WO2012125894A2 - Inhibiteurs d'oxydation pour la dégradation d'amines - Google Patents

Inhibiteurs d'oxydation pour la dégradation d'amines Download PDF

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WO2012125894A2
WO2012125894A2 PCT/US2012/029367 US2012029367W WO2012125894A2 WO 2012125894 A2 WO2012125894 A2 WO 2012125894A2 US 2012029367 W US2012029367 W US 2012029367W WO 2012125894 A2 WO2012125894 A2 WO 2012125894A2
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acid
amine
chelating agents
methylene phosphonic
mea
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WO2012125894A3 (fr
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Alexander K. VOICE
Gary T. Rochelle
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University of Texas System
University of Texas at Austin
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University of Texas System
University of Texas at Austin
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/386—Polyphosphonic acids containing hydroxy substituents in the hydrocarbon radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/10—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with one amino group and at least two hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C07C59/265—Citric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/202—Alcohols or their derivatives
    • B01D2252/2023—Glycols, diols or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20405—Monoamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20442—Cyclic amines containing a piperidine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20436—Cyclic amines
    • B01D2252/20447—Cyclic amines containing a piperazine-ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B01D2252/20484—Alkanolamines with one hydroxyl group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B01D2252/20478—Alkanolamines
    • B01D2252/20489—Alkanolamines with two or more hydroxyl groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/604—Stabilisers or agents inhibiting degradation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60—Additives
    • B01D2252/606—Anticorrosion agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates in general to carbon dioxide (CO 2 ) capture and removal, and more particularly to compounds for preventing oxidative degradation in amine scrubbing systems.
  • a method for improving degradation resistance of monoethanolamine solutions used in purification of natural gas is provided by Singh in U.S. Patent Registration No. 3,535,260 (1970).
  • the Singh patent provides for the inclusion of tertiary amines alkanolamines like triethanolamine to improve degradation resistance of monoethanolamine solutions towards certain impurities like hydrogen sulfide, carbonyl sulfide, and mercaptans in the natural gas.
  • Johnson and McElwain in U.S. Patent Registration No. 3,137,654 (1964) provide a method of stabilizing aqueous alkanolamines employed in gas treating processes.
  • a process for the purification of a gas stream containing impurities is described in U.S. Patent Registration No. 4,840,777 issued to Faucher (1989).
  • the method of the Faucher patent comprises the steps of: (i) passing the gas stream through an aqueous solution of stabilized monoethanolamine or diethanolamme in such a manner that the impurities are absorbed into the monoethanolamine solution or diethanolamme solution to form a rich solution; and (ii) regenerating the monoethanolamine or diethanolamme solvent from the rich solution so as to remove the impurities; (iii) recycling the solvent into the aqueous solution in a closed loop and introducing a stabilizer into the recirculating solvent solution in an amount of about 4 to about 25 percent by weight based on the total weight of solution, the stabilizer being methyldiethanolamine.
  • U.S. Patent Application Publication No. 2010/0256347 discloses amine stabilizing agents containing an azeotrope comprising water, an alcohol, and sodium hydride.
  • Methods of making of amine stabilizing agents where solid silicon rock and sodium hydroxide are mixed with an ammonium/water solution to produce a green liquid in a first stage of the reaction.
  • Alcohol is added and the alcohol fraction is separated from the non-alcohol fraction to produce an alcohol fraction product and a bottom fraction that is not soluble in alcohol or organics.
  • the agents can be added to amines for stabilizing amines in anime processing of gases, in C02 capture, in C02 abatement systems and in other systems where amines are utilized to remove contaminants.
  • the Idem invention relates to a method of inhibiting 0 2 - and/or S0 2 - induced degradation of amines using sodium sulfite (Na 2 S0 3 ), potassium sodium tartrate tetrahydrate (KNaC 4 H 4 0 6 .4H 2 0), ethylenediaminetetraacetic acid (EDTA) or hydroxylamine (NH 2 OH), or analogs or mixtures thereof during C0 2 capture by amines.
  • sodium sulfite Na 2 S0 3
  • KNaC 4 H 4 0 6 .4H 2 0 potassium sodium tartrate tetrahydrate
  • EDTA ethylenediaminetetraacetic acid
  • NH 2 OH hydroxylamine
  • WIPO Patent Application Publication No. WO/2009/156619 disclose compositions and uses of a small quantity of degradation inhibiting agents derived from thiadiazole to substantially reduced degradation of an absorbing solution containing organic compounds having an amine function in aqueous solution.
  • the absorbing solution is used to deacidify a gaseous effluent.
  • the present invention discloses compositions and methods for preventing oxidative degradation of amine solvents used in amine scrubbing systems.
  • the composition of the invention described herein below comprises one or more metal chelating agents for trapping or sequestering metal ions (specifically Fe(II), Fe (III) or both) to prevent metal catalyzed oxidative degradation of the amine solvent.
  • the instant invention discloses a composition for inhibiting, preventing, or slowing oxidative degradation of one or more amine solvents comprising: one or more or a mixture of metal chelating agents or salts thereof, wherein the one or more metal chelating agents inhibit, prevent, or slow oxidative degradation of the one or more amine solvents.
