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
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/46—Removing components of defined structure
  • B01D53/62—Carbon oxides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/09—Diamines
  • C07C211/12—1,6-Diaminohexanes
• • 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
  • C07C215/08—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 only one hydroxy group and one amino group bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/10—Working-up natural gas or synthetic natural gas
  • C10L3/101—Removal of contaminants
  • C10L3/102—Removal of contaminants of acid contaminants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2251/00—Reactants
  • B01D2251/80—Organic bases or salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/30—Sulfur compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2257/00—Components to be removed
  • B01D2257/50—Carbon oxides
  • B01D2257/504—Carbon dioxide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/05—Biogas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2258/00—Sources of waste gases
  • B01D2258/06—Polluted air
• • 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
  • B01D53/34—Chemical or biological purification of waste gases
  • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
  • B01D53/77—Liquid phase processes
• • 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 to the removal of acidic compounds in a gaseous effluent.
• the present invention relates to the treatment of acid gases (H 2 S, CO 2 , COS, CS 2 , mercaptans, etc.) by means of a particular tertiary diamine, N, N, N ', N'-tetramethylhexane. 1,6-diamine in the form of an absorbent aqueous solution.
• acid gases H 2 S, CO 2 , COS, CS 2 , mercaptans, etc.
• the invention is advantageously applicable to the treatment of natural gas and gas of industrial origin.
• gaseous effluents that can be treated is various, and may be mentioned without limitation the synthesis gases, the combustion fumes, the refinery gases, the gases obtained at the bottom of the Claus process, the fermentation gases of biomass, cement gases and blast furnace gases.
• All these gases contain acidic compounds such as carbon dioxide (CO 2 ), hydrogen sulfide (H 2 S), carbon oxysulfide (COS), carbon disulfide (CS 2 ) and mercaptans (RSH). ), mainly methyl mercaptan (CH 3 SH), ethyl mercaptan (CH 3 CH 2 SH) and propylmercaptans (CH 3 CH 2 CH 2 SH).
• CO 2 is the acid compound that is to be removed.
• carbon dioxide is one of the greenhouse gases largely produced by different human activities and has a direct impact on air pollution.
• a post-combustion CO 2 capture unit aims to reduce the CO 2 emissions of a thermal power plant by 90%.
• the first step which is deacidification, aims to eliminate acid compounds such as carbon dioxide (CO 2 ), but also hydrogen sulphide (H 2 S), carbon oxysulfide (COS), carbon disulfide (CS 2 ) and mercaptans (RSH), mainly methyl mercaptan (CH 3 SH), ethyl mercaptan (CH 3 CH 2 SH) and propyl mercaptans (CH 3 CH 2 CH 2 SH).
• acid compounds such as carbon dioxide (CO 2 ), but also hydrogen sulphide (H 2 S), carbon oxysulfide (COS), carbon disulfide (CS 2 ) and mercaptans (RSH), mainly methyl mercaptan (CH 3 SH), ethyl mercaptan (CH 3 CH 2 SH) and propyl mercaptans (CH 3 CH 2 CH 2 SH).
• the generally accepted specifications for the deacidified gas are 2% CO 2 , or 50 ppm CO 2 to subsequently liquefy the natural gas; 4 ppm H 2 S, and 10 to 50 ppm volume of total sulfur.
• the dehydration step then controls the water content of the deacidified gas against transport specifications.
• the natural gas degassing step ensures the dew point of hydrocarbons in natural gas, again based on transport specifications.
• the deacidification is therefore often carried out first, in particular in order to eliminate toxic acid gases such as I 1 H 2 S in the first stage of the process chain and to avoid the pollution of the different unit operations by these acidic compounds. including the dehydration section and the heavier hydrocarbon condensation and separation section.
• Deacidification of gaseous effluents is usually carried out by washing with an absorbent solution.
• the absorbent solution makes it possible to absorb the acid compounds present in the gaseous effluent (in particular H 2 S, mercaptans, CO 2 , COS, CS 2 ).
• the solvents commonly used today are aqueous solutions of primary, secondary or tertiary alkanolamine, in combination with a possible physical solvent.
• document FR 2 820 430 can be cited which proposes processes for deacidification of gaseous effluents.
