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    • 专利摘要:
    AQUEOUS ALKANOLAMINE SOLUTION AND PROCESS TO REMOVE ACID GASES FROM A GAS MIXTURE The present invention relates to an aqueous solution of alkanolamine for the removal of hydrogen sulfide from gas mixtures containing hydrogen sulfide. The aqueous alkanolamine solution comprises (i) an amino compound having the formula R1R2NCH2CH (OH) CH2OH, where R1 and R2 independently represent lower alkyl groups of 1 to 3 carbon atoms, (ii) piperazine and (iii) optionally a solvent physical, and that solution does not contain a strong acid. In addition, the present invention relates to a process for removing hydrogen sulfide from a gas mixture containing hydrogen sulfide, and additionally other acid gases, if present, for example, carbon dioxide, comprising the step of contacting the gas mixture containing hydrogen sulfide with the aqueous alkanolamine solution, preferably the temperature of the aqueous alkanolamine solution is equal to or greater than 140ºF. Examples of gas mixtures include natural gas, synthesis gas, waste gas, and refinery gas.
    公开号:BR112014029375B1
    申请号:R112014029375-9
    申请日:2013-06-06
    公开日:2021-01-12
    发明作者:Christophe R. Laroche；Gerardo Padilla；Timothy D. Halnon
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    Technical field
    The present invention relates to a composition comprising an aqueous solution of piperazine and alkanolamine, preferably 3- (dimethylamino) -1,2-propanediol, and to a process for using said aqueous composition to remove acid gases, including H2S, of gas mixtures containing H2S. History of the Invention
    [002] Fluid streams from natural gas, oil or coal reservoirs often contain a significant amount of acid gases, for example, carbon dioxide (CO2), hydrogen sulfide (H2S), sulfur dioxide (SO2), carbon disulfide (CS2), hydrogen cyanide (HCN), carbonyl sulfide (COS) or mercaptans as impurities. Said fluid streams can be gaseous, liquid or mixtures thereof, for example, gases such as natural gas, refinery gas, hydrocarbon gases from shale pyrolysis, synthesis gas, and the like or liquids, such as liquefied petroleum gas (LPG) and natural gas liquids (NGL).
    [003] Various compositions and processes for removing acid gases are known and described in the literature. It is well known to treat gas mixtures with aqueous amine solutions to remove these acid gases. Typically, the aqueous amine solution contacts the gas mixture comprising the acid gases in countercurrent at low temperature or high pressure in an absorption tower. The aqueous amine solution commonly contains an alkanolamine, such as triethanolamine (TEA), methyldiethanolamine (MDEA), diethanolamine (DEA), monoethanolamine (MEA), diisopropanolamine (DIPA) or 2- (2-aminoethoxy) ethanol (sometimes referred to as diglycolamine or DGA). In some cases, an accelerator is used in combination with alkanolamines, for example, piperazine and MDEA as described in USP 4,336,233; 4,997,630; and 6,337,059, all of which are incorporated herein by reference in their entirety. Alternatively, EP 0134948 describes mixing an acid with selected alkaline materials, such as MDEA, to provide increased removal of acid gas.
    [004] Tertiary amines, such as 3-dimethylamino-1,2-propanediol (DMAPD), have demonstrated their effectiveness in removing CO2 from gas mixtures, see USP 5,736,116. In addition, in specific processes, such as the Girbotol Process, tertiary amines have demonstrated their effectiveness in removing H2S, although they have reduced capacity at elevated temperatures, as observed, for example, in “Organic Amines-Girbotol Process”, Bottoms, RR, The Science of Petroleum, volume 3, Oxford University Press, 1938, pags. 1810-1815.
    [005] Although the above compounds are effective, they have limitations that restrict their universal use. In particular, it would be desirable to have an aqueous composition comprising an alkanolamine to remove acid gases, including H2S from a gas mixture and / or an aqueous solution of alkanolamine, which is efficient in removing acid gases, at a commercially viable level when the aqueous solution is used at an elevated temperature, for example, above 60 ° C (140 ° F).