  • the one or more metal chelating agents of the instant invention entrap or sequester one or more metals or metal contaminants in the amine solvent by forming a complex, wherein the metal comprises iron, nickel, copper, manganese, vanadium, chromium, transition metals, or any combinations thereof. More specifically the one or more metal chelating agents disclosed hereinabove entrap or sequester iron (Fe) from the amine solvent.
  • the amine solvent comprises monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIPA), methyldiethanolamine (MDEA), piperazine, (PZ), 2-methyl-piperazine, 1-methyl-piperazine, 2-amino-2-methyl-propanol, 2-piperidine-ethanol, and 1,4- dimethylpiperazine or combinations thereof.
  • MEA monoethanolamine
  • DGA diglycolamine
  • DEA diethanolamine
  • DIPA diisopropanolamine
  • MDEA methyldiethanolamine
  • PZ piperazine
  • 2-methyl-piperazine 1-methyl-piperazine, 2-amino-2-methyl-propanol, 2-piperidine-ethanol, and 1,4- dimethylpiperazine or combinations thereof.
  • the amine solvent is MEA.
  • the one or more chelating agents are selected from the group consisting of hydroxyethylidene diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTP A), diethylenetriamine penta (methylene phosphonic acid) (DTPMP), cyclohexane 1,2-diamino tetra(acetic acid) (COT A), cyclohexane 1,2-diamino tetra(methylene phosphonic acid) (CDTMP), Ethyleneglycol bis nitrilotetracetic acid (EGTA), hexamethylenediamine tetraacetic acid (HMDTA), nitrilo triacetic acid (NT A), citric acid, hydroxy ethylidene diphosphonic acid, 2-Phosphonobutane-l,2,4-Tricarboxylic acid (PBTCA), 2-hydroxy-2-phosphono-acetic acid (HPAA), diethylenetriamine penta acetic acid,
  • the one or more or a mixture of metal chelating agents or salts thereof are added to the amine solvent at a concentration ranging from 0.01-1.5 wt%. In another aspect the one or more or a mixture of metal chelating agents or salts thereof are added to the amine solvent at concentrations of 0.01, 0.02, 0.03, 0.04, 0.05, 0.075, 0.1, 0.150, 0.2, 0.3, 0.4, 0.5, 0.75, 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5 wt%. In another aspect the one or more or a mixture of metal chelating agents or salts thereof inhibit, prevent, or slow oxidative degradation of one or more amine solvents by reducing an ammonia release rate.
  • composition of the present invention results in a reduction in the ammonia release rate ranges from 15-99%.
  • one or more amine solvents are used in an amine scrubbing system for carbon dioxide (C0 2 ) capture from a flue gas, removal of CO 2 and H 2 S from a gas mixture or both.
  • Another embodiment of the instant invention provides a method for inhibiting, preventing or slowing down oxidative degradation of one or more amine solvents in an amine scrubbing system comprising the steps of: (i) providing the amine scrubbing system comprising an absorber, wherein the amine scrubbing system is used for carbon dioxide (C0 2 ) capture from a flue gas, removal of C0 2 and H 2 S from a gas mixture or both; (ii) introducing the amine solvent in the absorber comprising one or more or a mixture of metal chelating agents or salts thereof, wherein the one or more metal chelating agents inhibit, prevent, or slow oxidative degradation of the one or more amine solvents, wherein the metal chelating agents or salts thereof are pre-mixed with amine solvent prior to introduction in the absorber or is contacted with the amine solvent in the absorber; and (iii) operating the amine scrubbing system for carbon dioxide (C0 2 ) capture from a flue gas, removal of C
  • the method as disclosed hereinabove further comprises the step of measuring an ammonia release rate by one or more analytical techniques, wherein a reduction in the ammonia release rate is indicative of the inhibition, the prevention, or the slowing down of the oxidative degradation of one or more amine solvents.
  • the analytical technique is Fourier-Transform Infrared (FTIR).
  • FTIR Fourier-Transform Infrared
  • the one or more metal chelating agents entrap or sequester one or more metals or metal contaminants in the amine solvent by forming a complex, wherein the metal comprises iron, nickel, copper, manganese, vanadium, chromium, transition metals, or any combinations thereof.
  • the one or more metal chelating agents entrap or sequester iron (Fe) from the amine solvent.
  • the amine solvent comprises monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIPA), methyldiethanolamine (MDEA), piperazine, (PZ), 2-methyl-piperazine, 1-methyl-piperazine, 2-amino-2- methyl-propanol, 2-piperidine-ethanol, and 1,4-dimethylpiperazine or combinations thereof.
  • the amine solvent is MEA.
  • the one or more chelating agents are selected from the group consisting of hydroxyethylidene diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), diethylenetriamine penta (methylene phosphonic acid) (DTPMP), cyclohexane 1,2-diamino tetra(acetic acid) (COT A), cyclohexane 1,2-diamino tetra(methylene phosphonic acid) (CDTMP), Ethyleneglycol bis nitrilotetracetic acid (EGTA), hexamethylenediamine tetraacetic acid (HMDTA), nitrilo triacetic acid (NT A), citric acid, hydroxy ethylidene diphosphonic acid, 2-Phosphonobutane-l,2,4-Tricarboxylic acid (PBTCA), 2-hydroxy-2-phosphono-acetic acid (HPAA), diethylenetriamine penta acetic acid, He
  • the salts of the one or more metal chelating agents comprise sodium or potassium salts.
