US20170081275A1 - Novel beta-hydroxylated tertiary diamines, a process for their synthesis and their use for eliminating acid compounds a gaseous effluent - Google Patents

Novel beta-hydroxylated tertiary diamines, a process for their synthesis and their use for eliminating acid compounds a gaseous effluent Download PDF

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US20170081275A1
US20170081275A1 US15/311,232 US201515311232A US2017081275A1 US 20170081275 A1 US20170081275 A1 US 20170081275A1 US 201515311232 A US201515311232 A US 201515311232A US 2017081275 A1 US2017081275 A1 US 2017081275A1
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reaction
diamino
absorbent solution
tetramethyl
amine
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Julien GRANDJEAN
Bruno Delfort
Dominique Le Pennec
Thierry Huard
Aurelie WENDER
Armelle NIGON
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IFP Energies Nouvelles IFPEN
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Definitions

  • the present invention relates to novel nitrogen compounds belonging to the family of beta-hydroxylated tertiary diamines.
  • the invention also relates to the synthesis method of said compounds and to their use in a method of deacidizing a gaseous effluent.
  • Tertiary amines notably some tertiary diamines, are of interest for various applications. They can for example be used as catalysts in the preparation of polyurethanes, as quaternary ammonium salt precursors or as bases for acid gas deacidizing.
  • Tertiary amines can be utilized in acid gas deacidizing methods using an aqueous solution comprising such amines for removing acid compounds, notably carbon dioxide (CO2), hydrogen sulfide (H2S), carbon oxysulfide (COS), carbon disulfide (CS 2 ), sulfur dioxide (SO 2 ) and mercaptans (RSH) such as methylmercaptan (CH 3 SH), ethylmercaptan (CH 3 CH 2 SH) and propylmercaptan (CH 3 CH 2 CH 2 SH), present in a gas.
  • the gas is deacidized by being contacted with the absorbent solution, then the absorbent solution is thermally regenerated.
  • a chemical solvent corresponds to an aqueous solution comprising a reactant that reacts selectively with the acid compounds (H 2 S, CO 2 , COS, CS 2 , etc.) present in the treated gas so as to form salts, without reacting with the other non-acid compounds in the gas.
  • the treated gas is depleted in acid compounds that are selectively transferred as salts into the solvent.
  • the chemical reactions are reversible, which allows the acid compound-laden solvent to be subsequently deacidized, for example under the action of heat, so as to release on the one hand the acid compounds in form of gas that can then be stored, converted or used for various applications, and on the other hand to regenerate the solvent that goes back to its initial state and can thus be used again for a new reaction stage with the acid gas to be treated.
  • the reaction stage of the solvent with the acid gas is commonly referred to as absorption stage, and the stage where the solvent is deacidized is referred to as solvent regeneration stage.
  • the performances of the separation of acid compounds from the gas in this context mainly depend on the nature of the reversible reaction selected.
  • Conventional acid gas deacidizing methods are generally referred to as “amine methods”, i.e. based on the reactions of the acid compounds with amines in solution. These reactions are part of the overall framework of acid-base reactions.
  • H 2 S, CO 2 or COS are for example acid compounds, notably in the presence of water, whereas amines are basic compounds.
  • the reaction mechanisms and the nature of the salts obtained generally depend on the structure of the amines used.
  • document U.S. Pat. No. 6,852,144 describes a method of removing acid compounds from hydrocarbons using a water-N-methyldiethanolamine or water-triethanolamine absorbent solution with a high proportion of a compound belonging to the following group: piperazine and/or methylpiperazine and/or morpholine.
  • the performances of acid gas deacidizing methods using amine scrubbing directly depend on the nature of the amine(s) present in the solvent. These amines can be primary, secondary or tertiary. They can have one or more equivalent or different amine functions per molecule.
  • H 2 S absorption selectivity over CO 2 .
  • selective H 2 S removal is sought by limiting to the maximum CO 2 absorption. This constraint is particularly important for gases to be treated already having a CO 2 content that is less than or equal to the desired specification.
  • a maximum H 2 S absorption capacity is then sought with maximum H 2 S absorption selectivity over CO 2 .
  • This selectivity allows to maximize the amount of treated gas and to recover an acid gas at the regenerator outlet having the highest H 2 S concentration possible, which limits the size of the sulfur chain units downstream from the treatment and guarantees better operation.