    [006] As such, there is a need for an aqueous absorbent composition and method for using said composition, which is effective in removing acid gases, including hydrogen sulfide from gas mixtures, preferably at elevated operating temperatures. Summary of the Invention
    [007] The present invention is a composition of aqueous alkanolamine solution and a process that uses said composition of aqueous alkanolamine solution to remove acid gases, including hydrogen sulfide by contact with gas mixtures containing hydrogen sulfide, preferably when the temperature of the aqueous alkanolamine solution is equal to or greater than 60 ° C (140 ° F), said composition comprising (i) an amino compound, preferably in an amount of 0.1 to 75 weight percent, having the following general formula:
    where R1 and R2 independently represent lower alkyl groups of 1 to 3 carbon atoms, for example, methyl, ethyl, propyl and isopropyl groups, more preferred R1 and R2 groups include methyl and ethyl groups, especially preferred amino compounds include 3- ( dimethylamino) -1,2-propanediol, where R1 and R2 are both methyl groups, and 3- (diethylamino) -1,2-propanediol where R1 and R2 are both ethyl groups; (ii) piperazine, preferably in an amount of 0.1 to 15 weight percent; and (iii) optionally a physical solvent, preferably selected from cyclotetramethylenesulfone, polyethylene glycol dimethyl ethers, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, Nformylmorpholine, N-acetylmorpholine, triethylene monomethyl ether glycol, or mixtures thereof, where weight percentages are based on the total weight of the aqueous alkanolamine solution, said aqueous alkanolamine solution not containing an acid with a pKa of 8 or less or an acid-forming material capable of forming , in aqueous medium, with a pKa of 8 or less.
    [008] In one embodiment of the present invention, the amino compound (i) is preferably 3- (dimethylamino) -1,2-propanediol or 3- (diethylamino) -1,2-propanediol.
    [009] In one embodiment of the present invention, the process further comprises the step of steam extracting the aqueous alkanolamine solution, so that an aqueous solution of alkanolamine low in acid gas is formed and can be used in said contact step . Brief Description of Drawings
    [010] Figure 1 illustrates a process flow diagram of an absorption process according to the present invention; and
    [011] Figure 2 is a graph of H2S concentration in a mixture of purified gas versus absorbent circulation rate. Detailed description of the Invention
    [012] The aqueous alkanolamine solution of the present invention comprises an amino compound and piperazine. The amino compounds useful in the aqueous alkanolamine solutions of the present invention have the following formula:
    where R1 and R2 independently represent lower alkyl groups of 1 to 3 carbon atoms, for example, methyl, ethyl, propyl and isopropyl groups. More preferred groups R1 and R2 include methyl and ethyl groups. Especially preferred amino compounds include 3- (dimethylamino) -1,2-propanediol, where R1 and R2 are both methyl groups, and 3- (diethylamino) -1,2-propanediol where R1 and R2 are both ethyl groups.
    [013] The aqueous alkanolamine solution of the present invention contains alkanolamine in an amount equal to or greater than 0.1 weight percent, preferably equal to or greater than 5 weight percent, more preferably equal to or greater than 10 weight percent. weight and even more preferably equal to or greater than 20 weight percent, where the weight percentage is based on the total weight of the solution. The aqueous alkanolamine solution of the present invention contains the alkanolamine in an amount equal to or less than 75 weight percent, preferably equal to or less than 65 weight percent, more preferably equal to or less than 55 weight percent and even more preferably equal to or less than 50 weight percent, where the weight percentage is based on the total weight of the aqueous solution.
    [014] The aqueous alkanolamine solution of the present invention contains piperazine in an amount equal to or greater than 0.1 weight percent, preferably equal to or greater than 1 weight percent, more preferably equal to or greater than 2 weight percent, the weight percentage being based on the total weight of the aqueous solution. The aqueous alkanolamine solution of the present invention contains piperazine in an amount equal to or less than 20 weight percent, preferably less than or equal to 15 weight percent, more preferably equal to or less than 10 weight percent, and even more preferably equal or less than 8 weight percent, where the weight percentage is based on the total weight of the solution.
