WO2011080406A1 - Procede d ' elimination de composes acides d ' un effluent gazeaux avec une solution absorbante a base de triamines - Google Patents
Procede d ' elimination de composes acides d ' un effluent gazeaux avec une solution absorbante a base de triamines Download PDFInfo
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- WO2011080406A1 WO2011080406A1 PCT/FR2010/000786 FR2010000786W WO2011080406A1 WO 2011080406 A1 WO2011080406 A1 WO 2011080406A1 FR 2010000786 W FR2010000786 W FR 2010000786W WO 2011080406 A1 WO2011080406 A1 WO 2011080406A1
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- diethyl
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- absorbent solution
- propanediamine
- triamine
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- 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
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- 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
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- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- 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
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- 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
- B01D2252/10—Inorganic absorbents
- B01D2252/103—Water
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- 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
- B01D2252/20415—Tri- or polyamines
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- 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
- B01D2252/20426—Secondary amines
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- 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
- B01D2252/20431—Tertiary amines
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- 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
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- 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
- B01D2252/20452—Cyclic amines containing a morpholine-ring
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- 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
- B01D2257/304—Hydrogen sulfide
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- 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
Definitions
- the present invention relates to the removal of acidic compounds (H 2 S, C0 2 ,
- the invention is advantageously applicable to the treatment of gas of industrial origin and natural gas.
- 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 for example carbon dioxide (C0 2 ), hydrogen sulphide (H 2 S), carbon oxysulfide (COS), carbon disulphide (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).
- C0 2 carbon dioxide
- H 2 S hydrogen sulphide
- COS carbon oxysulfide
- CS 2 carbon disulphide
- a post-combustion C0 2 capture unit aims, in general, to reduce by 90% the C0 2 emissions of a thermal power station.
- Decarbonation is generally carried out by washing the gas with an absorbent solution containing one or more amines.
- the gaseous effluent contains carbon monoxide CO, hydrogen H 2 , water vapor and carbon dioxide C0 2 . It contains, in addition, sulfur (H 2 S, COS, etc.), nitrogen (NH 3 , HCN) and halogenated impurities which must be removed so that the gas contains only residual levels.
- the impurities present in the unpurified synthesis gas can lead to accelerated corrosion of the plants and are likely to poison the catalysts used for chemical synthesis processes such as those used in the Fischer-Tropsch synthesis or methanol, or mitigate the performance of materials used in fuel cells.
- Environmental considerations also require the removal of impurities present in the gases.
- the input specifications of the Fischer-Tropsch unit are particularly severe, the contents present in the synthesis gas generally being less than 10 ppb weight for the sulfur impurities.
- the gas is generally washed with an absorbent solution containing amines, combined with the use of capture masses.
- the deacidification of natural gas aims to eliminate acid compounds such as carbon dioxide (C0 2 ), but also hydrogen sulphide (H 2 S), carbon oxysulfide (COS), carbon disulphide (CS 2 ) and mercaptans (SH), mainly methyl mercaptan (CH 3 SH), ethyl mercaptan (CH 3 CH 2 SH) and propyl mercaptans (CH 3 CH 2 CH 2 SH).
- the specifications generally carried out on the deacidified gas are 2% of C0 2 , or even 50 ppm volume of C0 2 to subsequently liquefy the natural gas; 4 ppm H 2 S, and 10 to 50 ppm volume of total sulfur.
- Deacidification is therefore often carried out first, in particular in order to eliminate toxic acid gases such as 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 is generally performed by washing the gas with an absorbent solution containing one or more amines.
- the deacidification of the gaseous effluents is generally carried out by washing with an absorbent solution.
- the absorbent solution makes it possible to absorb the acidic compounds present in the gaseous effluent (in particular C0 2 , H 2 S, mercaptans, 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.
- Patent US 4240923 recommends the use of so-called sterically hindered amines for removing acidic compounds from a gaseous effluent comprising, these amines having in particular advantages in terms of absorption capacity and regeneration energy.