  • an H 2 S enrichment unit is necessary for concentrating the acid gas in H 2 S.
  • Tertiary amines such as N-methyldiethanolamine or hindered secondary amines exhibiting slow reaction kinetics with CO 2 are commonly used, but they have limited selectivities at high H 2 S loadings.
  • tertiary amines or secondary amines with severe steric hindrance have slower CO 2 capture kinetics than less hindered primary or secondary amines.
  • tertiary or secondary amines with severe steric hindrance have instantaneous H 2 S capture kinetics, which allows to achieve selective H 2 S removal based on distinct kinetic performances.
  • patent U.S. Pat. No. 4,405,582 describes a method for selective absorption of sulfur-containing gases with an absorbent containing a diaminoether at least one amine function of which is tertiary and whose other amine function is tertiary or secondary with severe steric hindrance, the nitrogen atom being in the latter case linked to either at least one tertiary carbon or to two secondary carbon atoms.
  • the two amine functions and the carbons of the main chain can be substituted by alkyl or hydroxyalkyl radicals.
  • Patent U.S. Pat. No. 4,405,583 also describes a method for selective removal of H 2 S in gases containing H 2 S and CO 2 with an absorbent containing a diaminoether whose two secondary amine functions exhibit severe steric hindrance as defined above.
  • the substituents of the amine functions and of the carbons of the main chain can be substituted by alkyl and hydroxyalkyl radicals.
  • Patent FR-2,934,172 describes the use of an absorbent solution based on a tertiary diamine in an acid compound removal method advantageously applied to the treatment of natural gas and combustion fumes, said amine being N,N,N′,N′-tetramethyl-1,6-hexanediamine.
  • This cyclic capacity corresponds to the loading difference ( ⁇ designates the number of moles of absorbed acid compounds n acid gas per kilogram of absorbent solution) between the absorbent solution discharged from the bottom of the absorption column and the absorbent solution fed to said column.
  • ⁇ designates the number of moles of absorbed acid compounds n acid gas per kilogram of absorbent solution
  • Another essential aspect of gas or industrial fumes treatment operations using a solvent remains the regeneration of the separation agent.
  • Regeneration through expansion and/or distillation and/or entrainment by a vaporized gas referred to as “stripping gas” is generally considered depending on the absorption type (physical and/or chemical).
  • the energy consumption required for solvent regeneration can be very high, which is in particular the case when the partial pressure of acid gases is low, and it can represent a considerable operating cost for the CO 2 capture process.
  • the energy required for regeneration by distillation of an amine solution can be divided into three different items: the energy required for heating the absorbent solution between the top and the bottom of the regenerator, the energy required for lowering the acid gas partial pressure in the regenerator by vaporization of a stripping gas, and the enthalpy required for breaking the chemical bond between the amine and the CO 2.
  • the inventors have discovered novel nitrogen compounds belonging to the family of beta-hydroxylated tertiary diamines which can be advantageously used in the field of gas deacidizing.
  • tertiary or secondary diamines with severe steric hindrance are not equivalent in terms of performance for use in absorbent solution formulations for acid gas treatment in an industrial process.
  • novel nitrogen compounds according to the invention are particular tertiary diamines whose main chain, i.e. the chain linking the two tertiary amine functions, is a hydrocarbon chain substituted by two hydroxyl groups, each hydroxyl group being carried by a carbon atom at nitrogen beta position.
  • the term beta-hydroxylated tertiary diamine is used in the present invention in reference to the position of a hydroxyl group with respect to an amine function as described.
  • the invention relates to a nitrogen compound belonging to the family of tertiary diamines meeting general formula (I) as follows:
  • the nitrogen compound according to the invention is N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol meeting the formula as follows, with n equal to 2 and R being an ethylidene radical:
  • the nitrogen compound according to the invention is N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol meeting the formula as follows, with n equal to 4 and R being a butylidene radical:
  • the invention relates to a synthesis method of a nitrogen compound according to general formula (I) comprising the following reactions:
  • the first reaction is an epoxidation reaction of 1,5-hexadiene to produce 1,2,5,6-diepoxyhexane
  • the second reaction is an addition reaction of two moles of dimethylamine and one molecule of 1,2,5,6-diepoxyhexane to produce N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol.