• US Pat. No. 6,852,144 describes a method for removing acidic compounds from hydrocarbons.
• the method uses a water-methyldiethanolamine or water-triethanolamine absorbent solution containing a high proportion of a compound belonging to the following group: piperazine and / or methylpiperazine and / or morpholine.
• the absorbed CO 2 reacts with the alkanolamine present in solution according to a reversible exothermic reaction, well known to those skilled in the art and leading to the formation of hydrogenocarbonates, carbonates and or carbamates, allowing elimination of CO 2 in the gas to be treated.
• I 1 H 2 S absorbed reacts with the alkanolamine present in solution according to a reversible exothermic reaction, well known to those skilled in the art and leading to the formation of hydrogen sulfide.
• regeneration energy represents about 3.7 GJ per tonne of CO 2 captured (reference case, project CASTOR, post-combustion capture pilot of the Esbjerg thermal power plant, reference Knudsen, JN; Jensen, JN; Vilhelmsen, PJ; Biede, O.
• CO 2 capture from coal-fueled pilot-scale Testing of different amine solvents Energy Procedia, Volume 1, Issue 1, February 2009, Pages 783-790).
• Such energy consumption represents a considerable operating cost for the CO 2 capture process.
• Regeneration of aqueous solutions of alkanolamines, such as MonoEthanolAmine is therefore carried out at regenerator bottom temperatures of the order of 110 0 C, see 130 0 C for more stable amines, such as MethylDiEthanolAmine. Because of these temperatures at the bottom of the regenerator, the acid gases (CO 2 , H 2 S, COS, CS 2 , etc.) are obtained at moderate pressures, from 1 to 3 bars. Depending on the nature of the regenerated acid gas and the applications, the acid gas may be sent to a treatment unit, or reinjected for sequestration.
• alkanolamines such as MonoEthanolAmine
• N, N, N ', N'-TetraMethylHexane-1,6-DiAmin or TMHDA is of significant interest in all processes for treating gaseous effluents for elimination. of acidic compounds.
• N, N, N1, N'-tetramethylhexane-l, 6-diamine in a mixture with other alkyl derivatives of hexane-l, 6-diamine, also of interest important in all processes for treating gaseous effluents for the removal of acidic compounds.
• the present invention therefore aims to overcome one or more of the disadvantages of the prior art by providing a method for removing acidic compounds, such as CO 2 , I 1 H 2 S, COS, CS 2 and mercaptans. , a gas by the use of a specific amine whose properties allow to limit the flow of absorbent solution used, especially at low partial pressure of acid gas, and which has a very high stability.
• acidic compounds such as CO 2 , I 1 H 2 S, COS, CS 2 and mercaptans.
• a first subject of the invention is a process for removing acidic compounds contained in a gaseous effluent, such as natural gas and industrial gases, comprising: a step of absorption of the acidic compounds by contacting the effluent with an aqueous solution comprising N, N, N ', N'-tetramethylhexane-1,6-diamine.
• At least one regeneration step of the absorbent solution loaded with acid compounds at least one regeneration step of the absorbent solution loaded with acid compounds.
• the present invention also relates to an aqueous absorbent solution comprising N, N ' / N'-Tetramethylhexane-1-diamine, in admixture with other alkylated derivatives of 1,6-hexane diamine.
• the invention also relates to the application of said process for the elimination of acidic compounds to the treatment of natural gas or to the treatment of gases of industrial origin, in particular CO 2 capture after combustion.
• the invention relates to an absorption process using an absorbent solution for absorbing the acidic compounds of a gaseous effluent, comprising: at least 10% by weight of water; at least one amine of formula (I) (commonly known as
• the absorbent solution advantageously comprises from 10 to 90% by weight of N, N ', N'-tetramethylhexane-1-diamine, preferably from 20 to 60% by weight of N, N, N', N'-tetramethylhexane-1,6-diamine, and most preferably 30 to 50% by weight of N, N'-tetramethylhexane-1,4-diamine.
• the absorbent solution may further comprise a non-zero and less than 50% by weight, preferably less than 20% by weight, amount of an activator compound.
• the activator compound is an amine containing at least one primary or secondary amine function.