    [015] The aqueous absorbent composition of the present invention can optionally contain one or more additional amino compounds. Preferably, the additional amino compound is a second or different alkanolamine not described by formula (1) above, such as tris (2-hydroxyethyl) amine (triethanolamine, TEA); tris (2-hydroxypropyl) amine (triisopropanol); tributanolamine; bis (2-hydroxyethyl) methylamine (methyldiethanolamine), MDEA); 2- diethylaminoethanol (diethylethanolamine, DEEA); 2-dimethylaminoethanol (dimethylethanolamine, DMEA); 3-dimethylamino-1-propanol; 3-diethylamino-1-propanol; 2- diisopropylaminoethanol (DIEA); N, N-bis (2-hydroxypropyl) methylamine (methyldiisopropanolamine, MDIPA); N, N-bis (2-hydroxyethyl) piperazine (dihydroxyethylpiperazine, DiHEP)); diethanolamine (DEA); 2- (tert-butylamino) ethanol; 2- (tert-butylaminoethoxy) ethanol; or 2-amino-2-methylpropanol (AMP), 2- (2-amino-ethoxy) ethanol.
    [016] Preferred additional amino compounds comprise one or more tertiary amino groups.
    [017] Preferably, the additional amino compound has one or more sterically hindered amino groups. An aqueous absorption composition comprising a 1-hydroxyethyl-4-pyridylpiperazine compound and an amine having one or more sterically hindered amino groups is particularly suitable for the removal of H2S.
    [018] If present, the amount of optional amino compound in the aqueous alkanolamine solution can vary from a value equal to or greater than 0.1 weight percent, preferably equal to or greater than 1 weight percent, more preferably equal to or greater than 5 percent by weight based on the total weight of the solution. If present, the amount of optional amino compound in the aqueous alkanolamine solution can vary from 75 percent by weight or less, preferably less than 50 percent by weight, more preferably less than 25 percent by weight, based on the total weight of the solution.
    [019] The temperature of the aqueous alkanolamine solution that is brought into contact with the gas to be treated is equal to or greater than 120 ° F, preferably equal to or greater than 130 ° F, more preferably equal to or greater than 60 ° C (140 ° F), and even more preferably equal to or greater than 65.6 ° C (150 ° F).
    [020] In addition to the amino compound and piperazine, the aqueous alkanolamine solution may comprise one or more other compounds used in fluid treatment following well-known practices. Illustrative compounds that can optionally be provided include, but are not limited to one or more of the following: antifoaming agents; physical solvents that include glycols and the mono- and diethers or esters thereof, aliphatic acid amides, N-alkylated pyrrolidones, sulfones, sulfoxides, and the like; antioxidants; corrosion inhibitors; film formers; chelating agents such as metals; pH adjusters, such as alkaline compounds; and the like. The number of these optional components is not critical, but can be provided in an effective amount following known practices.
    [021] In addition to the amino compound, piperazine, and one or more other optional compounds used in fluid treatment, the aqueous alkanolamine solution may comprise a physical solvent. Preferably, a solvent such as cyclotetramethylenesulfone (available as SULFOLANE), polyethylene glycol dimethyl ethers (available as SELEXOL from The Dow Chemical Company) and triethylene glycol monomethyl ether (TGME or METOXITRIGLICOL from The Dow Chemical Company), 1,3-dimethyl- 3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N-formylmorpholine, N-acetylmorpholine or mixtures thereof.
    [022] If present, the amount of physical solvent in the aqueous alkanolamine solution may be present in an amount equal to or greater than 1 weight percent, preferably equal to or greater than 5 weight percent, more preferably equal to or greater than 10 weight percent, based on the total weight of the solution. If present, the amount of physical solvent in the aqueous alkanolamine solution may be present in an amount equal to or less than 75 weight percent, preferably equal to or less than 65 weight percent, more preferably equal to or less than 50 percent by weight, based on the total weight of the solution.
    [023] The aqueous alkanolamine solutions of the present invention do not contain an acid or acid-forming material, preferably the acids and acid-forming materials are those characterized as strong acids that include any organic or inorganic acid having a pKa of 8 or less, preferably 7 or less, more preferably 6 or less. Examples of acids that are excluded include phosphoric acid, phosphorous acid, hydrochloric acid, sulfuric acid, sulfurous acid, nitrous acid, pyrophosphoric acid, tellurous acid, and the like. Organic acids too, such as acetic acid, formic acid, adipic acid, benzoic acid, n-butyric acid, chloroacetic acid, citric acid, glutaric acid, lactic acid, malonic acid, oxalic acid, o-phthalic acid, succinic acid, o-toluic and the like are excluded from the aqueous alkanolamine solutions of the present invention. In addition, acid-forming materials that are capable of forming acids upon contact with water cannot be present in the aqueous alkanolamine solutions of the present invention.