  • the first reaction is an epoxidation reaction of 1,7-octadiene to produce 1,2,7,8-diepoxyoctane
  • the second reaction is an addition reaction of two moles of dimethylamine and one molecule of 1,2,7,8-diepoxyoctane to produce N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol.
  • the first epoxidation reaction consists in reacting the alpha-omega-diene with a peracid or a peroxide or a hydroperoxide or oxygen associated with a suitable catalytic system, and said peracid can be generated in situ by reaction between a carboxylic acid and a hydrogen peroxide.
  • the second addition reaction is carried out in the presence of excess dimethylamine, preferably more than two moles.
  • the first epoxidation reaction and the second addition reaction are carried out in two successive stages.
  • the invention relates to a method of removing acid compounds contained in a gaseous effluent wherein an acid compound absorption stage is carried out by contacting the gaseous effluent with an absorbent solution comprising water and a nitrogen compound according to the invention or likely to be obtained by a synthesis method according to the invention.
  • the absorbent solution comprises between 5 wt. % and 95 wt. % of said nitrogen compound, preferably between 10 wt. % and 90 wt. % of said nitrogen compound, and between 5 wt. % and 95 wt. % of water, preferably between 10 wt. % and 90 wt. % of water.
  • the absorbent solution can comprise between 5 wt. % and 95 wt. % of at least one additional amine, said additional amine being either a tertiary amine or a secondary amine having two secondary carbons at nitrogen alpha position or at least one tertiary carbon at nitrogen alpha position.
  • Said additional amine can be a tertiary amine selected from among the group made up of:
  • the absorbent solution can also comprise a non-zero amount, less than 30 wt. %, of at least one additional amine such as a primary amine or a secondary amine.
  • Said additional primary or secondary amine can be selected from among the group made up of:
  • the absorbent solution can furthermore comprise at least one physical solvent selected from among the group made up of methanol, ethanol, 2-ethoxyethanol, triethylene glycoldimethylether, tetraethylene glycoldimethylether, pentaethylene glycoldimethylether, hexaethylene glycoldimethylether, heptaethylene glycol-dimethylether, octaethylene glycoldimethylether, diethylene glycol butoxyacetate, glycerol triacetate, sulfolane, N-methylpyrrolidone, N-methylmorpholin-3-one, N,N-dimethylformamide, N-formylmorpholine, N,N-dimethyl-imidazolidin-2-one, N-methylimidazole, ethylene glycol, diethylene glycol, triethylene glycol, thiodiglycol and tributyl phosphate.
  • at least one physical solvent selected from among the group made up of methanol, ethanol, 2-ethoxyethanol, triethylene glycol
  • the gaseous effluent can be selected from among natural gas, syngases, combustion fumes, refinery gas, acid gas from an amine plant, Claus tail gas, biomass fermentation gas, cement plant gas and incinerator fumes.
  • the method according to the invention can be implemented for selectively removing the H 2 S over the CO 2 from a gaseous effluent comprising H 2 S and CO 2 , preferably natural gas.
  • FIG. 1 is a block diagram of the implementation of an acid gas treating method.
  • novel nitrogen compounds according to the invention are tertiary diamines meeting general formula (I) as follows:
  • a tertiary diamine is understood to be a chemical compound comprising two amine functions which are tertiary amine functions.
  • the hydroxyl groups are carried by carbon atoms at amine beta position.
  • R is selected from among one of the following groups:
  • a compound according to the invention is N,N,N′,N′-(tetra-methyl)-1,6-diamino-2,5-hexanediol or N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octane-diol.
  • the nitrogen compounds of general formula (I) can be prepared by carrying out the following reactions:
  • alpha-omega-diene is understood to be a diene comprising two alkene functions at the ends, such as 1,5-hexadiene and 1,7-octadiene.
  • a reaction of epoxidation of each one of the two alkene functions of the 1,5-hexadiene to oxirane functions is first conducted in order to obtain 1,2,5,6-diepoxyhexane.
  • This epoxidation reaction can be carried out with any means known to the person skilled in the art for conducting epoxidation of a carbon-carbon double bond.
  • a peroxide, a hydroperoxide, a peracid such as peracetic acid or 3-chloroperbenzoic acid, or a perester can be used for example. It is also possible to use the combination of an acid such as acetic acid and of a peroxide such as hydrogen peroxide allowing in-situ generation of a peracid.