• the activator is chosen from the group formed by:
• the absorbent solution may comprise a non-zero and less than 50% by weight, preferably less than 20% by weight, amount of one or more other alkyl derivatives of 1,6-hexane diamine.
• the alkyl derivatives are chosen from: Hexane-1,6-diamine, N, N'-dimethylhexane-1,6-diamine, N, N'-dibutylhexane-1,6-diamine, N, N, N ', N'-tetrabutylhexane; 1,6-diamine, N-methylhexane-1,6-diamine, N, N-dimethylhexane-1,6-diamine, N, N'-dimethylhexane-1,6-diamine, and N, N, N'-trimethylhexane-l, 6-diamine.
• the absorbent solution may comprise a physical solvent.
• the absorbent solution may comprise an organic or inorganic acid.
• the process for removing the acidic compounds contained in a gaseous effluent may comprise the following steps:
• a step of absorption of the acidic compounds by contacting the effluent with an absorbent solution according to the invention so as to obtain a gaseous effluent depleted in acidic compounds and an absorbent solution loaded with acid compounds, at least one step of regeneration of the absorbent solution loaded with acid compounds.
• the absorption step of the acidic compounds is carried out at a pressure of between 1 bar and 120 bar, and at a temperature of between 30 ° C. and 100 ° C.
• the thermal regeneration step is carried out at a temperature of between 100 ° C. and 180 ° C. and at a pressure of between 1 bar and 10 bars.
• the regeneration in the distillation column is carried out at a temperature of between 155 and 165 ° C. and at a pressure of between 6 and 8.5 bars in the case where it is desired to reinject the acid gases.
• the regeneration in the distillation column is carried out at a temperature of 115 ° C. and 130 ° C. and at a pressure of between 1.7 and 3 bars. in cases where the acid gas is sent to the atmosphere or in a downstream treatment process, such as a Claus process or a tail gas treatment process.
• a first step of expansion of the absorbent solution loaded with acidic compounds is carried out before the regeneration step.
• a second step of relaxation of the absorbent solution loaded with acidic compounds is carried out, the second expansion step being carried out after the first expansion step and before the regeneration step, the absorbent solution being heated before undergoing the reaction. second stage of relaxation.
• the invention also relates to a process according to the invention for the treatment of natural gas.
• the invention also relates to a process according to the invention for the treatment of gases of industrial origin, preferably for the capture of CO 2 .
• the process according to the invention is particularly well suited to capture acidic compounds present at low partial pressure in a gas.
• the absorption step of the acidic compounds is carried out for a gas having a partial pressure of acid gas (ie the sum of the partial pressure of H 2 S and CO 2 ) less than 20 bar.
• the absorption step of the acidic compounds is carried out at a partial pressure of acid gas of less than 5 bar.
• the absorption step of the acidic compounds is carried out at a partial pressure of acid gas of less than 2 bars.
• FIG. 1 given by way of example and showing a block diagram of a process for treating acid gas effluents.
• N, N, N ', N'-tetramethylhexane-l, 6-diamine, or TMHDA is of interest in all the acid gas treatment processes (natural gas, flue gases, etc.) / in aqueous composition of absorbent solution.
• the present invention proposes to eliminate the acidic compounds of a gaseous effluent by using an absorbent compound in aqueous solution.
• the absorbent compound according to the invention N, N, N ', N'-tetramethylhexane-1,6-diamine, has a greater absorption capacity with acid gases (CO 2 , H 2 S, COS, SO 2 , CS 2 and mercaptans) than the alkanolamines conventionally used.
• the use of an aqueous absorbent solution according to the invention makes it possible to economize on the investment cost and the operating costs of a deacidification unit (gas treatment and CO 2 capture).
• the molecule N ⁇ / N ⁇ N'-Tetramethylhexane-1 / ⁇ -diamine is interesting for its resistance to degradation, including thermal. Therefore, it is possible to regenerate the solvent at a higher temperature and thus to obtain an acid gas at higher pressure if this is of interest as the case where it is desired to perform the reinjection of the acid gas. This is particularly interesting in the case of post-combustion CO 2 capture where the acid gas must be compressed before reinjection and sequestration.
• the use of an aqueous absorbent solution according to the invention saves on the investment cost and operating costs associated with the compression of the acid gas.