- the structures described are in particular nitrogen heterocyclics derived from piperidine, the position of which at the nitrogen atom is congested by an alkyl or alcohol group in particular.
- the absorbed H 2 S reacts instantaneously with the alkanolamine present in solution according to a reversible exothermic reaction, which is well known to a person skilled in the art and leading to to the formation of hydrogen sulfide.
- H 2 S enrichment unit is needed to concentrate the acid gas in H 2 S.
- the most selective amine will be sought.
- Tertiary amines such as Methyldiethanolamine, or hindered with slow reaction kinetics with C0 2 are commonly used, but have limited selectivities at high H 2 S loading rates.
- the absorption step Sizing of the absorption column is crucial to ensure proper operation of the unit. If as mentioned above the C0 2 uptake kinetics is a criterion determining the column height, the cyclic capacity of the solvent is a criterion determining the diameter of the column. Indeed, the more the solvent has a high cyclic capacity, the lower the flow of solvent required to treat the acid gas will be. Thus, the lower the flow of solvent to circulate in the column, the smaller the diameter of the absorption column can be, without the occurrence of clogging phenomenon of the column. In an application where the absorption column is under pressure, such as the treatment of natural gas or synthesis gas, the diameter of the column has a huge impact on the steel mass constituting the absorption column, and therefore its cost.
- the last item concerns the energy to be supplied to break the bond created between the amine used and the C0 2 .
- To reduce the energy consumption associated with the regeneration of the solvent it is therefore preferable to -minimize the binding enthalpy ⁇ .
- the best solvent from an energy point of view is therefore that which will have the best compromise between a strong cyclic capacity ⁇ and a low enthalpy of connection ⁇ .
- 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 C0 2 , H 2 S, COS, CS 2 , S0 2 and mercaptans, a gas by the use of a specific amine whose absorbing properties are greater than those of the reference amines used in post-combustion C0 2 capture applications and in treatment applications.
- acidic compounds such as C0 2 , H 2 S, COS, CS 2 , S0 2 and mercaptans
- natural gas namely monoethanolamine (MEA) and methyldiethanolamine (MDEA) respectively.
- the present invention describes a process for removing the acidic compounds contained in a gaseous effluent, in which an absorption step of the acidic compounds is carried out by contacting the effluent with an absorbent solution comprising:
- each of the radicals R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 is independently chosen from:
- alkyl or alkylene hydrocarbon radical containing from 1 to 6 carbon atoms
- each of the radicals X and Y is independently chosen from structures A and B,
- each of the radicals R.9 and R10 is independently selected from an alkyl or alkylene hydrocarbon radical containing 1 to 6 carbon atoms,
- each of R 1 and R 12 is independently selected from hydrogen or an alkyl or alkylene hydrocarbon radical having 1 to 6 carbon atoms, and wherein Z is an ether function or Z is a covalent bond and wherein x and y are integers independently selected from 1 to 3, the choice of X, Y, and R 1, R 2, R 3 and R 4 respecting any of the following rules:
- o rule 2 X meets the definition of A and Y meets the definition of B
- o rule 3 X meets the definition of B and Y meets the definition of A
- o rule 4 X and Y meet each at the definition of A and at least one of the four radicals R 1, R 2, R 3 and R 4 is an alkyl or alkylene hydrocarbon radical containing between 1 and 6 carbon atoms.
- Each of the radicals R 1, R 2, R 3, R 4, R 5, R 6, R 7 and R 8 may be independently chosen from a hydrogen atom, a methyl radical or an ethyl radical,
- Each of the numbers a and b can be independently selected as 1 or 2,
- radicals R 9 and R 10 can be independently chosen from a methyl radical or an ethyl radical
- Ru and Ri2 can be hydrogen atoms
- the triamine may be selected from the group consisting of N, N-dimethyl-N'- [1 (dimethylamino) -2-propyl] -1,2-ethanediamine, N, N-diethyl-N'- [(1-Dimethylamino) -2-propyl] -1,2-ethanediamine, (N, N-dimethylaminopropyl) imino-2- (N, N-dimethylpropylamine), N, N-diethyl-N 1 - [1 (dimethylamino) ) -2-propyl] -l, 3-propanediamine / the [N, N-dimethyl-N '- (3-N- morphormopropyl] -l, 2-propanediamine, N, N-diethyl-N'- [1 (dimethylaminoethyl) -1,4-pentanediamine, N, N-diethyl-N '- [2-e
- the secondary amine function may be linked to at least one quaternary carbon or to two tertiary carbons.