  • the reaction can be conducted under mild conditions, for example at a temperature close to ambient temperature, and in the presence of a solvent, which can be a chlorinated solvent such as dichloromethane or an aliphatic or aromatic hydrocarbon solvent.
  • a solvent which can be a chlorinated solvent such as dichloromethane or an aliphatic or aromatic hydrocarbon solvent.
  • the epoxidation reaction of an unsaturation can also be performed by means of oxygen and of a suitable catalytic system.
  • a reaction of addition of two moles of dimethylamine to one molecule of 1,2,5,6-diepoxyhexane to form N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol is carried out.
  • This reaction can be conducted with excess dimethylamine.
  • It is an exothermic reaction that is preferably performed with suitable temperature control. For example, the temperature is maintained within the ⁇ 15° C./100° C. range.
  • This synthesis is based on the same reactions, the same procedures and the same conditions as those described above for preparing N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol, but using 1,7-octadiene instead of 1,5-hexadiene as the precursor for the first epoxidation reaction.
  • the epoxidation reaction yields 1,2,7,8-diepoxyoctane used in the second addition reaction with dimethylamine.
  • the first epoxidation reaction and the second addition reaction are conducted in two successive stages during the preparation of the nitrogen compounds according to the invention.
  • the compounds according to the invention can be used in different fields of chemistry and they can be advantageously used in the treatment of gas of industrial origin and of natural gas.
  • the present invention aims to remove acid compounds from a gaseous effluent using an aqueous solution comprising at least one nitrogen compound according to general formula (I), and advantageously N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol and N,N,N′,N ′-(tetramethyl)-1,8-diamino-2,7-octanediol.
  • the solution is contacted with the gaseous effluent to remove acid compounds contained therein.
  • the method of removing acid compounds contained in a gaseous effluent according to the invention can in particular be implemented for selective removal of H 2 S over CO 2 from a gaseous effluent comprising H 2 S and CO 2 , for example natural gas.
  • the method of removing acid compounds contained in a gaseous effluent according to the invention can also be advantageously implemented for CO 2 capture from gas of industrial origin and from natural gas, for example combustion fumes.
  • beta-hydroxylated tertiary diamines allows to obtain good performances in terms of cyclic capacity of acid gas absorption and/or of absorption selectivity towards H 2 S, notably higher absorption selectivity towards H 2 S than reference amines such as N-methyldiethanolamine (MDEA) for an equivalent or higher acid gas cyclic absorption capacity.
  • MDEA N-methyldiethanolamine
  • the absorbent solution used for removing the acid compounds contained in a gaseous effluent comprises:
  • the absorbent solution can comprise N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol or N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol, or a mixture of the two compounds.
  • the amines of general formula (I) can be in variable concentration in the absorbent solution, ranging for example between 5 wt. % and 95 wt. %, preferably between 10 wt. % and 90 wt. %, more preferably between 20 wt. % and 60 wt. %, and most preferably between 25 wt. % and 50 wt. %, inclusive.
  • the absorbent solution can contain between 5 wt. % and 95 wt. % of water, preferably between 10 wt. % and 90 wt. %, more preferably between 40 wt. % and 80 wt. %, and most preferably between 50 wt. % and 75 wt. %, inclusive.
  • the sum of the mass fractions expressed in wt. % of the various compounds of the absorbent solution is 100 wt. % of the absorbent solution.
  • the absorbent solution can furthermore contain at least one additional amine that is a tertiary amine, such as N-methyldiethanolamine, triethanolamine, diethylmonoethanolamine, dimethylmonoethanolamine or ethyl-diethanolamine, or a secondary amine with severe steric hindrance, this hindrance being defined by either the presence of two secondary carbons at nitrogen alpha position or at least one tertiary carbon at nitrogen alpha position.
  • Said additional amine is understood to be any compound having at least one severely hindered tertiary or secondary amine function.
  • the concentration of said severely hindered tertiary or secondary additional amine in the absorbent solution can range between 5 wt. % and 95 wt. %, preferably between 5 wt. % and 50 wt. %, more preferably between 5 wt. % and 30 wt. %.
  • the amines of general formula (I) can be formulated with one or more compounds containing at least one primary or secondary amine function.
  • the absorbent solution comprises up to a concentration of 30 wt. %, preferably below 15 wt. % and more preferably below 10 wt. % of said compound containing at least one primary or secondary amine function.
