Classifications

• • 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
  • B01D53/1493—Selection of liquid materials for use as absorbents
• • 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
  • B01D53/1475—Removing carbon dioxide
• • 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
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
  • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• • 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

Definitions

• the present invention relates to the decarbonation of a gaseous effluent.
• Carbon dioxide is one of the greenhouse gases largely produced by different human activities and has a direct impact on air pollution.
• gaseous effluents such as for example natural gas, synthesis gases, combustion fumes, refinery gases, bottoms gases from the Claus process, biomass fermentation gases, cement gases and Blast furnace gas is usually made by washing with an absorbent solution.
• gaseous effluents such as for example natural gas, synthesis gases, combustion fumes, refinery gases, bottoms gases from the Claus process, biomass fermentation gases, cement gases and Blast furnace gas is usually made by washing with an absorbent solution.
• the physico-chemical characteristics of the solutions employed are closely related to the nature of the gas to be treated: selective removal of an impurity, specification expected on the treated gas, thermal and chemical stability of the solvent with respect to the various compounds present in the gas to be treated. treat.
• Some decarbonation processes by washing with an absorbent solution are based on a physical absorption of CO 2 .
• the CO 2 extraction medium used in a process for capturing carbon dioxide contained in a gaseous effluent, comprises the product obtained by an acid-base reaction between two species B and R ( ZH) n, where B is a base or a mixture of bases chosen from amines such as amidines or guanidines and R (ZH) n is a compound or a mixture of compounds comprising at least one alcohol function or a thiol function ( R being is a monovalent or multivalent aliphatic, alicyclic, mono- or polyaromatic, or heterocyclic group, Z an oxygen atom and / or a sulfur atom and n being between 1 and 20).
• the process for capturing carbon dioxide consists in carrying out the following steps: a) contacting the gas to be treated containing CO 2 with said extraction medium, so as to obtain a gas depleted of CO 2 and a medium of carbon dioxide; extraction rich in CO 2 , b) the regeneration of the CO 2 -rich extraction medium, to obtain an extraction medium that can be used again and to generate a gas rich in CO 2 .
• FIG. 1 represents the evolution of the regeneration rate as a function of time and compares the regeneration rate at 40 ° C. under 20 Nl / h of nitrogen of two CO 2 loaded extraction media (mixture A according to the invention). and reference mixture C).
• the present invention proposes to use a CO 2 extraction medium different from the prior art.
• This extraction medium makes it possible to capture CO 2 contained in a gaseous effluent. Once loaded with CO 2 , said medium can also be regenerated under easier conditions than the absorbent solutions of the prior art.
• the process for capturing carbon dioxide consists in carrying out the following steps: a) the gas to be treated containing CO 2 is brought into contact with an extraction medium, so as to obtain a gas depleted in CO 2 and a medium CO 2 rich extraction medium, b) the CO 2 -rich extraction medium is regenerated, so as to obtain a reusable extraction medium and to generate a very rich gas CO 2 .
• the extraction medium comprises the product obtained by an acid-base type reaction between two species B and R (ZH) n defined as follows:
• B is a base or a mixture of bases chosen from amines such as amidines or guanidines, of general structure:
• R1, R2 and R3 are independently selected from a hydrogen atom, an aliphatic hydrocarbon group, saturated or unsaturated, branched or unbranched, alicyclic, saturated or unsaturated, substituted or unsubstituted, heterocyclic, saturated or unsaturated, substituted or unsubstituted, mono or substituted or unsubstituted polyaromatic;
• R4 is chosen from a hydrogen atom, an aliphatic hydrocarbon group, saturated or unsaturated, branched or unbranched, alicyclic, saturated or unsaturated, substituted or unsubstituted, heterocyclic, saturated or unsaturated, substituted or unsubstituted, mono- or polyaromatic substituted or unsubstituted ; or R4 is constituted by the pattern:
• R5 and R6 are independently selected from a hydrogen atom, an aliphatic hydrocarbon group, saturated or unsaturated, branched or unbranched, alicyclic, saturated or unsaturated, substituted or unsubstituted, heterocyclic, saturated or unsaturated, substituted or unsubstituted, mono or polyaromatic substituted or not.
• R5 and R6 may contain, for example, one or more halogens, one or more heteroatoms or nitrile, ketone, amide or nitro groups.
• R4 represents a hydrogen atom, an aliphatic, alicyclic, heterocyclic, mono or polyaromatic hydrocarbon group
• the bases B belong to the family of amidines.
• R1, R2, R3 and R4 may contain, for example, one or more halogens, one or more heteroatoms or nitrile, ketone, amide or nitro groups.
• R1, R2, R3 and R4 may be linked together to form rings or heterocycles.
