 1.48 CO2 molecules per molecule of MEA, or -106.7% w of MEA.
    [0097] Comparative Example C3. CO2 absorption with MEA in aqueous / non-aqueous solutions [0098] A procedure similar to that described in Example 3 was performed using a solution of -15% w of MEA in DMSO-de. After CO2 treatment for -3 hours, a new 13 c NMR resonance was detected at -161.07 ppm (not shown). Detailed analysis of 13 c and 1 H NMR spectra appeared to confirm the formation of carbamate / carbamic acid at the primary amine site of MEA. The alcohol groups appeared to remain inactive due to the low basicity of the primary amine. The total CO2 load at room temperature was about 0.68 CO2 molecules per MEA, or -49.9% wt MEA. This was about 4 times less than the CO2 load of MEA in TMG solution.
    [0099] A procedure similar to that described in Example 3 was carried out using a solution of -15% w of MEA in H2O. After CO2 treatment for -2 hours, two new 13 c NMR resonances were detected at -164.42 and -160.59 ppm (not shown), indicating formation of carbamate (eg, -N-COO) and bicarbonate (p. HCO3), respectively, in the primary amine of MEA. Integration of product peaks versus structural peaks provided a total CO2 load of about 0.85 CO2 molecules per MEA, or -61.3% w of TEA. This was about 3 times less than the CO2 load of MEA in TMG solution.
    [00100] Example 4. CO2 absorption with HEEDA / TMG sorbent system [00101] A solution of approximately 50% w of a -1: 3 molar mixture of hydroxyethyl ethylenediamine (HEED) and tetramethylguanidine (TMG) was prepared in deDMSO in a -5 mm tube, equipped with a plastic cap and capillary immersion tube. After speciation and quantification of the prepared solution, CO2 was
    Petition 870190062486, of 07/04/2019, p. 35/42
    32/34 bubbled through the solution at room temperature for approximately 1 hour. The initial spectra of the starting materials appeared to change with the addition of CO2.
    [00102] Peak 13 c NMR at ~ 156.95 ppm was attributed to carbonation-0 (eg, -O-COO products) of the alcohol group of HEEDA molecules in the presence of strong base TMG. Peaks at ~ 161.82 and ~ 157.91 ppm seemed to indicate mixed carbamate formation (eg, -N-COO) and mixed dicarbamate formation (eg, OOCN-C00 '), respectively, in the amines secondary and primary HEEDA. The integration of the product peaks versus structural peaks at ~ 62.91 and ~ 47.26 ppm suggested carbonation-0 of ~ 99% of HEEDA molecules. At the same time, secondary and primary amines of HEEDA molecules appeared to form a single N-carbamate and a dicarbamate product. The total CO2 load (including both carbonation-0 and N-carboxylation products) was estimated to be about 1.95 CO2 molecules per HEEDA molecule.
    [00103] A similar procedure was performed using a ~ 1: 6 mixture of HEEDA and TMG in DMSO-de. Peak 13 c NMR at ~ 156.71 ppm was attributed to carbonation-0 products (eg, -O-COO ') of the alcohol group of HEEDA molecules in the presence of strong base TMG (not shown). Peaks at -161.85 and ~ 157.87 ppm appeared to indicate mixed carbamate formation (eg, -N-COO ') and dicarbamate formation (eg, OOC-N-C00'), respectively, in HEEDA amines. The integration of the product peaks versus structural peaks at ~ 62.87 and ~ 46.50 ppm suggested carbonation-0 of ~ 78% of HEEDA molecules. At the same time, carbonated-0 and free HEEDA molecules appeared to react with CO2 through secondary and primary amine carboxylation, forming a single carbamate and a dicarbamate with TMG. The total CO2 load (including both carbonation-0 and N-carboxylation products) was estimated to be about 3.79 CO2 molecules per HEEDA molecule.
    [00104] Table 1 below summarizes the results of the Examples (the solvent is deDMSO, except where noted).
    [00105] Example 5. Steam-liquid balance of DMAE / TMG and CO2 in deposition 870190062486, from 07/04/2019, pg. 36/42
    33/34
    DMSO.