    [024] The invention cited here finds wide application in the petrochemical and energy industries. For example, the present invention can be used for the treatment of streams of fluid, gas, liquid, or mixtures, in an oil refinery, in the treatment of acid gas, in the treatment of coal vapor gas, in the treatment of harmful emissions chimneys, in the treatment of landfill gases, and a new series of devices that control emissions harmful to human security.
    [025] The fluid streams to be treated by the process of the present invention contain an acid gas mixture that includes H2S and that can include other gases such as CO2, N2, CH4, C2H6, C3H8, H2, H2O, COS, HCN, NH3, O2, mercaptans, and the like. Often, such gas mixtures are found in flue gases, refinery gases, city gas, natural gas, synthesis gas, waste gas, aqueous gas, propane, propylene, heavy hydrocarbon gases, etc. The aqueous alkanolamine solution is particularly effective when the fluid stream is a gaseous mixture, obtained, for example, from shale oil retort gas, coal or heavy oil gasification with thermal air / steam or oxygen / steam conversion of heavy residual oil in lower molecular weight liquids and gases, or in residual gas purification operations in a sulfur plant.
    [026] The process of the present invention is preferably used to remove H2S from a gas stream comprising H2S and CO2, optionally in the presence of one or more other acid gas impurities, such as, for example N2, CH4, C2H6, C3H8, H2, CO, H2O, COS, HCN, NH3, O2 and / or mercaptans. However, the present invention can be used to remove H2S, CO2 and one or more of N2, CH4, C2H6, C3H8, H2, CO, H2O, COS, HCN, NH3, O2 and / or mercaptans from a gas stream comprising H2S , CO2 and one or more of SO2, CS2, HCN, COS and / or mercaptans.
    [027] The absorption step of the present invention generally involves contacting the fluid stream, preferably gas mixture, with the aqueous alkanolamine solution in any suitable contact vessel, for example, representative absorption processes, see USP 5,736,115 and 6,337 .059, both of which are incorporated herein by reference in their entirety. In these processes, the fluid stream containing H2S and / or other impurities from which acidic gases must be removed, can be placed in close contact with the aqueous solution of alkanolamine using conventional means, such as a tower or container equipped, for example, with rings or sieve plates, or a bubbling reactor.
    [028] In a typical mode of practice of the invention, the absorption step is conducted by feeding the fluid stream to the lower portion of the absorption tower, while fresh aqueous alkanolamine solution is fed to the upper region of the tower. The fluid stream, largely released from H2S and CO2, if present, emerges from the upper portion (sometimes referred to as treated or purified gas) of the tower, and the charged aqueous alkanolamine solution, which contains the absorbed H2S and CO2, emanates from the tower nearby or at its bottom. Preferably, the inlet temperature of the absorbent composition during the absorption step is in the range of 48.9 ° C (120 ° F) to 98.9 ° C (210 ° F), and more preferably 60 ° C (140 ° F) F) at 93.3 ° C (200 ° F) and, more preferably, from 60 ° C (140 ° F) to 93.3 ° C (200 ° F). Pressures can vary widely; Acceptable pressures are between 5 and 2,000 pounds per square inch (psi), preferably 20 to 1,500 psi, and most preferably 25 to 1,000 psi in the absorber. The contact occurs under conditions such that the H2S is preferably absorbed by the solution. The absorption conditions and apparatus are designed to minimize the residence time of the aqueous alkanolamine solution in the absorber to reduce CO2 uptake, while at the same time maintaining sufficient residence time of the fluid stream with the aqueous absorbent composition to absorb an amount maximum H2S gas. Fluid streams with low partial pressures, such as those found in thermal conversion processes, require less of the aqueous alkanolamine solution under the same absorption conditions as fluid streams with higher partial pressures, such as retort gases of shale oil.