  • the one or more or a mixture of metal chelating agents or salts thereof are added to the amine solvent at a concentration ranging from 0.01-1.5 wt%.
  • the one or more or a mixture of metal chelating agents or salts thereof are added to the amine solvent at concentrations of 0.01, 0.02, 0.03, 0.04, 0.05, 0.075, 0.1, 0.150, 0.2, 0.3, 0.4, 0.5, 0.75, 1.0, 1.1, 1.2, 1.3, 1.4, and 1.5 wt%.
  • the reduction in the ammonia release rate ranges from 15-99%.
  • the instant invention provides a method for increasing efficiency of one or more amine solvents used in an absorber of an amine scrubbing system for carbon dioxide (CO 2 ) capture from a flue gas, removal of CO 2 and H 2 S from a gas mixture or both comprising the step of: contacting or mixing the amine solvent with one or more or a mixture of iron chelating agents or salts thereof, wherein the one or more chelating agents inhibit, prevent, or slow the oxidative degradation of the one or more amine solvents, wherein the chelating agents or salts thereof are pre-mixed with amine solvent prior to introduction in the absorber or is contacted with the amine solvent in the absorber.
  • CO 2 carbon dioxide
  • the amine solvent comprises monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIPA), methyldiethanolamine (MDEA), piperazine, (PZ), 2-methyl- piperazine, 1-methyl-piperazine, 2-amino-2-methyl-propanol, 2-piperidine-ethanol, and 1,4- dimethylpiperazine or combinations thereof.
  • MEA monoethanolamine
  • DGA diglycolamine
  • DEA diethanolamine
  • DIPA diisopropanolamine
  • MDEA methyldiethanolamine
  • PZ piperazine
  • 2-methyl- piperazine 1-methyl-piperazine, 2-amino-2-methyl-propanol, 2-piperidine-ethanol, and 1,4- dimethylpiperazine or combinations thereof.
  • the amine solvent is MEA.
  • the one or more chelating agents are selected from the group consisting of hydroxyethylidene diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTP A), diethylenetriamine penta (methylene phosphonic acid) (DTPMP), cyclohexane 1,2-diamino tetra(acetic acid) (COT A), cyclohexane 1,2-diamino tetra(methylene phosphonic acid) (CDTMP), Ethyleneglycol bis nitrilotetracetic acid (EGTA), hexamethylenediamine tetraacetic acid (HMDTA), nitrilo triacetic acid (NT A), citric acid, hydroxy ethylidene diphosphonic acid, 2-Phosphonobutane-l,2,4-Tricarboxylic acid (PBTCA), 2-hydroxy-2-phosphono-acetic acid (HPAA), HexaMethyleneDiamineTetra (HEDP),
  • the one or more or a mixture of metal chelating agents or salts thereof are added to the amine solvent at a concentration ranging from 0.01-1.5 wt%.
  • the one or more or a mixture of iron chelating agents or salts thereof inhibit, prevent, or slow oxidative degradation of one or more amine solvents by reducing an ammonia release rate, wherein a reduction in the ammonia release rate ranges from 15-99%.
  • the present invention further discloses a composition for inhibiting, preventing, or slowing oxidative degradation of monoethanolamine (MEA), piperazine (PZ) or both comprising: one or more or a mixture of metal chelating agents or salts thereof, wherein the one or more metal chelating agents inhibit, prevent, or slow an oxidative degradation of the MEA or the PZ, wherein the metals comprise iron, nickel, copper, manganese, vanadium, chromium, transition metals, or any combinations thereof.
  • MEA monoethanolamine
  • PZ piperazine
  • the one or more chelating agents are selected from the group consisting of hydroxy ethylidene diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTP A), diethylenetriamine penta (methylene phosphonic acid) (DTPMP), cyclohexane 1,2-diamino tetra(acetic acid) (COT A), cyclohexane 1,2-diamino tetra(methylene phosphonic acid) (CDTMP), Ethyleneglycol bis nitrilotetracetic acid (EGTA), hexamethylenediamine tetraacetic acid (HMDTA), nitrilo triacetic acid (NT A), citric acid, hydroxy ethylidene diphosphonic acid, 2-Phosphonobutane-l,2,4-Tricarboxylic acid (PBTCA), 2-hydroxy-2-phosphono-acetic acid (HPAA), diethylenetriamine penta acetic acid (HE
  • Another embodiment of the present invention relates to a method for inhibiting, preventing, or slowing oxidative degradation of monoethanolamine (MEA), piperazine (PZ), increasing efficiency of MEA and PZ for C02 removal from a flue gas, or both comprising the step of: adding or contacting the MEA or the PZ with one or more or a mixture of metal chelating agents or salts thereof, wherein the one or more metal chelating agents inhibit, prevent, or slow an oxidative degradation of the MEA or the PZ, wherein the metals comprise iron, nickel, copper, manganese, vanadium, chromium, transition metals, or any combinations thereof.