• amidines mention may be made, for example, without being exhaustive, imidazoline, 2-methyl-2-imidazoline, 1, 4,5,6-tetrahydropyrimidine, N-methyltetrahydropyrimidine, 6- (dibutylamino) 1,8-diazabicyclo (5.4.0) undec-7-ene, 4-azabenzimidazole, anabasin, N'-tertbutyl-NN-dimethylformamidine, 1,5-diazabicyclo (4.3.0) non-5- ene of formula:
• the bases B belong to the family of guanidines.
• R1, R2, R3, R5 and R6 can be connected together to form rings or heterocycles.
• R 1, R 2, R 3, R 5 and R 6 may include, for example, one or more halogens, one or more heteroatoms or nitrile, ketone, amide or nitro groups.
• guanidine tetramethylguanidine
• pentamethylguanidine butyltetramethylguanidine
• tert-butyltetramethylguanidine phenylguanidine
• 1,7-triazabicyclo (4.4.0) dec-5-ene formula :
• R (ZH) n is a compound or a mixture of compounds having a structure in which:
• R is chosen from a monovalent or multivalent aliphatic group, saturated or unsaturated, branched or unbranched, alicyclic, saturated or unsaturated, substituted or unsubstituted, heterocyclic, saturated or unsaturated, substituted or unsubstituted, mono or polyaromatic substituted or unsubstituted.
• R may contain for example one or more halogens, one or more heteroatoms or functions alcoholic, thiols, ethers, thioethers, nitriles, ketones, sulfones, sulfoxides, amides, amines or nitrates.
• Z is an oxygen atom and / or a sulfur atom, linked on the one hand to the radical R and on the other hand to a hydrogen atom.
• n is between 1 and 20, preferably between 1 and 6.
• monovalent and multivalent means that the group is substituted by at least one or more (from 1 to n) -ZH units as defined above and provided that the rules of organic chemistry.
• R (ZH) n has at least one alcohol function or a thiol function.
• R (ZH) n can have both one or more alcohol functions with one or more thiol functions.
• R (ZH) n is chosen for example, without being exhaustive, from monoalcohols such as methanol, ethanol, propanols, butanols, pentanols, hexanols, octanols, decanols, dodecanol, fatty alcohols, polyols such as ethylene glycols, propylene glycols, polyethylene glycols, polypropylene glycols, ethylene glycol-propylene glycol copolymers, monoethers of glycols, glycerol, C 4 , C 5 and C 6 polyols.
• monoalcohols such as methanol, ethanol, propanols, butanols, pentanols, hexanols, octanols, decanols, dodecanol, fatty alcohols, polyols such as ethylene glycols, propylene glycols, polyethylene glycols,
• R (ZH) n is chosen for example, without being exhaustive, among thiols such as decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, ethylenedithiol, 2-methyltetrahydrofuran-3- thiol, pyrimidine-2-thiol, 1H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol,
• n is greater than 1 and Z is a sulfur atom and an oxygen atom
• R (ZH) n is chosen, for example, without being exhaustive, from 1-thioglycerol, 2-mercaptoethanol and 1-mercapto.
• the base B and the species R (ZH) n can be linked by at least one chemical bond so as to constitute only one molecule.
• ⁇ depends on the nature of the two chemical species involved. ⁇ is a positive number. Preferably, ⁇ must satisfy the condition that a basic function provided by B must be associated with at least one hydrogen atom bonded to Z in the formula R (ZH) n. In the case of a monobase B associated with a monohydric alcohol or a monothiol RZH, ⁇ is preferably greater than or equal to 1.
• Carbon dioxide may be in excess or in default with respect to
• the operation of regeneration of the extraction medium can be carried out under conditions that require little energy and in particular less energy than the operation that would be necessary to regenerate the same amount of CO 2 when it is extracted.
• this operation of regeneration of the extraction medium can be carried out under conditions that require little energy and in particular less energy than the operation that would be necessary to regenerate the same amount of CO 2 when the latter is extracted using species B when used alone in the absence of R (ZH) n.
• the extraction medium comprises a mixture of bases B in combination with a mixture of compounds R (ZH) n.
• the extraction medium may further comprise one or more solvents, defined as having the property of dissolving one or more species present in the extraction medium before and / or after capture of CO 2 .