  • the absorbent solution comprises at least 0.5 wt. % of said compound containing at least one primary or secondary amine function. Said compound allows to accelerate the absorption kinetics of the CO 2 and, in some cases, of the COS contained in the gas to be treated.
  • the absorbent solution comprising at least one compound according to the invention can contain a mixture of additional amines as defined above.
  • the absorbent solution can contain organic compounds non reactive towards the acid compounds (commonly referred to as “physical solvents”), which allow to increase the solubility of at least one or more acid compounds of the gaseous effluent.
  • the absorbent solution can comprise between 5 wt. % and 50 wt.
  • % of physical solvent such as alcohols, ethers, ether alcohols, glycol and polyethylene glycol ethers, glycol thioethers, glycol and polyethylene glycol esters and alkoxyesters, glycerol esters, lactones, lactames, N-alkylated pyrrolidones, morpholine derivatives, morpholin-3-one, imidazoles and imidazolidinones, N-alkylated piperidones, cyclotetramethylenesulfones, N-alkylformamides, N-alkylacetamides, ether-ketones, alkyl carbonates or alkyl phosphates and derivatives thereof.
  • physical solvent such as alcohols, ethers, ether alcohols, glycol and polyethylene glycol ethers, glycol thioethers, glycol and polyethylene glycol esters and alkoxyesters, glycerol esters, lactones, lactames, N-alky
  • it can be methanol, ethanol, 2-ethoxyethanol, triethylene glycoldimethylether, tetraethylene glycoldimethylether, pentaethylene glycol-dimethylether, hexaethylene glycoldimethylether, heptaethylene glycol-dimethylether, octaethylene glycoldimethylether, diethylene glycol butoxyacetate, glycerol triacetate, sulfolane, N-methylpyrrolidone, N-methylmorpholin-3-one, N,N-dimethylformamide, N-formyl-morpholine, N,N-dimethyl-imidazolidin-2-one, N-methyl-imidazole, ethylene glycol, diethylene glycol, triethylene glycol, thiodiglycol, propylene carbonate, tributylphosphate.
  • the absorbent solutions comprising at least one nitrogen compound according to the invention can be used for deacidizing the following gaseous effluents: natural gas, syngas, combustion fumes, refinery gas, acid gas from an amine plant, Claus tail gas, biomass fermentation gas, cement plant gas and incinerator fumes.
  • gaseous effluents contain one or more of the following acid compounds: CO 2 , H 2 S, mercaptans (for example methylmercaptan (CH 3 SH), ethylmercaptan (CH 3 CH 2 SH), propyl-mercaptan (CH 3 CH 2 CH 2 SH)), COS, CS 2 , SO 2 .
  • Combustion fumes are produced notably by the combustion of hydrocarbons, biogas, coal in a boiler or for a combustion gas turbine, for example in order to produce electricity.
  • a deacidizing method using the compounds according to the invention can be implemented for absorbing at least 70%, preferably at least 80% or even at least 90% of the CO 2 contained in combustion fumes.
  • These fumes generally have a temperature ranging between 20° C. and 60° C., a pressure ranging between 1 and 5 bar, and they can comprise between 50 and 80% nitrogen, between 5 and 40% carbon dioxide, between 1 and 20% oxygen, and some impurities such as SOx and NOx if they have not been removed upstream from the deacidizing process.
  • the deacidizing method using the compounds according to the invention is particularly well suited for absorbing the CO 2 contained in combustion fumes having a low CO 2 partial pressure, for example a CO 2 partial pressure below 200 mbar.
  • the deacidizing method using the compounds according to the invention can be implemented for deacidizing a syngas.
  • Syngas contains carbon monoxide CO, hydrogen H 2 (generally with a H 2 /CO ratio of 2), water vapour (generally at saturation at the wash temperature) and carbon dioxide CO 2 (of the order of 10%).
  • the pressure generally ranges between 20 and 30 bar, but it can reach up to 70 bar. It can also comprise sulfur-containing (H 2 S, COS, etc.), nitrogen-containing (NH 3 , HCN) and halogenated impurities.
  • the deacidizing method using the compounds according to the invention can be implemented for deacidizing a natural gas.
  • Natural gas predominantly consists of gaseous hydrocarbons, but it can contain some of the following acid compounds: CO 2 , H 2 S, mercaptans, COS, CS 2 .
  • the proportion of these acid compounds is very variable and it can reach up to 70 vol. % for CO 2 and up to 40 vol. % for H 2 S.