• the absorbent solutions according to the invention can be obtained by mixing water and at least one alkylated derivative of hexane-1,6-diamine, of which N, N, N ', N'-tetramethylhexane-1, 6-diamine separately obtained by synthesis at a purity level greater than 90%.
• the absorbent solutions according to the invention can be obtained by mixing water and commercially available hexane-1,6-diamine alkyl derivatives, such as N, N, N 'and N'.
• tetramethylhexane-1,6-diamine optionally in a mixture with hexane-1,6-diamine, N, N'-dimethylhexane-1,6-diamine, N, N'-dibutylhexane-1,6 diamine, N, N, N ', N'-tetrabutylhexane-1,6-diamine.
• the absorbent solution according to the invention can be obtained by mixing water and a mixture of alkyl derivatives of hexane-l, 6-diamine, this mixture being obtained by one of the modes of synthesis A / and B / described below.
• the absorbent solutions according to the invention can be obtained by mixing water and a mixture of alkyl derivatives of hexane-l, 6-diamine, obtained during the same synthesis, as for example N, N, N ', N' ⁇ tetramethylhexane-l, 6-diamine optionally in mixture with hexane-1,6-diamine, N-methylhexane-l, 6-diamine, N, N-dimethylhexane-1,6-diamine, N, N '-dimethylhexane-1,6-diamine, N, N, N'-trimethylhexane-1,6-diamine.
• the mixture of alkyl derivatives of hexane-1,6-diamine can be obtained by partial alkylation of hexane-1,6-diamine.
• the mixture of alkyl derivatives of hexane-1,6-diamine can be obtained by condensation reaction of a compound X, or a mixture of compounds X, with a compound Y.
• X denotes here ammonia, methylamine, ethylamine, propylamines, butylamines.
• Y is here hexane-1,6-diol, hexane-1,6-dial or hexane-1,6-dinitrile.
• a methylation of hexane-l, 6-diamine by addition of formaldehyde or methanol, in the presence of a catalyst, under hydrogen pressure. If the methylation is carried out partially, for example in the absence of one of the reactants, a mixture of hexane-1,6-diamine, N-methylhexane-1,6-diamine and N, N-dimethylhexane can be obtained.
• 1,6-diamine N, N'-dimethylhexane-1,6-diamine, N, N, N'-trimethylhexane-1,6-diamine and N, N, N ', N'-tetramethylhexane-1 , 6-diamine.
• This mixture of methyl derivatives of hexane-l, 6-diamine can be used to produce the absorbent solution according to the invention by method of preparation 2. If the methylation is carried out completely, N, N, N 'can be obtained. N'-tetramethylhexane-1,6-diamine with a purity higher than 90%, which can be used to produce the absorbent solution according to the invention by the method of preparation 1.
• condensation of hexane-1,6-diol with, for example, a mixture of methylamine and dimethylamine in the presence of a catalyst can be carried out.
• a mixture of N, N'-dimethylhexane-1,6-diamine, N, N, N'-trimethylhexane-1,6-diamine and N N can be obtained.
• N ', N'-tetramethyIhexane-l, 6-diamine This mixture of methyl derivatives of hexane-l, 6-diamine can be used to produce the absorbent solution according to the invention by method of preparation 2.
• N can be obtained.
• the absorbent solutions according to the invention can be used to deacidify the following gaseous effluents: natural gas, synthesis gases, combustion fumes, refinery gases, gases obtained at the bottom of the Claus process, the gases of fermentation of biomass, cement gas, incinerator fumes.
• gaseous effluents contain one or more of the following acidic compounds: CO 2 , I 1 H 2 S, mercaptans, COS, CS 2 .
• Combustion fumes are produced notably by the combustion of hydrocarbons, biogas, coal in a boiler or for a turbine combustion gas, for example in order to produce electricity. These fumes have a temperature of between 20 and 60 ° C., a pressure of between 1 and 5 bars and can comprise between 50 and 80% of nitrogen, between 5 and 40% of carbon dioxide, between 1 and 20% of oxygen, and some impurities such as SOx and NOx, if they have not been removed downstream of the deacidification process.