    [00106] A solution of approximately 63.3 wt% molar mixture of ~ 1: 1 dimethylaminoethanol (DMAE) and 1,1,3,3-tetramethylguanidine (TMG) in de-DMSO was heated to ~ 45 ° C and then treated with a continuous flow of ~ 1% vol CO2 in N2 at ~ 1 atm (~ 100 kPag), as described in the General Procedure. The solution was then treated with ~ 10% vol CO2 in N2 at ~ 1 atm (~ 100 kPag) and finally with ~ 100% vol CO2 at ~ 1 atm (~ 100 kPag). The CO2 equilibrium charge in these conditions was ~ 2.2, ~ 34.9 and ~ 67.6 mol%, respectively, and represented a vapor-liquid balance of dimethylaminoethanol / CO2 at ~ 10 mbar (~ 1 kPa), ~ 100 mbar (~ 10 kPa) and ~ 1 bar (~ 100 kPa) CO2 at -45 ° C.
    [00107] The same procedure was performed with a molar mixture of ~ 1: 1 of DMAE and TMG in DMSO-de solution at ~ 65 ° C and ~ 90 ° C. The monitoring results shown in Figure 5 indicated a strong temperature dependence on CO2 absorption capacity. This result seemed to confirm the low stability of the reaction product, which can be beneficial to obtain less regeneration energy.
    [00108] Table 1. Summary of the results of Examples 1-4.
    alkanolamine non-nucleophilic base relationshipmolar % molO-Carb(1) % mol N-Carb (2) mol% CO2 absorption by alkanolamine Triethanolamine(TEA) Tetramethylguanidine (TMG) 1: 3 80.6 0 242% TEA TMG 1: 4 90.8 0 272% TEA - - 0 0 3.8% (3) TEA - - 0 86 86% (5) diethanolamine(TEA) TMG 1: 3 79 91 250% TEA TMG 1: 2 55 97 208% TEA - - 0 61 61%
    Petition 870190062486, of 07/04/2019, p. 37/42
    34/34
    monoethanolamine (TEA) TMG 1: 3 100 163 263% TEA TMG 1: 2 74 118 192% TEA TMG 1: 1 39 109 148% TEA - - 0 68 68% TEA - - 0 85 (4) 85% (4) hydroxyethyl ethylenediamine(HEEDA) TMG 1: 3 99 96 195% HEEDA TMG 1: 6 78 301 379%
    1. mol% of Carbonation-Ο (eg, -O-COO) for each -OH alkanolamine group
    2. Mole% Carboxylation-N (eg, -N-COO 'and _ OOC-N-COO + ) by secondary or primary alkanolamine amine
    3. Physisorvious CO2
    4. Solvent H2O, chemical chemo-product CO2 in forms of carbamate (-N-COO - ... + H3N 4 ·) and bicarbonate (HCO2 ... + H3N 4 ·)
    5. Solvent H2O, chemical product as bicarbonate (HCO3 + ... + H3N 4 ·).
    权利要求:
    Claims (11)
    [1]
    1. Cyclic process for separating CO2 from a gas stream, said process being characterized by the fact that it comprises contacting the gas stream with an absorbent comprising a primary or secondary nucleophilic alkanolamine CO2 sorbent and a non-nucleophilic base, more strongly basic than said alkanolamine in terms of pKa, in a non-aqueous liquid solvent, to form a reaction product by oxygen carbonation (s) in the hydroxyl group (s) and nitrogen carboxylation (s) of the ) alkanolamine amine group (s) in order to absorb CO2 in the sorbent.
    [2]
    2. Process according to claim 1, characterized by the fact that it also includes the step of treating the absorbent containing the sorbed CO2 under conditions sufficient to cause desorption of at least a part of the CO2.
    [3]
    Process according to claim 2, characterized in that the non-nucleophilic base has a pKa, measured at 25 ° C in an aqueous solution, higher than the amine measured at 25 ° C in an aqueous solution and the solvent is a polar solvent, and wherein said treatment step comprises:
    (i) passing the absorbent liquid containing the sorbed CO2 to a desorption zone, to release CO2 from the absorbent liquid containing CO2 and regenerating the absorbent liquid by treating the absorbent containing the sorbed CO2 under conditions sufficient to cause the desorption of at least part CO2; and (ii) return the absorbent liquid from which the CO2 was released to the sorption zone.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the alkanolamine comprises: one or more nucleophilic hydroxyl groups and one or more amino groups; comprises one or more of monoethanolamine (MEA), diethanolamine (DEA), diglycolamine (DGA), 2-amino-2methyl-1-propanol (AMP), hydroxyethyl-ethylenediamine (HEEDA), 2-amino-hydroxymethyl1,3-propanediol ( Tris), diisopropanolamine (DIPA) and tertiary ethoxyethanol-butylamine (EETB): and / or comprises an alkanolamine with at least one primary amine group, which reacts with CO2 in at least some of its amine groups
    Petition 870190062486, of 07/04/2019, p. 39/42
    2/3 in a double carboxylation reaction, in which two moles of CO2 are absorbed by the reacting amine groups.