    [029] A typical procedure for the H2S removal phase of the process involves absorbing H2S via countercurrent contact of a gas mixture containing H2S and CO2 with the aqueous solution of the alkanolamine of the amino compound in a column containing a plurality of trays at one temperature of at least 120 ° F, and a gas velocity of at least 0.3 feet per second (feet / sec), based on the “active” or aerated tray surface, depending on the operating pressure of the gas, said column tray having less than 20 contact trays, with, for example, 4 to 16 trays being typically employed.
    [030] After contacting the fluid stream with the aqueous alkanolamine solution, which becomes saturated or partially saturated with H2S, the solution can be at least partially regenerated so that it can be recycled back to the absorber. As with absorption, regeneration can occur in a single liquid phase. The regeneration or desorption of the acidic gases from the aqueous alkanolamine solution can be carried out by conventional means of heating, expansion, extraction with an inert fluid, or a combination thereof, for example, reducing the pressure of the solution or increasing the temperature until the point at which the absorbed H2S evaporates, or by passing the solution to a container of construction similar to that used in the absorption step, in the upper portion of the container, and passing an inert gas, such as air or nitrogen or preferably steam. upwardly through the container. The temperature of the solution during the regeneration step should be in the range of 48.9 ° C (120 ° F) to 98.9 ° C (210 ° F) and preferably 60 ° C (140 ° F) to 93.3 ° C (200 ° F), and the solution pressure at regeneration should vary from 0.5 psi to 100 psi, preferably from 1 psi to 50 psi. The aqueous alkanolamine solution, after being purified from at least a portion of the H2S gas, can be recycled back to the absorption container. If necessary, reprocessing absorbent can be used.
    [031] In a preferred regeneration technique, the aqueous solution of alkanolamine rich in H2s is sent to the regenerator where the absorbed components are removed by steam, generated by boiling the solution. The pressure in the flashing drum and extractor is generally 1 psi to 50 psi, preferably 15 psi to 30 psi, and the temperature is typically in the range of 120 ° F to 340 ° F, preferably 170 ° F to 250 ° F. Extractor and flashing temperatures will obviously depend on the extractor pressure; thus, at extractor pressures from 15 psi to 30 psi, the temperature will be 170 ° F to 250 ° F during desorption. The heating of the solution to be regenerated may be duly affected by indirect heating with low pressure steam. However, it is also possible to use direct steam injection. The resulting aqueous solution of alkanolamine poor in hydrogen sulfide can be used to contact a gas mixture containing H2S.
    [032] Preferably, the purified gas contains an amount equal to or less than 10 ppm H2S, meeting some environmental requirements, more preferably equal to or less than 4 ppm H2S, meeting typical specifications for plumbing / ducts.
    [033] A preferred embodiment of the present invention involves conducting the method of the present invention continuously, or as a continuous process. However, the method can be conducted in batches or semi-continuously. The choice of the type of process used must be determined through the conditions, equipment used, and the amount of gaseous current, and other factors evident for those skilled in the art, based on this description. Examples
    [034] Examples 1 to 9 are an aqueous amine absorbent solution comprising an alkanolamine, deionized water, and optionally a second amine, the amounts are in parts by weight based on the total weight of the absorbent composition. A gas stream comprising a synthetic mixture containing 4.2 percent H2S, 16 percent CO2 and 79.8 percent N2, where the percentage is percent by volume, is treated in a pilot scale absorber to remove the H2S and CO2. For each aqueous amine absorbent solution, the gas stream is treated at three different flow rates. The compositions, process parameters, and residual levels of H2S and CO2 for Examples 1 to 9 are listed in Table 1. In Table 1:
    [035] "DGA" is 98% 2- (2-aminoethoxy) ethanol from Acros Organics;
    [036] “MDEA” is 98% methyldiethanolamine from The Dow Chemical Company;
    [037] "DMAPD" is 98% 3-dimethylamino-1,2-propanediol from AK Scientific;
    [038] "Piperazine" is 99% piperazine from Aldrich Chemical.
    [039] An aqueous amine absorbent solution is introduced into the absorber on a pilot scale Fig. 1 via supply line 5 to the upper portion of an absorption column with a bed loaded with counter-current liquid gas 2. The gas stream is introduced by feed line 1 to the bottom of column 2 at a gas flow rate of 10 liters per minute. The absorber pressure is adjusted to 238 psia. Clean gas (ie reduced amounts of H2S and CO2) is discharged to the top of absorber 2 via line 3 and residual levels of H2S and CO2 are determined by gas chromatography (GC) analysis. The aqueous amine solution is loaded with flows of H2S and CO2 in the lower portion of the absorber, and egress through line 4.