• the natural gas consists mainly of gaseous hydrocarbons, but can contain several of the following acidic compounds: CO 2 , I 1 H 2 S, mercaptans, COS, CS 2 .
• the content of these acidic compounds is very variable and can be up to 40% for CO 2 and I 1 H 2 S.
• the temperature of natural gas can be between 20 0 C and 100 0 C.
• the pressure of natural gas to be treated may be between 10 and 120 bar.
• N, N, N ', N'-Tetramethylhexane-1,6-diamine may be in variable concentration, for example between 10% and 90% by weight, preferably between 20% and 60% by weight, very preferably between 30% and 60% by weight. % and 50% by weight in the aqueous solution.
• the absorbent solution may contain at least 10% by weight of water, in general between 10% and 90% by weight of water, very preferably at least 50% by weight, for example 60 to 70% by weight of water.
• N, N, N ', N'-Tetramethylhexane-1,6-diamine can be formulated with another amine, containing at least one primary or secondary amine function (activator), up to a concentration. 50% by weight, preferably less than 15% by weight, preferably less than 10% by weight.
• This type of formulation is particularly interesting in the case of the capture of CO 2 in industrial fumes, or the treatment of natural gas containing CO 2 above the desired specification. Indeed, for this type of applications, it is sought to increase the CO 2 capture kinetics, in order to reduce the size of the equipment.
• the absorbent solution according to the invention contains from 62 to 68% by weight of water, from 32 to 38% by weight of N, N, N ', N'-Tetramethylhexane-1,6-diamine.
• the absorbent solution according to the invention contains from 62 to 68% by weight of water, from 32 to 38% by weight of amines comprising N, N'-tetramethylhexane-1 / 6-diamine. mixing with a primary or secondary amine as an activator, the activator representing between 1% and 10% by weight of the final absorbent solution.
• the N, N, N 1 , N'-tetramethylhexane-1,6-diamine absorbent solution contains other organic compounds.
• the absorbent solution according to the invention may contain organic compounds which are not reactive with respect to acidic compounds (commonly called "physical solvents"), which make it possible to increase the solubility of at least one or more acidic compounds of the gaseous effluent.
• the absorbent solution may comprise between 5% and 50% by weight of physical solvent such as alcohols, glycol ethers, lactams, N-alkylated pyrrolidones, N-alkylated piperidones, cyclotetramethylenesulfone, N-alkylformamides. , N-alkylacetamides, ethers-ketones or alkyl phosphates and their derivatives.
• physical solvent such as alcohols, glycol ethers, lactams, N-alkylated pyrrolidones, N-alkylated piperidones, cyclotetramethylenesulfone, N-alkylformamides. , N-alkylacetamides, ethers-ketones or alkyl phosphates and their derivatives.
• it may be methanol, tetraethyleneglycoldimethylether, sulfolane or N-formyl morpholine.
• the N, N, N 1 , N'-tetramethylhexane-1,6-diamine absorbent solution may comprise an organic or inorganic acid.
• acid compounds that can be used for this purpose is given below:
• N, N, N ', N'-tetramethylhexane-1,6-diamine may be formulated with a derivatized alkyl derivative of 1,6-HexaneDiAmine.
• an alkyl derivative of 1,6-HexaneDiAmine is a
• R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom or a linear or branched alkyl group of 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.
• alkyl derivatives are chosen from: hexane-1,6-diamine,
• N, N, N ', N'-tetrabutylhexane-l, 6-diamine These derivatives can be obtained by the method of preparation 1.
• HexaneDiAmine are selected from: hexane-1,6-diamine, N-methylhexane-
• 1,6-diamine N, N-dimethylhexane-1,6-diamine, N, N'-dimethylhexane-1,6-diamine, or N, N, N'-trimethylhexane-1,6-diamine.
• These derivatives can be obtained according to the method of preparation 2.
• the absorbent solution according to the invention may comprise at least
• TMHDA 10% by weight of TMHDA and at least 1% by weight, preferably at least 5% by weight, or even 10% by weight, of an alkylated derivative of 1,6-HexaneDiAmine, said alkylated derivative being different from TMHDA.