• the solvents may be chosen, for example, from aliphatic hydrocarbons, saturated or unsaturated, branched or otherwise, alicyclic, saturated or unsaturated, substituted or unsubstituted, mono- or polyaromatic substituted or unsubstituted, saturated or unsaturated heterocyclic, branched or unbranched, glycols, polyethylene glycols, polypropylene glycols, ethylene glycol-propylene glycol copolymers, glycol ethers, thioglycols, thioalcohols, sulfones, sulfoxides, alcohols, thiols, ureas, lactams, N-alkylated pyrrolidones, N-piperidones, alkylated cyclotetramethylenesulfone
• chlorobenzenes fluorobenzenes, perfluoroalkanes such as perfluorohexanes, perfluorodecanes, perfluorododecanes, perfluorohexadecane, tetraethyleneglycoldimethylether, sulfolane, N-methylpyrrolidone, 1,3-dioxan-2-one, propylene carbonate, ethylene carbonate, diethyl carbonate, diisobutyl carbonate, diphenyl carbonate, glycerol carbonate, dimethylpropyleneurea, N-methylcaprolactam, dimethylformamide, dimethylacetamide, formamide, acetamide, 2-methoxy -2-methyl-3-butanone, 2-methoxy-2-methyl-4-pentanone, tetrahydropyrimidone, dimethylthiodipropionate, bis (2-hydroxyethyl) sulfone, 3-mercapto-1, 2-propan
• the system for capturing CO 2 according to the invention can be implemented according to a gas treatment process containing CO 2 , which according to the invention can be represented schematically as follows:
• the method for capturing CO 2 comprises a step of bringing the gaseous effluent to be treated into contact with the extraction medium as described above and a step of regenerating said extraction and generation medium. a gas rich in CO 2 .
• the stripping gas may, for example, be formed in situ by vaporization of one or more compounds present in the extraction medium: it may be one of the compounds defined according to the invention, but it may also be a compound from the gas to be treated which would have been absorbed with the CO 2 , such as water for example in the case of a smoke.
• the stripping gas may also be supplied to the regeneration step: it may be, for example, nitrogen, water vapor or a part of the treated gas resulting from the absorption step.
• Example 1 (according to the invention):
• the extraction medium consists of mixture A, obtained by mixing 10.01 g (81 mmol) of 1,5-diazabicyclo (4.3.0) non-5-ene (DBN) with 16.65 g (82 mmol). of dodecanethiol.
• a CCVN 2 gas mixture containing 10% volume of CO 2 is brought into contact with the mixture A at atmospheric pressure and at a flow rate of 20 Nl / h in a double-jacketed glass bubble column thermostated at 40 ° C.
• the gas in FIG. column outlet is analyzed online by gas chromatography. When the capture is complete, the number of moles of CO 2 captured divided by the number of moles of DBN is equal to 0.38.
• Regeneration of the extraction medium is then carried out by stripping under a stream of nitrogen at 20 Nl / h at 40 ° C. in the same equipment at atmospheric pressure.
• the gas at the outlet of the column is analyzed online by gas chromatography.
• the regeneration rate defined by the ratio of the quantity of CO 2 released by regeneration divided by the quantity of CO 2 captured, of the mixture A is 90 ° C. % after 45 minutes and 100% after 60 minutes.
• the extraction medium consists of mixture B, obtained by mixing 30.5 g (200 mmol) of 1,8-diazabicyclo (5.4.0) undec-7-ene (DBU) with 21.6 g (211 mmol). hexanol.
• a CO 2 / N 2 gas mixture containing 10% CO 2 volume is contacted with the mixture B at atmospheric pressure and at a flow rate of 30 Nl / h in a glass bubble column at 22 ° C.
• the gas at the outlet of the column is analyzed online by gas chromatography.
• the number of moles of captured CO 2 divided by the number of moles of DBU is equal to 0.52.
• the regeneration of the extraction medium is then carried out by stripping under a stream of nitrogen at 20 Nl / h at 22 ° C. in the same equipment at atmospheric pressure.
• the gas at the outlet of the column is analyzed online by gas chromatography.
• This example shows the absorption and the regeneration of an aqueous solution of ethanolamine (MEA) at 30% by weight for comparison with an extraction medium according to the invention. It is a reference solvent for capturing CO 2 in fumes.
• the extraction medium consists of the mixture C, obtained by mixing 4.92 g
• the number of moles of MEA introduced is the same as the number of moles of DBN used in Example 1.
• a CO 2 / N 2 gas mixture containing 10% CO 2 volume is brought into contact with the mixture C at atmospheric pressure. and at a flow rate of 20 Nl / h in a double-jacketed glass bubble column thermostated at 40 ° C.
• the experimental conditions are the same as in Example 1.
• the gas at the outlet of the column is analyzed online by gas chromatography. When the capture is complete, the number of moles of CO 2 captured divided by the number of moles of MEA, is equal to 0.48.
• Regeneration of the extraction medium is then carried out by stripping under a stream of nitrogen at 20 Nl / h at 40 ° C. in the same equipment at atmospheric pressure as in Example 1.
• the gas at the outlet of the column is analyzed in line by gas chromatography.
• the regeneration rate defined by the ratio of the quantity of CO 2 released by regeneration divided by the quantity of CO 2 captured, of the mixture C is 19 ° C. % after 45 minutes, 21% after 60 minutes and 30% after 180 minutes.

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• 2006
  • 2006-11-27 FR FR0610495A patent/FR2909010B1/fr not_active Expired - Fee Related
• 2007
  • 2007-11-09 EP EP07870269A patent/EP2099551A2/de not_active Withdrawn
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