    [040] The aqueous amine in line 4 has its pressure reduced by the level 8 control valve and flows through line 7 to the heat exchanger 9, which heats the loaded aqueous solution. The hot, rich solution enters the upper portion of the regenerator 12 via line 10. The regenerator 12 is equipped with a random fill / charge that performs the desorption of H2S and CO2 gases. The regenerator pressure is set to 17 psia. The gases are passed through line 13 to condenser 14 where cooling and condensation of any residual water and amine occurs. The gases enter a separator 15 where the condensed liquid is separated from the vapor phase. The condensed aqueous solution is pumped via pump 22 through line 16 to the upper portion of the regenerator 12. The remaining condensation gases are removed by line 17 for collection and / or final disposal. The regenerated aqueous solution flows through the regenerator 12 and closed coupled cooler 18. Cooler 18, equipped with an electric heating device, vaporizes a portion of the aqueous solution to remove any residual gases. The vapors emerge from the cooler and are returned to the regenerator 12 which are mixed with the falling liquid and then egress through line 13 to enter the condensation stage of the process. The regenerated aqueous solution from the cooler 18 exits the line 19 and is cooled in the heat exchanger 20, and then pumped via pump 21 back to the absorber 2 via the supply line 5.
    [041] The flow rate for the aqueous amine absorber is determined by slowly adjusting it down until the amount of H2S in the purified gas line 3 shows a dramatic increase.
    [042] The results for Examples 1 to 9 are graphically represented in the graph shown in Fig. 2. H2S levels, in parts per million by volume (ppmv), are plotted against the amine flow rate in cubic centimeters per minute (cc / min).
    权利要求:
    Claims (4)
    [0001]
    1. Process for removing hydrogen sulfide from a gas mixture comprising hydrogen sulfide, said process characterized by the fact that it consists of the steps of: A) contacting the gas mixture with an aqueous solution of alkanolamine, providing an aqueous solution of alkanolamine hydrogen sulfide and a clean gas, the aqueous alkanolamine solution consisting of: (i) 3- (dimethylamino) -1,2-propanediol; (ii) piperazine; (iii) optionally a physical solvent selected from cyclotetramethylene sulfone, polyethylene glycol dimethyl ethers, 1,3-dimethyl-3,4,5,6-tetrahydro-2- (1H) - pyrimidinone, N-formylmorpholine, N -acetylmorpholine, or mixtures thereof; said aqueous alkanolamine solution does not contain an acid having a pKa of 8 or less, or an acid forming material capable of forming, in aqueous medium, an acid having a pKa of 8 or less; B) optionally, extract steam from the aqueous solution of alkanolamine loaded with hydrogen sulfide, providing an aqueous solution of alkanolamine low in acid gas; and C) optionally contacting the gas mixture in step (A) with the aqueous solution of alkanolamine poor from acidic gas from step (B).
    [0002]
    2. Process according to claim 1, characterized by the fact that: (i) 3- (dimethylamino) -1,2-propanediol is present in an amount of 0.1 to 75 weight percent; and (ii) the piperazine is present in an amount of 0.1 to 15 weight percent; the weight percentage being based on the total weight of the aqueous alkanolamine solution.
    [0003]
    Process according to claim 1, characterized in that the physical solvent is present in an amount of 1 to 75 weight percent based on the total weight of the aqueous alkanolamine solution.
    [0004]
    4. Process according to claim 1, characterized in that the temperature of the aqueous alkanolamine solution in step (A) is equal to or greater than 60 ° C (140 ° F).
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    同族专利:
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-04-28| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2020-11-03| B09A| Decision: intention to grant|
    2021-01-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261666332P| true| 2012-06-29|2012-06-29|
    US61/666,332|2012-06-29|
    PCT/US2013/044467|WO2014004019A1|2012-06-29|2013-06-06|Aqueous alkanolamine absorbent composition comprising piperazine for enhanced removal of hydrogen sulfide from gaseous mixtures and method for using the same|
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