  • the one or more chelating agents are selected from the group consisting of hydroxyethylidene diphosphonic acid (HEDP), diethylene triamine penta acetic acid (DTPA), diethylenetriamine penta (methylene phosphonic acid) (DTPMP), cyclohexane 1,2- diamino tetra(acetic acid) (COT A), cyclohexane 1,2-diamino tetra(methylene phosphonic acid) (CDTMP), Ethyleneglycol bis nitrilotetracetic acid (EGTA), hexamethylenediamine tetraacetic acid (HMDTA), nitrilo triacetic acid (NTA), citric acid, hydroxy ethylidene diphosphonic acid, 2- Phosphonobutane -1,2,4-Tricarboxylic acid (PBTCA), 2-hydroxy-2-phosphono-acetic acid (HPAA), HexaMethyleneDia
  • the present invention discloses a composition for inhibiting, preventing, or slowing oxidative degradation of one or more amine solvents comprising: one or more amine compounds having a general molecular structure given by:
  • the one or more amine solvents are used in an amine scrubbing system for carbon dioxide (C0 2 ) capture from a flue gas, removal of C0 2 and H 2 S from a gas mixture or both, wherein the amine solvent comprises monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIP A), methyldiethanolamine (MDEA), piperazine, (PZ), 2-methyl-piperazine, 1-methyl-piperazine, 2-amino-2- methyl-propanol, 2-piperidine-ethanol, and 1,4-dimethylpiperazine or combinations thereof.
  • the present invention discloses a composition for inhibiting, preventing, or slowing oxidative degradation of one or more amine solvents comprising: a short-
  • the one or more amine solvents are used in an amine scrubbing system for carbon dioxide (C0 2 ) capture from a flue gas, removal of C0 2 and H 2 S from a gas mixture or both, wherein the amine solvent comprises monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIP A), methyldiethanolamine (MDEA), piperazine, (PZ), 2-methyl-piperazine, 1-methyl-piperazine, 2-amino-2- methyl-propanol, 2-piperidine-ethanol, and 1,4-dimethylpiperazine or combinations thereof.
  • the present invention relates to a method for inhibiting, preventing, or slowing the oxidative degradation of the one or more amine solvents or both comprising the step of: contacting or mixing the amine solvent with a composition comprising one or more amine compounds having a general molecular structure given by:
  • the composition may comprise the amine compound dissolved in an aqueous or an organic solvent.
  • the composition inhibits, prevents, or slows oxidative degradation of one or more amine solvents by reducing an ammonia release rate, wherein a reduction in the ammonia release rate ranges from 15-99%.
  • One embodiment of the present invention relates to a method for inhibiting, preventing, or slowing the oxidative degradation of the one or more amine solvents or both comprising the step of: contacting or mixing the amine solvent with a composition comprising a short-chain alkane having a eneral molecular structure given by:
  • n 0-4, wherein the short-chain alkane comprises at least one
  • the composition inhibits, prevents, or slows oxidative degradation of one or more amine solvents by reducing an ammonia release rate, wherein a reduction in the ammonia release rate ranges from 15-99%.
  • the amine solvent comprises monoethanolamine (MEA), diglycolamine (DGA), diethanolamine (DEA), diisopropanolamine (DIP A), methyldiethanolamine (MDEA), piperazine, (PZ), 2-methyl-piperazine, 1- methyl-piperazine, 2-amino-2-methyl-propanol, 2-piperidine-ethanol, and 1,4-dimethylpiperazine or combinations thereof.
  • the one or more amine solvents are used in an amine scrubbing system for carbon dioxide (C0 2 ) capture from a flue gas, removal of C0 2 and H 2 S from a gas mixture or both.
  • FIG. 1 is a schematic representation of amine oxidation in C0 2 capture
  • FIG. 2 is a schematic representation showing the metal catalyzed (Fe) oxidation of monoethanolamine (MEA);
  • FIG. 3 A is a schematic showing the structures of some known inhibitors of MEA oxidation
  • FIG. 3B shows general molecular structures of some inhibitors described in various embodiments of the present invention.
  • FIG. 4 shows a flow diagram for the high gas flow (HGF) oxidation apparatus
  • FIG. 5 shows a photograph of the HGF oxidation apparatus
  • FIG. 6 is a plot showing the oxidation of 9 m pilot plant MEA in the HGF at 70°C, 98 kPa air, 2 kPa C0 2 ;
  • FIG. 7 is a plot showing the oxidation of 7 m MEA in the HGF at 70°C, 98kPa air, 2kPa C0 2 ;
  • FIG. 8 is a plot comparing known inhibitors of MEA oxidation using 9 m solution at 70°C, 98kPa air, 2kPa C0 2 ;
  • FIG. 9 is a plot showing the comparison of inhibitors tested in the present invention using 9 m MEA at 70°C, 98kPa air, 2kPa C0 2 ;
  • FIG. 10 is a plot showing the inhibited oxidation of 9 m pilot plant MEA with Sulfite at 70°C, 98 kPa air, 2kPa C0 2 ;
  • FIG. 11A is a plot showing the inhibition of oxidation by hydroxyethylidene diphosphonic acid (HEDP) on 9 m pilot plant MEA at 70°C, 98kPa air, 2kPa C0 2 ;
  • HEDP hydroxyethylidene diphosphonic acid
  • FIGS. 1 lB-1 ID are plot showing the oxidation of 9 m pilot plant MEA at 70°C, 98kPa air, 2kPa C0 2 with different inhibitors: 0.08 %wt diethylenetriamine penta acetic acid (13B), 0.04 %wt ethylenediamine terra (methylene phosphonic acid) (13C), and 0.02 and 0.2 %wt diethylene triamine penta (methylene phosphonic acid);
  • FIG. 12 shows the metal-catalyzed oxidation of 8 m PZ at 70°C, 98kPa air, 2kPa C0 2 .