- the triamine may be selected from the group consisting of N, N-diethyl-N '- [1 (dimethylamino) -2-propyl] -1,4-pentanediamine, N, N-diethyl-N 1- [1- (dimethylamino) -3-butyl] -1,4-pentanediamine, N, N -diethyl-N'-trimethylaminol-S-butyl-1H-pentanediamine and N, N-diethyl-N ' - [l (diethylamino) -2-methyl-3-pentyl] -l, 4-pentanediamine.
- the absorbent solution may comprise between 10% and 60% by weight of triamine and between 10 and 90% by weight of water.
- the absorbent solution may further comprise a non-zero amount and less than 20% by weight of an activator compound, said compound comprising a primary or secondary amine function.
- the activator compound may be selected from the group consisting of:
- the absorbent solution may further comprise a physical solvent selected from methanol and sulfolane.
- the absorption step of the acidic compounds can be carried out at a pressure of between 1 bar and 120 bar and at a temperature of between 20 ° C. and 100 ° C.
- a regeneration step of the absorbent solution loaded with acid compounds in which at least one of the following operations is carried out: heating, expansion, distillation.
- the regeneration step can be carried out at a pressure of between 1 bar and 10 bar and a temperature of between 100 ° C. and 180 ° C.
- the gaseous effluent may be chosen from natural gas, synthesis gases, combustion fumes, refinery gases, bottoms gases from the Claus process, biomass fermentation gases, cement gases, fumes. incinerator.
- the process according to the invention can be implemented for the selective removal of H 2 S from a gaseous effluent comprising H 2 S and CO 2 .
- the compounds corresponding to the definition of the triamines according to the invention make it possible to obtain higher cyclic capacities than the reference amines, both in applications where the partial pressure of acid gas is low, only in applications where the partial pressure of acid gas is high.
- This performance is certainly increased because of a higher density of amine sites relative to the molecular weight of the molecules, but also of having on the same molecule a secondary amine function, and two tertiary amino functions that can not form carbamates around the secondary amine function.
- by varying the steric hindrance of the secondary amine function it is possible to obtain high performance amines both in total deacidification applications and in applications where selective removal of PH 2 S is required. .
- the invention relates to a method for absorbing acidic compounds from a gaseous effluent by contacting the gaseous effluent with a liquid absorbent solution comprising:
- the triamine responding to the following eneral form (I) and conditioned by the rules specified below.
- radicals R 1, R 2, R 3 and R 4 are independently chosen from:
- alkyl or alkylene hydrocarbon radical containing 1 to 6 carbon atoms preferably an alkyl hydrocarbon radical containing from 1 to 3 carbon atoms and preferably 1 or 2 carbon atoms.
- R5, R6, R7 and R8 is independently selected from:
- alkyl or alkylene hydrocarbon radical containing 1 to 6 carbon atoms preferably an alkyl hydrocarbon radical containing from 1 to 3 carbon atoms and preferably 1 or 2 carbon atoms.
- R5, R6, R7 and R8 are preferably hydrogen atoms.
- integers a and b are independently selected from 1 to 5 and preferably each of the numbers a and b is independently 1 or 2.
- radicals X and Y are independently selected from structures A and B defined below and according to the rules specified below.
- A is a radical of the general formula: 0
- R9 and R10 are independently selected from an alkyl or alkylene hydrocarbon radical having 1 to 6 carbon atoms, preferably an alkyl hydrocarbon radical having 1 to 3 carbon atoms and preferably 1 to 2 carbon atoms.
- the radical A is a dimethylamine or diethylamine radical.