  • the temperature of the natural gas can range between 20° C. and 100° C.
  • the pressure of the natural gas to be treated can range between 10 and 200 bar.
  • the invention can be implemented in order to reach specifications generally imposed on deacidized gas, which are less than 2% CO 2 , or even less than 50 ppm CO 2 so as to subsequently carry out liquefaction of the natural gas, less than 4 ppm H 2 S, and less than 50 ppm or even less than 10 ppm by volume of total sulfur.
  • an aqueous solution comprising a compound according to general formula (I) for deacidizing a gaseous effluent is schematically done by carrying out an absorption stage followed by a regeneration stage, as shown in FIG. 1 for example.
  • the plant for deacidizing a gaseous effluent comprises an absorption column C 1 provided with means for contacting the gas and the liquid, for example a random packing, a structured packing or trays.
  • the gaseous effluent to be treated is fed through a line 1 opening into the bottom of column C 1 .
  • a line 4 allows the absorbent solution to be fed to the top of column C 1 .
  • a line 2 allows the treated (deacidized) gas to be discharged and a line 3 allows the absorbent solution enriched in acid compounds following absorption to be sent to a regeneration column C 2 .
  • This regeneration column C 2 is provided with gas-liquid contacting internals, for example trays, random or structured packings.
  • the bottom of column C 2 is equipped with a reboiler R 1 that provides the heat required for regeneration by vaporizing a fraction of the absorbent solution.
  • the acid compound-enriched solution is fed to the top of regeneration column C 2 through a line 5 .
  • a line 7 allows to discharge at the top of column C 2 the gas enriched in acid compounds released upon regeneration, and a line 6 arranged in the bottom of column C 2 allows the regenerated absorbent solution to be sent to absorption column C 1 .
  • a heat exchanger E 1 allows the heat of the regenerated absorbent solution from column C 2 to be recovered so as to heat the acid compound-enriched absorbent solution leaving absorption column C 1 .
  • the absorption stage consists in contacting the gaseous effluent delivered through line 1 with the absorbent solution delivered through line 4 .
  • the amine functions of the molecules according to general formula (I) of the absorbent solution react with the acid compounds contained in the effluent so as to obtain an acid compound-depleted gaseous effluent that is discharged through line 2 at the top of column C 1 and an acid compound-enriched absorbent solution that is discharged through line 3 in the bottom of column C 1 to be regenerated.
  • the acid compound absorption stage can be carried out at a pressure in column C 1 ranging between 1 and 200 bar, preferably between 1 and 120 bar, more preferably between 20 and 100 bar for natural gas treatment, preferably between 1 and 3 bar for industrial fumes treatment, and at a temperature in column C 1 ranging between 20° C. and 100° C., preferably between 30° C. and 90° C., or even between 30° C. and 60° C.
  • the regeneration stage notably consists in heating and optionally in expanding the acid compound-enriched absorbent solution so as to release the acid compounds in gas form.
  • the acid compound-enriched absorbent solution leaving column C 1 is fed to heat exchanger E 1 where it is heated by the stream circulating in line 6 and coming from regeneration column C 2 .
  • the heated solution at the outlet of E 1 is fed to regeneration column C 2 through line 5 .
  • the regeneration stage can be carried out by thermal regeneration, optionally complemented by one or more expansion stages.
  • the acid compound-enriched absorbent solution discharged through line 3 can be sent to a first flash drum (not shown) prior to being sent to heat exchanger E 1 .
  • expansion allows to obtain a gas discharged at the top of the drum that contains the major part of the aliphatic hydrocarbons co-absorbed by the absorbent solution.
  • This gas can be optionally washed by a fraction of the regenerated absorbent solution and the gas thus obtained can be used as fuel gas.
  • the flash drum preferably operates at a pressure lower than in absorption column C 1 and higher than in regeneration column C 2 . This pressure is generally determined by the conditions of use of the fuel gas, and it is typically of the order of 5 to 15 bar.
  • the flash drum operates at a temperature substantially identical to the temperature of the absorbent solution obtained in the bottom of absorption column C 1 .
  • Regeneration can be carried out at a pressure in column C 2 ranging between 1 and 5 bar, or even up to 10 bar, and at a temperature in column C 2 ranging between 100° C. and 180° C., preferably between 110° C. and 170° C., more preferably between 120° C. and 140° C.