    [5]
    5. Process according to any of the preceding claims, characterized by the fact that the non-nucleophilic base: has a pKa, measured at 25 ° C in aqueous solution, higher than that of the alkanolamine amine site (s) , measured at 25 ° C in aqueous solution; has a pKa of at least 10, for example, at least 13; and comprises an amine, an imine, an amidine and / or a guanidine, such as 1,1,3,3-tetramethylguanidine.
    [6]
    Process according to any one of claims 1 to 5, characterized in that the gas stream is contacted with the absorber at an ambient temperature of 70 ° C, for example, from 20 ° C to 50 ° C or from 50 ° C to 70 ° C.
    [7]
    Process according to any one of claims 1 to 6, characterized in that the CO2 is desorbed from the absorbent containing the absorbed CO2 at a temperature of not more than 90 ° C, to cause desorption of at least part of the CO2 sorbed.
    [8]
    Process according to any one of claims 1 to 7, characterized in that the molar ratio of the non-nucleophilic base to the alkanolamine is at least one mole of the non-nucleophilic base for each of the group (s) ( s) amine and hydroxyl reactive (s) of alkanolamine.
    [9]
    Process according to any one of claims 1 to 8, characterized in that both the alkanolamine and the non-nucleophilic base are integrated in a porous support, optionally comprised of carbon, alumina, silica, silica-alumina, magnesia, titania, zeolites, solid porous polymers or a combination of them.
    [10]
    Process according to any one of claims 1 to 9, characterized in that the solvent is selected from the group consisting of toluene, sulfolane (tetramethylene sulfone), DMSO (dimethyl sulfoxide); acetonitrile, Ν, Ν-dimethylformamide (DMF), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), propylene carbonate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether,
    Petition 870190062486, of 07/04/2019, p. 40/42
    3/3 methyl ethyl ketone (MEK), ethyl acetate, amyl acetate, 1,2-dichlorobenzene (ODCB).
    [11]
    Process according to any one of claims 1 to 10, characterized in that the solvent is toluene, sulfolane (tetramethylene sulfone) or DMSO (dimethyl sulfoxide).
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    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
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    2019-07-16| B06G| Technical and formal requirements: other requirements|Free format text: NA PETICAO DE RESPOSTA AO PARECER DE EXIGENCIA DE PRE-EXAME (PETICAO 870190062486, DE 04/07/2019) FORAM APRESENTADAS 11 REIVINDICACOES. CONTUDO, NO PEDIDO DE EXAME (PETICAO 800140130240, DE 13/06/2014) FOI REQUISITADO O EXAME PARA APENAS 10 REIVINDICACOES, TENDO SIDO RECOLHIDA A TAXA RELATIVA AO EXAME DE 10 REIVINDICACOES.ASSIM SENDO, CONFORME A IN INPI/DIRPA NO 03 DE 30/09/2016, O DEPOSITANTE DEVERA COMPLEMENTAR A RETRIBUICAO RELATIVA AO PEDIDO DE EXAME DO PRESENTE PEDIDO, DE ACORDO COM TABELA VIGENTE, REFERENTE A(S) GUIA(S) DE RECOLHIMENTO 0000921404549527 (PETICAO 870190062486, DE 04/07/2019). |
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    优先权:
    申请号 | 申请日 | 专利标题
    US38135110P| true| 2010-09-09|2010-09-09|
    US38129410P| true| 2010-09-09|2010-09-09|
    US38128110P| true| 2010-09-09|2010-09-09|
    US42104810P| true| 2010-12-08|2010-12-08|
    US42096010P| true| 2010-12-08|2010-12-08|
    US42097810P| true| 2010-12-08|2010-12-08|
    PCT/US2011/051037|WO2012034040A1|2010-09-09|2011-09-09|Alkanolamine co2 scrubbing process|
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