- B is a radical of general formula
- Ru and R12 are independently chosen from a hydrogen atom or an alkyl or alkylene hydrocarbon radical, containing 1 to 6 carbon atoms, preferably an alkyl hydrocarbon radical containing from 1 to 3 carbon atoms and preferably 1 or 2 carbon atoms, and
- R 11 and R 12 are preferably hydrogen atoms
- Z is an ether function, that is to say a -O- unit, or Z is a covalent bond
- integers x and y are independently selected from 1 to 3.
- Z is an ether function, i.e. a -O-
- x and y are preferably each equal to 2.
- Z is a bond covalently, the sum (x + y) is preferably 4 or 5.
- radical B is a piperidine, morpholine or pyrrolidine ring.
- X and Y each correspond to the definition of A and in this case at least one of the four radicals R 1, R 2, R 3 and R 4 is imperatively different from a hydrogen atom, in other words the steric hindrance of the secondary amine function is imperatively reinforced.
- preferably one or two of the four radicals R 1, R 2, R 3 and R 4 are necessarily different from a hydrogen atom, in other words preferably one or two of the four radicals R 1, R 2, R 3 and R4 are alkyl hydrocarbon radicals as described above.
- X and Y, and the radicals R 1, R 2, R 3 and R 4 are chosen according to one of the rules 2, 3 and 4.
- the invention relates to a method for selectively removing H 2 S in a gas containing H 2 S and CO 2 .
- the triamine according to the invention is chosen such that the secondary amine function is severely congested, that is to say that the secondary amine function is connected to at least one quaternary carbon or to two tertiary carbons .
- the severely hindered secondary amino function is connected to a quaternary carbon and a secondary carbon, a quaternary carbon and a tertiary carbon, two tertiary carbons, or two quaternary carbons.
- the compound of general formula (I) is such that the radicals R 1 and R 2 are both hydrogens and that the radicals R3 and R4 are both methyls.
- the compound of general formula (I) is such that the radicals R 1 and R 3 are both hydrogens and that the radicals R2 and R4 are both methyls.
- FIG. 1 FIG. principle of a process for treating acid gas effluents.
- the compounds of general formulas (I) are of interest in all processes for treating acid gases (natural gas, combustion fumes, synthesis gas, etc.) in an aqueous absorbent solution composition.
- the present invention proposes to eliminate the acidic compounds of a gaseous effluent by using an absorbent compound in aqueous solution.
- the triamines according to the invention have a greater capacity of absorption with the acidic compounds, in particular the CO 2 / the H 2 S, the COS, the SO 2 , the CS 2 and the mercaptans, as monoethanolamine (MEA) and methyldiethanolamine (MDEA), conventionally used.
- the use of an aqueous absorbent solution according to the invention makes it possible to save on the investment cost and the operating costs of a deacidification unit (gas treatment and C0 2 capture).
- the invention makes it possible to reduce the amount of CO 2 captured for a higher H 2 S loading rate relative to the MDEA. This gain in capacity and selectivity leads to savings in investment costs and operating costs of the deacidification unit as well as the downstream Claus unit which will process a gas richer in H 2 S.
- 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: C0 2 , H 2 S, mercaptans, COS, CS 2 , SO 2 .
- the combustion fumes are produced in particular by the combustion of hydrocarbons, biogas, coal in a boiler or for a combustion gas turbine, for example for the purpose of producing electricity.
- These fumes have a temperature of between 20 and 60 ° C., a pressure of between 1 and 5 bar 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 synthesis gas contains carbon monoxide CO, hydrogen H 2 (generally in a ratio H 2 / CO equal to 2), water vapor (generally at saturation at the temperature where the washing is carried out) and carbon dioxide C0 2 (of the order of ten%).
- the pressure is generally between 20 and 30 bar, but can reach up to 70 bar. It contains, in addition, sulfur impurities (H 2 S, COS, etc.), nitrogen (NH 3 , HCN) and halogenated impurities.
- the natural gas consists mainly of gaseous hydrocarbons, but can contain several of the following acidic compounds: C0 2 , H 2 S, mercaptans, COS, CS 2 .