  • flue gas includes the exhaust gas from any sort of combustion process (including coal, oil, natural gas, glass raw material, etc.).
  • the term "scrubber system” refers to the process of gas absorption whereby one or more of the constituents of a gas mixture, in this case C0 2 , H 2 S, or other gases in flue gas may be dissolved or absorbed in a circulating liquid scrubbing medium, in this case an aqueous amine solvent, for the purposes of gas purification and product recovery.
  • the gas absorption is typically carried out in a vertical countercurrent column wherein the aqueous amine solvent is fed into the top of the column and the gas mixture is introduced into the bottom of the column. As the gas mixture travels upward through the column, it contacts and reacts with the downward travelling aqueous amine solvent.
  • the reaction medium collects in the lower part of the column or in a separate circulation tank where it can be recirculated to the top of the column.
  • Oxidative degradation is a major problem in amine scrubbing systems (a schematic of the process is shown in FIG. 1) employing monoethanolamine (MEA), particularly for CO 2 capture from power plant flue gas. Flue gas contains 5-15% oxygen, in addition to other contaminants, which promote oxidation, such as NO 2 and transition metals (an example of the oxidative process is shown FIG. 2).
  • MEA monoethanolamine
  • FIG. 2 An example of the oxidative process is shown FIG. 2.
  • the present invention discloses that addition of a small amount (0.01- 1.5 %wt.) of an inhibitor to reduce the oxidation rate of aqueous MEA in the concentrations of 7-9 molal (m).
  • the substances disclosed in the present invention will be affective for aqueous solutions of other amines (particularly primary amines) prone to oxidation by molecular oxygen, as well as other concentrations of MEA, which are used in CO 2 capture systems (namely 3-11 m).
  • the present invention further discloses the potency of various chelating agents as inhibitors of oxidation of aqueous 7 and 9 m MEA.
  • Blachly and Ravner (1963) 2 proposed substitution of battery-grade for potable makeup water to prevent a significant portion of copper intake, and for extending the useful life of the monoethanolamine scrubber solutions.
  • the inventors also studied the effect of monosodium diethanol glycine-tetrasodium ethylenediaminetetraacetate (VFS-EDTA) as additive package to stabilize monoethanolamine (MEA) scrubber solutions in submarines.
  • VFS-EDTA monosodium diethanol glycine-tetrasodium ethylenediaminetetraacetate
  • MEA monoethanolamine
  • the classes of chelating inhibitors (FIGS. 3A and 3B) disclosed herein include tertiary mono-, di- , and tri-alkylene amines with one or more carboxylate or phosphonate substituent, as well as certain short, straight-chain alkanes with one or more carboxylate or phosphonate substituents.
  • Certain compounds have been tested and found to be highly effective: hydroxyethylidene diphosphonic acid (HEDP), citric acid, diethylene triamine penta acetic acid (DPTA), ethylenediamine tetra (methylene phosphonic acid), diethylenetriamine penta (methylene phosphonic acid) (DTPMP).
  • HMDTA hexam ethylenediamine tetra acetic acid
  • BHMDPA bis(hexamethylene) triamine penta acetic acid
  • ATMP amino tris(methylene phosphonic acid)
  • HMDTMP hexamethylene diamine tetra (methylene phosphonic acid)
  • BHMTPMP bis(hexamethylene) triamine penta (methylene phosphonic acid)
  • Other chelating agents were also found to be successful oxidation inhibitors, however, they were either less potent or less stable than the three inhibitors mentioned above.
  • HEDP, DPTA, EDTMP, and DTPMP are superior to previously known inhibitors, including ethylenediamine tetraacetic acid (EDTA), bicine, sodium sulfite, phosphate, methyl diethanolamine (MDEA), triethanolamine (TEA), and gluconate because they are either more effective at a lower concentration, more stable, or both.
  • EDTA ethylenediamine tetraacetic acid
  • MDEA methyl diethanolamine
  • TAA triethanolamine
  • gluconate gluconate because they are either more effective at a lower concentration, more stable, or both.
  • a further benefit of these inhibitors is that their bulk price is on the order very low ($l-2/kg for most).
  • a 90% reduction in the oxidation rate would save a typical 500 MW plant operating at 90% capture efficiency approximately $6.2 million annually, considering only the cost of amine makeup.