• the mixture of alkyl derivatives of hexane-l, 6-diamine can have a proportion of non-alkylated IMH bonds of between 1 and 100%, preferably between 1 and
• HexaneDiAmine is between 10 to 90% by weight, preferably 20 to
• An absorbent solution comprising TMHDA and alkylated derivatives of hexane-1,6-diamine provides high stability to the absorbent solution. Indeed, the main degradation reaction is a transfer of alkyl groups from one amine to another, thus giving a similar amine mixture.
• Process for removing acidic compounds in a gaseous effluent (Fig. 2)
• an absorbent solution for deacidifying a gaseous effluent is carried out schematically by performing an absorption step followed by a regeneration step.
• the absorption step consists of contacting the gaseous effluent containing the acidic compounds to be removed with the absorbing solution in an absorption column C1.
• the gaseous effluent to be treated ( ⁇ 1) and the absorbent solution ( ⁇ 4 ) during the contact, the organic compounds provided with an amine function of the absorbent solution ( ⁇ 4) react with the acidic compounds contained in the effluent ( ⁇ 1) so as to obtain a gaseous effluent depleted in acid compounds ( ⁇ 2) which leaves at the top of column Cl and an acid-enriched absorbent solution ( ⁇ 3) which leaves at the bottom of column Cl.
• the absorbent solution enriched in acidic compounds ( ⁇ 3) is sent to an exchanger El where it is reheated by the stream ( ⁇ 6) from the regeneration column C2.
• the absorbent solution charged and heated at the outlet of the exchanger E1 ( ⁇ 5) feeds the distillation column (or regeneration column) C2 in which the regeneration of the absorbent solution loaded with acidic compounds takes place.
• the regeneration step therefore consists in particular in heating and, optionally, expanding, the acid-enriched absorbent solution in order to release the acidic compounds which come out at the top of column C2 in gaseous form ( ⁇ 7).
• the regenerated absorbent solution that is to say depleted in acidic compounds ( ⁇ 6), leaves at the bottom of the column C2, then passes into the exchanger El, in which it gives heat to the flow ( ⁇ 3) as previously described.
• the regenerated and cooled absorbent solution ( ⁇ 4) is then recycled to the absorption column Cl.
• the absorption step of the acidic compounds can be carried out at a pressure of between 1 bar and 120 bar, preferably between 20 bar and 100 bar for the treatment of a natural gas, preferably between 1 and 3 bar for the treatment industrial fumes, and at a temperature of between 20 ° C. and 100 ° C., preferably between 30 ° C. and 90 ° C., more preferably still between 30 ° C. and 60 ° C.
• the process according to invention has an excellent capacity of absorption of the acidic compounds when the temperature in the absorption column Cl is between 30 ° C. and 60 ° C.
• the regeneration step of the process according to the invention can be carried out by thermal regeneration, optionally supplemented by one or more expansion steps.
• Regeneration can be carried out at a pressure of between 1 bar and 5 bar, or even up to 10 bar and at a temperature between 100 0 C and 180 0 C, preferably between 130 0 C and 170 0 C.
• Example 1 Capture capacity of aqueous solutions of TMHDA
• the performance of the absorbent solution at 35% by weight of TMHDA in terms of capture capacity is compared with that of an aqueous solution of MonoEthanolAmine at 30% by weight, which constitutes the reference solvent for a post-fume capture application. combustion, and that of a 40% wt.% aqueous solution of MethylDiEthanolAmine which constitutes the reference solvent for a natural gas treatment application.
• the performance of the absorbent solution at 35% by weight of TMHDA in terms of capture capacity is compared with that of an aqueous solution of N, N, N ', N'-tetramethylpropane-1,3-diamine or TMPDA at 35% by weight, another tertiary diamine structure very close to that of N, N, N ', N'-Tetramethylhexane-l, 6-diamine, for post-combustion fume extraction application.
• the N, N, N ', N'-tetramethylhexane-1,6-diamine molecule has the particularity of capturing a very large quantity of acid gas.
• filler ( ⁇ n gas ac i / n mine) obtained at 4O 0 C for different partial pressures of CO 2 from the absorbent solution according to the invention and an absorbent solution of MonoEthanolAmin at 30% by weight or an absorbent solution of N, N, N ', N'-Tetramethylpropane-1,3-diamine at 35% by weight:
• This example shows the high loading rates that can be obtained thanks to an absorbent solution according to the invention, comprising 35% by weight of N, N, N ', N'-Tetramethylhexane-1,6-diamine, especially for low pressures. partial acid gas.