- the content of these acidic compounds is very variable and can be up to 40% for C0 2 and H 2 S.
- the temperature of the natural gas can be between 20 ° C and 100 ° C.
- the pressure of the natural gas to be treated may be between 10 and 120 bar.
- the triamines of the invention can be synthesized according to different reaction paths. Without being exhaustive, we cite, by way of example, the following routes: for example
- W is a releasable group in the sense of organic chemistry. It is generally chosen from a halogen atom, especially a chlorine, bromine or iodine atom. W may also be a tosylate or mesylate radical well known as releasable groups. In some cases the nitro groups can satisfy the reaction.
- X and Y all carry a tertiary amine function which is specified with the definitions of X and Y.
- these functions may be present in the form of hydrohalides, for example hydrochlorides. or for example
- Triamines according to the invention can still be accessed by firstly reacting a synthon 1 bearing a primary amine function with a synthon 2 bearing an aldehyde or ketone function in order to obtain an imine and then proceeding to a hydrogenation step leading to a secondary amine.
- This synthesis route illustrated below, has the advantage of not generating by-products such as salts in the case of the condensation of an amine on a halide.
- the molecules of the list a) having a small or moderate bulk of the NH function are distinguished from the list b) of molecules having a severe congestion of the NH function.
- the molecules of list b) are particularly suitable for selective removal of H 2 S in a gas containing H 2 S and CO 2 a) Molecules with a small or moderate bulk
- the triamines according to the invention 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 50% by weight, in the aqueous solution.
- the absorbent solution may contain between 10% and 90% by weight of water, preferably 50 to 70% of water.
- the compounds of general formula (I) may be formulated with another amine, containing at least one primary or secondary amine function (activator), up to a concentration of 20% by weight, preferably less than 15%. % by weight, preferably less than 10% by weight.
- This type of formulation is particularly advantageous in the case of capture of C0 2 in industrial fumes, or the treatment of natural gas containing CO 2 and / or COS above the desired specification. Indeed, for this type of applications, it is sought to increase the capture kinetics of C0 2 and / or COS to reduce the size of equipment.
- the absorbent solution may comprise a physical solvent, for example methanol or sulfolane.
- an absorbent solution for deacidifying a gaseous effluent is carried out schematically by performing an absorption step followed by a regeneration step, for example as shown in FIG. It consists in contacting the gaseous effluent containing the acidic compounds to be eliminated with the absorbing solution in a Cl absorption column.
- the gaseous effluent to be treated 1 and the absorbent solution 4 feed the column C1.
- 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 acidic compounds 2 which leaves at the top of column C1 and an acid-enriched absorbent solution 3 which leaves at the bottom of column C1.
- the acid-enriched absorbent solution 3 is sent to an exchanger E1, where it is heated by stream 6 from the regeneration column C2.
- the absorbent solution 5 charged and heated at the outlet of the exchanger E1 feeds the distillation column (or regeneration column) C2 in which the regeneration of the absorbent solution loaded with acidic compounds takes place.
- the absorbent solution 3 or 5 loaded with acidic compounds can be relaxed.
- the regeneration step may therefore consist in heating, optionally to relax, or distilling 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 and cooled absorbent solution 4 is then recycled to the absorption column C1.
- 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 bar and 3 bar for treatment of industrial fumes, and at a temperature between 20 ° C and 100 ° C, preferably between 30 ° C and 90 ° C, or 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.
- the 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 of between 100 ° C. and 180 ° C., preferably between 130 ° C. and 170 ° C.
- the regeneration temperature is between 155 ° C. and 180 ° C. in the case where it is desired to reinject the acid gases.
- the regeneration temperature is between 115 and 130 ° C. in the 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.
- Absorbent solutions used in these examples are aqueous solutions comprising 30% by weight of triamines according to the invention.
- the performances are compared in particular with that of an aqueous solution of MonoEthanolAmine at 30% by weight, which constitutes the reference absorbent solution for a postcombustion and post-combustion fume capture application.