  • the regeneration temperature in column C 2 ranges between 155° C. and 180° C. in cases where the acid gases are intended to be reinjected.
  • the regeneration temperature in column C 2 ranges between 115° C. and 130° C. in cases where the acid gas is sent to the atmosphere or to a downstream treating process such as a Claus process or a tail gas treating process.
  • the CO 2 flow absorbed by the aqueous absorbent solution is measured in a closed reactor of Lewis cell type. 200 g solution is fed into the closed reactor at a controlled temperature of 50° C. Four successive CO 2 injections are carried out from 100 to 200 mbar in the vapour phase of the 200 cm 3 -volume reactor. The gas phase and the liquid phase are stirred at 100 rpm and entirely characterized from the hydrodynamic point of view. For each injection, the CO 2 absorption rate is measured through pressure variation in the gas phase. A global transfer coefficient Kg is thus determined using a mean of the results obtained for the four injections.
  • H 2 S absorption capacity performances at 40° C. of an aqueous solution of N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol according to the invention, containing 49 wt. % N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol, are compared with those of an MDEA aqueous solution containing 50 wt. % MDEA, which is a reference absorbent solution for deacidizing H 2 S-containing gas.
  • An absorption test is carried out at 40° C. on aqueous amine solutions in a thermostat-controlled equilibrium cell. This test consists in injecting into the equilibrium cell, previously filled with degassed aqueous amine solution, a known amount of acid gas, H 2 S in this example, then in waiting for the equilibrium state to be reached. The amounts of acid gas absorbed in the aqueous amine solution are then deduced from the temperature and pressure measurements by means of material and volume balances.
  • the solubilities are conventionally represented in form of H 2 S partial pressures (in bar) as a function of the H 2 S loading (in mol of H 2 S/kg absorbent solution and in mol of H 2 S/mol of amine).
  • the H 2 S partial pressures encountered in acid gases typically range between 0.1 and 1 bar at a temperature of 40° C.
  • Table 3 hereafter compares the H 2 S loadings obtained at 40° C. for various H 2 S partial pressures between the 50 wt. % MDEA absorbent solution and the 49 wt. % N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol absorbent solution.
  • the absorption capacity of the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol aqueous solution according to the invention is higher than that of the MDEA solution.
  • the difference between the H 2 S loadings of the two absorbent solutions is 1.38 mol/kg, with an absorption capacity for the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol absorbent solution increased by 157% in relation to the reference MDEA absorbent solution.
  • the H 2 S loading increase for the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol absorbent solution still is 42% in relation to the reference MDEA absorbent solution. It can thus be observed that the 49 wt. % N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol aqueous solution has a higher H 2 S absorption capacity than the reference 50 wt. % MDEA aqueous solution at 40° C., in the H 2 S partial pressure range between 0.1 and 1 bar corresponding to a partial pressure range representative of usual industrial conditions.
  • H 2 S absorption capacity performances at 40° C. of an aqueous solution of N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol according to the invention containing 50 wt. % of N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol are compared with those of an MDEA aqueous solution containing 50 wt. % MDEA, which is a reference absorbent solution for deacidizing H 2 S-containing gas.
  • the H 2 S partial pressures encountered in acid gases typically range between 0.1 and 1 bar, at a temperature of 40° C.
  • Table 4 hereafter compares the H 2 S loadings obtained at 40° C. for various H 2 S partial pressures between the 50 wt. % MDEA absorbent solution and the 50 wt. % N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solution.
  • the absorption capacity of the N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol aqueous solution according to the invention is higher than that of the MDEA solution.
  • the difference between the H 2 S loadings of the two absorbent solutions is 1.37 mol/kg, with an absorption capacity for the N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solution increased by 156% in relation to the reference MDEA absorbent solution.
  • the H 2 S loading increase for the N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solution still is 33% in relation to the reference MDEA absorbent solution. It can thus be observed that the 50 wt. % N,N,N′N′-(tetramethyl)-1,8-diamino-2,7-octanediol aqueous solution has a higher H 2 S absorption capacity than the reference 50 wt. % MDEA aqueous solution at 40° C., in the H 2 S partial pressure range between 0.1 and 1 bar corresponding to a partial pressure range representative of usual industrial conditions.
  • the CO 2 partial pressures encountered in acid gases typically range between 0.1 and 1 bar at a temperature of 40° C.