  • Other benefits would include less reclaimer waste, lower reclaimer steam duty, reduced corrosion rate, improved system performance, and reduced ammonia emissions from the absorber.
  • COTA cyclohexane diamino tetra(acetic acid)
  • CDTMP cyclohexane diamino tetra(methytene phosphonic acid)
  • EGTA Ethyleneglycol bis nitrilotetracetic acid
  • EDDS ethylene diamine disuccinic acid
  • tertiary amines including MDEA, TEA, EDTA, and bicine can be used to inhibit MEA oxidation.
  • Tertiary amines work on the principle of absorbing free radicals in solution to form molecular products, thus terminating the self-propagating free radical chain reaction.
  • MDEA was recommended for use at 10-20 %wt. concentration
  • TEA was recommended for 0.5 - 5 %wt.
  • EDTA is the most potent, likely as a result of the ability of EDTA to chelate dissolved iron, thus sequestering the catalyst and blocking initiation of the free radical reaction.
  • EDTA and bicinc were recommended for use 1.5%wt concentration each.
  • These chelating agents bind Fe(II) and Fe(III) relatively poorly and are therefore far less potent than inhibitors described in the present invention.
  • Sodium sulfite has been proposed as an oxidation inhibitor for MEA solutions, however this inhibitor is consumed fairly quickly over time and is thus unacceptable for long term use.
  • inhibitor systems including potassium tartarate tetrahydrate (at 0.26 %wt) and hydroxylamine (at 0.08 %wt). Hydroxylamine was found to increase oxidation of MEA in this work.
  • a sodium thiosulfate sodium sulfite blend was also proposed, however this blend would likely have the same problem as sulfite alone in that its performance would degrade rapidly over time.
  • DTP A, HEDP, DTPMP, EDTMP, and citric acid are excellent chelating agents, which is believed to be the underlying cause of their ability to inhibit MEA oxidation.
  • EDTMP was found to be highly unstable in the presence of MEA and oxygen at 70°C, whereas DTPA and HEDP showed no reduction in performance over 12 hours, and DTPMP was moderately stable.
  • DTPA HEDP
  • DTPMP DTPMP
  • EDTMP citric acid
  • DTPA, HEDP, and DTPMP are much more effective than other inhibitors, which are generally only effective at concentrations 1.5-20 %wt.
  • Inhibitors such as sodium sulfite that are effective at lower concentrations are less stable than the three inhibitors above.
  • these powerful chelating agents are more effective at preventing oxidation of MEA than other inhibitors, because they prevent free radicals from forming from the homolytic splitting of organic peroxides, rather than reacting with free- radicals in solution.
  • Chelating agents such as HEDP, EDTMP, DTPMP, HPAA, PBTCA, ATMP, HMDTMP, and BHMTPMP, which employ methylene phosphonic acid functionality (as opposed to only carboxylic acid functionality), have the additional advantage that they can chelate metals even after being oxidized (to the N-oxide).
  • HEDP has the additional advantage of not containing any nitrogen group, which may confer additional resistance to oxidation.
  • the presence of hydroxyl groups, such as those on HEDP and citric acid may also improve their chelation ability.
  • DTP A, DTPMP, HEDP, EDTMP, and citric acid solve the problem of oxidative degradation of MEA occurring in absorber in an amine stripping process by reducing the degradation rate by 50-90 %, depending on the concentration. Since the oxidation rate is highly dependent on temperature, the practical concentration would be selected according to the operating temperature of a particular absorber. For example, a system using intercooling would require less oxidation inhibitor. Oxidation appears to be the primary degradation pathway in industrial systems.
  • DTP A, HEDP, and DTPMP are 27- 33 times more effective than EDTA, which is the best inhibitor currently known. This reduces the overall cost of the solvent. HEDP and DTPMP will continue to chelate metals even after being oxidized, which would make these more effective for a longer period of time than their acetic acid analogs. Lower steady state concentrations reduce losses from thermal reclaiming and from destructive trace contaminants in the flue gas, such as NO 2 and SO 2 thus a lower inhibitor makeup rate is required compared with EDTA.
  • Ammonia has been used as a marker for oxidative degradation of MEA.
  • 1.5 %wt of various potential inhibitors was added to neat 7 m MEA with 0.4 mM Fe +2 , 0.1 mM Cr +2 , and 0.05 mM Ni +2 (Table 1).
  • a much lower concentration was added to a 9 m MEA solution received from a pilot plant. The solution was analyzed and found to comprise 0.56 mM Fe, 0.02 Cr, and 0.03 Ni.
  • Table 1 provides a summary of the reduction in degradation achieved by addition of various inhibitors. Tetrakis(hydroxyethyl) ethylene diamine (THEEDA) and imino diacetic acid (IMDA) were also tested and found to be relatively poor inhibitors.
  • THEEDA Tetrakis(hydroxyethyl) ethylene diamine
  • IMDA imino diacetic acid
  • Table 1 Summary of the reduction in degradation achieved by addition of various inhibitors at ⁇ 1.5wt%. Conditions: 7 m MEA, 70°C, 98 kPa air, 2 kPa C0 2 .