- aqueous solution of MethylDiethanolAmin at 40% by weight which constitutes the reference absorbent solution for a natural gas treatment application.
- N, N-diethyl-N '- [2-ethyl-N "-morpholino] -l, 3-propanediamine 537 g (4.13 mol) of 3-diethylaminopropylamine and 153.9 g (0.83 mol) of 4- (2-chloroethyl) morpholine in its hydrochloride form are introduced into a flask.
- the medium is brought to the temperature of 80 ° C. for 5 hours, then after returning to ambient temperature, the medium is neutralized with 69.5 g of sodium hydroxide pellets for 1 hour at 80 ° C. After filtration, the solid is washed with ether and the ethereal fraction is then added to the product and the medium is distilled off. 153.5 g of a fraction distilling around 127 ° C. under 1.5 mm Hg and whose purity is 97.7% by gas chromatography and whose NMR spectrum is consistent with the desired theoretical structure is collected.
- N, N-dimethyl-N '- [l (dimethylamino) -2-propyl] -l, 2-ethanediamine 338.9 g (3.85 mol) of ⁇ , ⁇ -dimethylethylenediamine and 121.7 g (0.77 mol) of 1-dimethylamino-2-chloropropane in its hydrochloride form are introduced into a flask.
- the medium is heated at a temperature of 80 ° C. for 5 hours. After evaporation of the excess amine, the medium is neutralized, at room temperature, with 64.7 g of sodium hydroxide in the presence of 80 ml of ethanol and 25 ml of water. After filtration, the medium is distilled. 89 g of a fraction distilling between 38 and 41 ° C. under 0.5 mm Hg are collected and whose NMR spectrum is in accordance with the desired theoretical structure.
- N, N-diethyl-N '- [1 (dimethylaminoethyl) -1,4-pentanediamine 438.9 g (2.78 mol) of 2-amino-5-diethylaminopentane and then 100.0 g (0.69 mol) of dimethylaminoethyl chloride in its hydrochloride form are introduced into a flask.
- the medium is brought to the temperature of 80 ° C. for 6 hours, then after returning to ambient temperature, the medium is neutralized with 58.3 g of sodium hydroxide in the presence of 50 ml of water. After filtration, the solid is washed with ether and then the washing fraction is added to the product and the medium is distilled off. After removal of the excess amine and the solvent, 74.7 g of a fraction distilling between 86 and 87 ° C. under 0.3 mm Hg are collected and whose NMR spectrum is in accordance with the desired theoretical structure.
- RNAi do nb m ole of acid gas / nb of moles RNAi do
- the partial pressures of C0 2 in the effluent to be treated are typically 0.1 bar with a temperature of 40 ° C., and wants to cut down 90% of the acid gas.
- the charge rate is therefore considered as the absorbing solution corresponding to a partial pressure of CO 2 of 0.1 bar at equilibrium.
- the partial pressures of CO 2 in the gas to be treated are for example 0.3 bar and 1 bar with a temperature of 40 ° C.
- 50ppm which in first approximation corresponds to a completely regenerated solvent (at 50 ppm ⁇ 0).
- the cyclic capacity AO is then calculated.
- L NG expressed as moles of C0 2 per kg of the absorbent solution, considering that the solvent reaches its thermodynamic capacity
- This example shows the higher loading rates that can be obtained thanks to an absorbent solution according to the invention, comprising 30% by weight of molecules of general formula (I) both at low and at high partial pressures of acid gases. .
- this example illustrates the greatest cyclic capacity in moles of C0 2 per kilogram.
- the absorbent solution obtained by means of an absorbent solution according to the invention comprising 30% by weight of molecules of general formula (I) to reach a specification of 50 ppm CO 2 in the treated gas.
- Example 3 Amines capture capacity of general formula (I) whose secondary nitrogen is congested in a
- This example shows the higher loading rates that can be obtained thanks to an absorbent solution according to the invention, comprising 30% by weight of molecules of general formula (I) both at low and at high partial pressures of acid gases. .