• Example 2 Capture Capacity of the aqueous solutions of TMHDA mixed with alkyl derivatives of hexane-1,6-diamine
• Absorbent solutions according to the invention containing TMHDA and alkyl derivatives of hexane-1,6-diamine, the cumulative amount of which is equal to 35% by weight or 40%, are used in these examples.
• the absorbent solutions according to the invention are obtained according to the method of preparation 1.
• Absorbent solutions according to the invention have the particularity of capturing a very large amount of acid gas.
• This example shows the significant loading rates that can be obtained thanks to an absorbent solution according to the invention especially for low partial pressures of acid gases.
• one can compare the charging rate ( ⁇ n acid gas / am ine n) obtained at 40 0 C to a partial pressure of CO 2 of 0.1 bar for various absorbent solutions of the invention ( B series) and an absorbent solution of MonoEthanolAmine at 30% by weight or an absorbent solution of N, N, N 1 , N 1 -tetramethylpropane-1,3-diamine at 35% by weight:
• This example shows the high charge rates that can be obtained thanks to an absorbent solution according to the invention are little affected, especially for low partial pressures of acid gases, by the proportion of non-alkylated NH bonds in the mixture of derivatives of I hexane-1,6-diamine, which varies between 0 and 75% of the absorbent solutions B1 to B5.
• the performances of the aqueous solutions of TMHDA in terms of stability are compared to that of an aqueous solution of MonoEthanolAmine at 30% by weight, which constitutes the reference solvent for an application of collection of fumes in post-combustion, and that of an aqueous solution of 40% wt% MethylDiEthanolAmin which constitutes the reference solvent for a natural gas treatment application.
• the performances of the aqueous solutions of TMHDA in terms of stability are compared with that of an aqueous solution of N, N, N ', N 1 -tetramethylpropane-1,3-diamine or 35% TMPDA, another diamine tertiary structure very close to that of N, N, N ', N'-Tetramethylhexane-l, 6-diamine, for post-combustion fumes collection application.
• the N, N, N'-tetramethylhexane-1,4-diamine molecule has the particularity of being particularly resistant to degradation that may occur in a deacidification unit.
• the aqueous amine solutions are degraded in a closed reactor, heated to a temperature T, and pressurized under a partial pressure PP of different gases (CO 2 , O 2 , H 2 S, N 2 ).
• the liquid phase is stirred using a magnetic bar.
• a representative sample of the liquid phase is taken and analyzed by various techniques, in particular by gas chromatography.
• the table below gives the degradation rate TD of the absorbing solution, under different conditions, for a duration of 15 days, defined by the equation below:
• [Amine] 0 is the concentration of the amine in the undegraded solution.
• the table below gives the degradation rate TD of different absorbent solutions, for a temperature of 140 ° C., in the absence and in the presence of different acid gases.
• the table below gives the degradation rate TD of various aqueous solutions of amine, for a temperature of 180 ° C., in the absence and in the presence of acid gas, which is representative of the degradations that could occur at the bottom of the regenerator. if it is desired to obtain a high pressure acid gas for reinjection applications.
• N, N, N ', N'-tetramethylhexane-1,6-diamine as an amine in an absorbent solution makes it possible to obtain a low degradation rate compared to the amine-based absorbent solutions of the prior art (MethylDiEthanoIAmine and MonoEthanolAmine). It may further be noted that the alkylated derivatives of hexane-l, 6-diamine are much more stable than a molecule of very close structure, such as N, N, N ', N'-TetraMethylPropane-l, 3- diamine (TMPDA).
• N, N, N'-trimethylhexane-1,6-diamine is produced by degradation of N, N, N ', N'-tetramethylhexane-1,6-diamine.
• the loss of an alkyl group can modify the proportion of non-alkylated NH bonds.
• CO 2 capture properties are affected by the proportion of non-alkylated NH bonds.
• the loss of an alkyl group results in the alkylation of a nucleophilic species present in solution. By Consequently, the degradation of the absorbent solutions according to the invention very little modifies the proportion of non-alkylated NH bonds.

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