  • Table 2 Effect of low concentrations of inhibitors at 70°C on 9 m MEA received from a pilot plant.
  • DTP A, DTPMP, and HEDP can be extended to many organic molecules, particularly to those prone to oxidative degradation at moderate temperatures ( ⁇ 90°C).
  • ⁇ 90°C the metal initiated splitting of peroxides to form free radicals is the most likely pathway for oxidation.
  • these inhibitors would be beneficial to other amines and amino acid solvents for amine scrubbing systems for C0 2 capture, which are prone to oxidation.
  • the inhibitor would be beneficial to prevent oxidation in any aqueous solution containing, 5 - 95 %wt MEA. In particular, 3 m and 11 m MEA solutions could use these inhibitors.
  • Inhibitors were only tested at the temperature of 70°C. These substances are expected to be similarly effective in the temperature range of 30 - 80°C, which is the temperature at which the amine is exposed to oxygen in the absorber. These inhibitors may be more or less effective at higher temperatures (80 - 150°C), namely those encountered in the cross exchanger and stripper where dissolved oxygen may be present.
  • the general class of the inhibitor compounds of the present invention is "chelating agents of iron.” More specifically, these include:
  • Carboxylate- and Phosphonate-substituted short, straight- chain alkane chelating agents examples include citric acid, hydroxy ethylidene diphosphonic acid, 2-Phosphonobutane, 1,2,4-Tricarboxylic acid, and 2-hydroxy-2-phosphono-acetic acid.
  • Acetate-substituted alkylene mono, di- and tri- tertiary amine chelating agents examples include diethylenetriamine penta acetic acid, HexaMethyleneDiammeTetra (acetic acid), Bis(HexaMethylene Triamine Penta (acetic acid).
  • Methylene Phosphonate-substituted alkylene mono, di- and tri- tertiary amine chelating agents examples include Amino Trimethylene Phosphonic Acid, Ethylenediamine tetra (methylene phosphonic acid), Diethylenetriamine penta (methylene phosphonic acid), HexaMethyleneDiammeTetra (MethylenePhosphonic Acid), Bis(HexaMethylene Triamine Penta (Methylene Phosphonic Acid).
  • Any blend or combination of the above inhibitors would also inhibit oxidation, possibly to an extent greater than that expected by the sum of each individual contribution.
  • this invention also includes the sodium and potassium salts of DPT A, HEDP, DTPMP, EDTMP, and citric acid.
  • oxidation inhibitors can be used in any amine scrubbing system where oxygen or another oxidant is present. This applies to C0 2 capture from a variety of sources, including power generation, cement production, steel mills, chemicals production (namely ammonia) as well as acid gas treating and other amine scrubbing processes. These oxidation inhibitors are especially valuable for carbon capture from flue gas from gas fired power plants, due to the higher oxygen concentration and higher gas rate encountered in this application.
  • HGF high gas flow
  • house air and high-purity CO 2 502 are fed to a saturator 504 via two mass flow controllers.
  • Two positive displacement pumps are used to maintain a constant level of water in the saturator 504.
  • Gas exiting the saturator is sparged into the bottom of the reactor, which is heated by recirculating oil 506 that flows between the jacket and a heated reservoir.
  • the condenser 508 is tuned to the correct temperature to prevent any net water loss from the reactor 504.
  • the gas After the condenser 508, the gas enters a heated line and is pumped to a hot gas Fourier-Transform Infrared (FTIR) analyzer 510.
  • FTIR Fourier-Transform Infrared
  • the pump 512 draws gas through the heated line at a rate of approximately ⁇ 5 SLPM.
  • the heated line has a vent after the condenser to maintain the reactor pressure at approximately atmospheric pressure.
  • the analyzer can analyze the oxidation gas leaving the reactor for up to 30 individual components simultaneously, including water, C0 2 , volatile amine, NH 3 , NO, N0 2 , and others.
  • a summary of the analysis regions used by the instrument for some components is shown in Table 3.
  • a photograph of the apparatus is shown in FIG. 5A.
  • Table 3 Summary of analysis areas used for FTIR gas analysis.
  • FIGS. 6 - 1 ID Results produced high gas flow (HGF) oxidation apparatus described hereinabove are presented in FIGS. 6 - 1 ID.
  • HGF high gas flow
  • FIG. 6 a typical computer output for oxidation of MEA is shown.
  • the plot shows data points at five -minute intervals for concentrations of water, CO 2 , MEA, and NH 3 in the gas phase.
  • NH 3 is used as an indicator of the instantaneous rate of MEA oxidation during the study. The rates of all four species reach a steady state after several hours.
  • FIG. 7 shows the oxidation of MEA in the presence of various transition metal catalysts. Addition of Fe, Cu, and Mn each cause a large step change in the rate of NH 3 production.
  • FIG. 8 shows only the state of the art inhibitors evaluated in the HGF apparatus.
  • the amount of inhibition was calculated as the percent decrease in the ammonia rate before and after the inhibitor was added.
  • Most known inhibitors are only able to achieve a 50% reduction in the NH 3 rate for a 0.5 - 5wt% concentration.
  • FIG. 9 is a comparison of the known inhibitors with those described in the present invention.