- EXAMPLE 4 Ability and selectivity of removal of H 2 S from a gaseous effluent containing H 2 S and CO 2 by an amine solution of formula (I), the secondary amine function of which is severely congested: An absorption test at 40 ° C. at atmospheric pressure is carried out on aqueous amine solutions.
- the absorption is carried out in a liquid volume of 50 cm 3 by bubbling a gaseous stream consisting of a nitrogen mixture: carbon dioxide: hydrogen sulphide of 89: 10: 1 in volume proportions, of a flow rate of 30NL / h for 4 hours.
- This selectivity S is defined as follows.
- This example illustrates the gains in charge ratio and selectivity that can be achieved with an absorbent solution according to the invention, comprising 35% by weight of molecules of general formula (I) with a severe bulk of the secondary amine function.
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10805439A EP2512631A1 (fr) | 2009-12-16 | 2010-11-25 | Procede d ' elimination de composes acides d ' un effluent gazeaux avec une solution absorbante a base de triamines |
AU2010338157A AU2010338157A1 (en) | 2009-12-16 | 2010-11-25 | Method for removing acid compounds from a gaseous effluent using a triamine-based absorbent solution |
CA2783719A CA2783719A1 (fr) | 2009-12-16 | 2010-11-25 | Procede d ' elimination de composes acides d ' un effluent gazeaux avec une solution absorbante a base de triamines |
US13/515,340 US20130023712A1 (en) | 2009-12-16 | 2010-11-25 | Method of removing acid compounds from a gaseous effluent with an absorbent solution based on i/ii/iii triamines |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR09/06.099 | 2009-12-16 | ||
FR0906099A FR2953736B1 (fr) | 2009-12-16 | 2009-12-16 | Procede d'elimination de composes acides d'un effluent gazeux avec une solution absorbante a base de triamines iii/ii/iii. |
Publications (1)
Publication Number | Publication Date |
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WO2011080406A1 true WO2011080406A1 (fr) | 2011-07-07 |
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ID=42340372
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2010/000786 WO2011080406A1 (fr) | 2009-12-16 | 2010-11-25 | Procede d ' elimination de composes acides d ' un effluent gazeaux avec une solution absorbante a base de triamines |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130023712A1 (fr) |
EP (1) | EP2512631A1 (fr) |
AU (1) | AU2010338157A1 (fr) |
CA (1) | CA2783719A1 (fr) |
FR (1) | FR2953736B1 (fr) |
WO (1) | WO2011080406A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102012200566A1 (de) | 2012-01-16 | 2013-07-18 | Evonik Degussa Gmbh | Verfahren zur Absorption von CO2 aus einer Gasmischung |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR112014008497A2 (pt) | 2011-11-14 | 2017-04-11 | Evonik Degussa Gmbh | método e dispositivo para a separação de gases acídicos a partir de uma mistura de gás |
DE102012200907A1 (de) | 2012-01-23 | 2013-07-25 | Evonik Industries Ag | Verfahren und Absorptionsmedium zur Absorption von CO2 aus einer Gasmischung |
DE102012207509A1 (de) | 2012-05-07 | 2013-11-07 | Evonik Degussa Gmbh | Verfahren zur Absorption von CO2 aus einer Gasmischung |
DE102015212749A1 (de) | 2015-07-08 | 2017-01-12 | Evonik Degussa Gmbh | Verfahren zur Entfeuchtung von feuchten Gasgemischen |
DE102016210481B3 (de) | 2016-06-14 | 2017-06-08 | Evonik Degussa Gmbh | Verfahren zum Reinigen einer ionischen Flüssigkeit |
DE102016210478A1 (de) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Verfahren zur Entfeuchtung von feuchten Gasgemischen |
EP3257568B1 (fr) | 2016-06-14 | 2019-09-18 | Evonik Degussa GmbH | Procede de deshumidification de melanges gazeux humides par des liquides ioniques |