  • Table 5 compares the CO 2 loadings obtained at 40° C. for various CO 2 partial pressures between the 47 wt. % MDEA absorbent solution and the 49 wt. % N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol absorbent solution.
  • the absorption capacity of the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol aqueous solution according to the invention is higher than that of the MDEA solution.
  • the difference between the CO 2 loadings of the two absorbent solutions is 1.24 mol/kg with an absorption capacity for the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol absorbent solution increased by 141% in relation to the reference MDEA absorbent solution.
  • the CO 2 loading increase for the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol absorbent solution still is 44% in relation to the reference MDEA absorbent solution. It can thus be observed that the 49 wt.% N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol aqueous solution has a higher CO 2 absorption capacity than the reference 47 wt. % MDEA aqueous solution at 40° C., in the CO 2 partial pressure range between 0.1 and 1 bar corresponding to a partial pressure range representative of usual industrial conditions.
  • the CO 2 partial pressures encountered in acid gases typically range between 0.1 and 1 bar, at a temperature of 40° C.
  • Table 6 hereafter compares the CO 2 loadings obtained at 40° C. for various CO 2 partial pressures between the 47 wt. % MDEA absorbent solution and the 47 wt. % N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solution.
  • the absorption capacity of the N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol aqueous solution according to the invention is higher than that of the MDEA solution.
  • the difference between the CO 2 loadings of the two absorbent solutions is 1.18 mol/kg with an absorption capacity for the N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solution increased by 134% in relation to the reference MDEA absorbent solution.
  • the CO 2 loading increase for the N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solution still is 34% in relation to the reference MDEA absorbent solution. It can thus be observed that the 47 wt. % N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol aqueous solution has a higher CO 2 absorption capacity than the reference 47 wt. % MDEA aqueous solution at 40° C., in the CO 2 partial pressure range between 0.1 and 1 bar corresponding to a partial pressure range representative of usual industrial conditions.
  • the CO 2 capture capacity performances of the N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol and N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol according to the invention are notably compared with those of a 30 wt. % MonoEthanolAmine (MEA) aqueous solution which is a reference solvent in capture applications for CO 2 contained in post-combustion fumes.
  • MEA MonoEthanolAmine
  • the CO 2 partial pressures in the effluent to be treated are typically 0.1 bar with a temperature of 40° C., and 90% of the acid gas is to be abated.
  • ⁇ PC ( ⁇ PPCO2-0.05 bar ⁇ PPCO2-0.005 bar) ⁇ [ A] ⁇ 10/M
  • [A] is the amine concentration expressed in wt. %
  • M the molar mass of the amine in g/mol
  • reaction enthalpy can be obtained by calculation from several CO 2 absorption isotherms by applying Van't Hoff's law.
  • this example illustrates the higher cyclic capacity obtained with 49 wt. % N,N,N′,N′-(tetramethyl)-1,6-diamino-2,5-hexanediol and 47 wt. % N,N,N′,N′-(tetramethyl)-1,8-diamino-2,7-octanediol absorbent solutions according to the invention, allowing to reach a 90% abatement ratio at the absorber outlet.
  • the amine according to the invention allows to obtain a much better compromise than MEA in terms of cyclic capacity and reaction enthalpy.

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US20170167639A1 (en) * 2015-12-15 2017-06-15 Bloom Energy Corporation Carbon dioxide shielded natural gas line and method of using thereof
US10173389B2 (en) * 2015-12-15 2019-01-08 Bloom Energy Corporation Carbon dioxide shielded natural gas line and method of using thereof
CN110981836A (zh) * 2019-12-20 2020-04-10 广东省石油与精细化工研究院 一种一锅法制备二环氧化物的方法
US20240002742A1 (en) * 2020-11-25 2024-01-04 Eni S.P.A. Removal of acid gases from gaseous mixtures containing them
US12509639B2 (en) * 2020-11-25 2025-12-30 Eni S.P.A. Removal of acid gases from gaseous mixtures containing them
CN120169139A (zh) * 2025-05-22 2025-06-20 瑞燃科技(上海)有限公司 一种高选择性胺法吸收剂及其制备方法

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US20180251421A1 (en) 2018-09-06
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FR3021049A1 (fr) 2015-11-20
EP3142771B1 (fr) 2018-09-12
US10399925B2 (en) 2019-09-03

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