  • inhibitors X ETMP
  • V HEDP
  • Z DTPA
  • FIG. 10 shows the effect of sodium sulfite as an inhibitor for oxidation of 9 m MEA at 70°C with 98 kPa air and 2 kPa CO 2 .
  • Sodium sulfite was able to reduce the ammonia rate for several hours, however the rate was not stable and slowly returned the original uninhibited condition.
  • FIG. 11A shows the effect of HEDP on oxidation of 9 m MEA at 70°C with 98 kPa air and 2 kPa CO 2 .
  • the NH 3 rate is assessed after several consecutive additions of HEDP. After the final addition, the NH 3 rate remains stable for over twelve hours.
  • FIG. 1 IB shows the effect of 0.08wt% DPTA on oxidation of 9 m MEA at 70°C with 98 kPa air and 2 kPa CO 2 .
  • a small addition of DPTA substantially decreases the NH 3 rate, and the rate remained low for over 10 hours after the addition of the inhibitor.
  • FIG. 11C shows the effect of 0.04wt% EDTMP on oxidation of 9 m MEA at 70°C with 98 kPa air and 2 kPa CO 2 .
  • the NH 3 rate dropped sharply with addition of the inhibitor, but was observed to rise back to the original rate after only a few hours.
  • FIG. 1 ID shows the effect of 0.02 and 0.18wt% DTPMP on oxidation of 9 m MEA at 70°C with
  • FIG. 14 shows the effect of metal catalysts on PZ, also using NH 3 as an indicator of oxidation.
  • NH3 is not expected to be a primary oxidation product of PZ, it is a secondary product derived from oxidation of ethylene diamine (which is a primary oxidation product of PZ) or other primary products.
  • Addition of 1 mM Fe 2+ has almost no effect on NH 3 production, however Cu 2+ has a dramatic effect on the NH 3 rate. This demonstrates that PZ oxidation is also likely metal-catalyzed, and can therefore be inhibited with inhibitors for MEA in this invention.
  • compositions of the invention can be used to achieve methods of the invention.
  • the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), "including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
  • A, B, C, or combinations thereof refers to all permutations and combinations of the listed items preceding the term.
  • A, B, C, or combinations thereof is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB.
  • expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth.
  • the skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.
  • compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims

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Abstract

L'invention concerne des inhibiteurs et des procédés permettant de prévenir une dégradation par oxydation dans un système d'épuration faisant intervenir des amines. Les substances de la présente invention sont efficaces pour des solutions aqueuses d'autres amines (en particulier, les amines primaires) ayant tendance à s'oxyder par l'oxygène moléculaire, ainsi que d'autres concentrations de MEA, qui sont utilisées dans des systèmes de capture de CO2 (à savoir 3-11 molal). Les inhibiteurs de l'invention comprennent de l'acide hydroxyéthylidène diphosphonique (HEDP), de l'acide diéthylène triamine penta acétique (DPTA), de l'acide diéthylènetriamine penta (méthylène phosphonique) (DTPMP), de l'acide éthylènediamine tétra (méthylène phosphonique) (EDTMP), et de l'acide citrique. Les composés de la présente invention agissent en tant que puissants chélateurs pour séquestrer des ions métalliques et prévenir la décomposition homolytique catalysée par des métaux de peroxides réactifs en solution, ce qui permet de prévenir l'oxydation des amines.
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WO2015173253A3 (fr) * 2014-05-12 2016-02-18 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé et appareil de purification du gaz naturel
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WO2025222298A1 (fr) * 2024-04-26 2025-10-30 Entropy Inc. Inhibiteur de dégradation de solvant dans la capture de carbone post-combustion

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US9816029B2 (en) 2013-06-18 2017-11-14 China Petroleum & Chemical Corporation Organic amine decarbonization solutions
US9815025B2 (en) 2014-03-13 2017-11-14 Fluor Technologies Corporation Removal of metals from CO2 capture solvents
US20150258497A1 (en) * 2014-03-13 2015-09-17 Fluor Technologies Corporation Removal of metals from co2 capture solvents
WO2015138940A1 (fr) * 2014-03-13 2015-09-17 Fluor Technologies Corporation Élimination de métaux de solvants de capture de co2
US10532317B2 (en) 2014-03-13 2020-01-14 Fluor Technologies Corporation Removal of metals from CO2 capture solvents
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WO2015173253A3 (fr) * 2014-05-12 2016-02-18 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé et appareil de purification du gaz naturel
WO2015176713A1 (fr) * 2014-05-21 2015-11-26 Technische Universität Dresden Procédé et dispositif pour extraire du dioxyde de carbone à partir de mélanges gazeux
CN113174603A (zh) * 2021-04-28 2021-07-27 河钢集团有限公司 用于捕获并电解co2的组合物以及方法
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CN117244384A (zh) * 2023-10-31 2023-12-19 大连理工大学 一种用于捕集烟道气中二氧化碳的抗氧化的少水胺液及其应用
WO2025222298A1 (fr) * 2024-04-26 2025-10-30 Entropy Inc. Inhibiteur de dégradation de solvant dans la capture de carbone post-combustion
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