DE102016210484A1 (de) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Verfahren zur Entfeuchtung von feuchten Gasgemischen |
DE102016210483A1 (de) | 2016-06-14 | 2017-12-14 | Evonik Degussa Gmbh | Verfahren und Absorptionsmittel zur Entfeuchtung von feuchten Gasgemischen |
EP3257843A1 (fr) | 2016-06-14 | 2017-12-20 | Evonik Degussa GmbH | Procédé pour préparer un sel tres pur d'imidazolium |
CN110787472B (zh) * | 2018-08-01 | 2024-02-13 | 上海凯赛生物技术股份有限公司 | 戊二胺浓缩系统及浓缩方法 |
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FR2820430A1 (fr) | 2001-02-02 | 2002-08-09 | Inst Francais Du Petrole | Procede de desacidification d'un gaz avec lavage des hydrocarbures desorbes lors de la regeneration du solvant |
US6852144B1 (en) | 1999-10-05 | 2005-02-08 | Basf Aktiengesellschaft | Method for removing COS from a stream of hydrocarbon fluid and wash liquid for use in a method of this type |
FR2895273A1 (fr) * | 2005-12-22 | 2007-06-29 | Inst Francais Du Petrole | Procede de desacidification d'un gaz avec une solution absorbante a regeneration fractionnee avec controle de la teneur en eau de la solution |
-
2009
- 2009-12-16 FR FR0906099A patent/FR2953736B1/fr not_active Expired - Fee Related
-
2010
- 2010-11-25 AU AU2010338157A patent/AU2010338157A1/en not_active Abandoned
- 2010-11-25 EP EP10805439A patent/EP2512631A1/fr not_active Withdrawn
- 2010-11-25 US US13/515,340 patent/US20130023712A1/en not_active Abandoned
- 2010-11-25 CA CA2783719A patent/CA2783719A1/fr not_active Abandoned
- 2010-11-25 WO PCT/FR2010/000786 patent/WO2011080406A1/fr active Application Filing
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US4271132A (en) * | 1966-02-01 | 1981-06-02 | Eickmeyer Allen Garland | Method and compositions for removing acid gases from gaseous mixtures |
US4240923A (en) | 1978-05-30 | 1980-12-23 | Exxon Research & Engineering Co. | Process and amine-solvent absorbent for removing acidic gases from gaseous mixtures |
US4405581A (en) | 1982-01-18 | 1983-09-20 | Exxon Research And Engineering Co. | Process for the selective removal of hydrogen sulfide from gaseous mixtures with severely sterically hindered secondary amino compounds |
EP0544515A1 (fr) * | 1991-11-25 | 1993-06-02 | Exxon Chemical Patents Inc. | Procédé et dispositif d'élimination de gaz acide d'une mélange de gaz |
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US6852144B1 (en) | 1999-10-05 | 2005-02-08 | Basf Aktiengesellschaft | Method for removing COS from a stream of hydrocarbon fluid and wash liquid for use in a method of this type |
FR2820430A1 (fr) | 2001-02-02 | 2002-08-09 | Inst Francais Du Petrole | Procede de desacidification d'un gaz avec lavage des hydrocarbures desorbes lors de la regeneration du solvant |
FR2895273A1 (fr) * | 2005-12-22 | 2007-06-29 | Inst Francais Du Petrole | Procede de desacidification d'un gaz avec une solution absorbante a regeneration fractionnee avec controle de la teneur en eau de la solution |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102012200566A1 (de) | 2012-01-16 | 2013-07-18 | Evonik Degussa Gmbh | Verfahren zur Absorption von CO2 aus einer Gasmischung |
WO2013107551A1 (fr) | 2012-01-16 | 2013-07-25 | Evonik Degussa Gmbh | Procédé d'absorption de co2 d'un mélange gazeux contenant des amines |
Also Published As
Publication number | Publication date |
---|---|
AU2010338157A1 (en) | 2012-07-12 |
EP2512631A1 (fr) | 2012-10-24 |
US20130023712A1 (en) | 2013-01-24 |
CA2783719A1 (fr) | 2011-07-07 |
FR2953736B1 (fr) | 2012-02-24 |
FR2953736A1 (fr) | 2011-06-17 |
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