Absorbent solution containing a breakdown inhibitor derived from pyrimidine or from triazine and absorption process for acid compounds contained in a gaseous effluent
The degradation of an absorbent solution comprising organic compounds provided with an amine function in aqueous solution is reduced considerably in the presence of a small amount of degradation-inhibiting additives belonging to the class of derivatives of pyrimidine or of triazine, at least one substituent of which contains a sulfur atom. The absorbent solution is employed for deacidifying a gaseous effluent.
1. A method of absorbing acidic compounds contained in a gaseous effluent, comprising:
bringing a gaseous effluent containing acidic compounds into contact with a solution comprising:
a) at least one amine selected from the group consisting of N,N,N′,N′,N″-pentamethyldiethylenetriamine, piperazine, monoethanolamine, diethanolamine, methyldiethanolamine, diisopropanolamine, diglycolamine, a glycine salt and a taurine salt,
b) water,
c) at least one degradation-inhibiting compound for limiting the degradation of said amine, said degradation-inhibiting compound corresponding to one of the following general formulas:
in which X is selected from
a hydrogen atom,
an alkali or alkaline-earth element,
a monovalent or multivalent metal,
NH 4 + or ammonium cation resulting from the protonation of an amine function,
a phosphonium cation,
in which each of the radicals R 1 , R 2 and R 3 is selected independently from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms,
a radical
in which W is selected from a sulfur atom and an oxygen atom and Y is selected from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms,
an alkali or alkaline-earth element,
a monovalent or multivalent metal,
NH 4 + or an ammonium cation resulting from the protonation of an amine function,
a phosphonium cation,
and in which each of the radicals R 4 and R 5 is selected independently from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms.
2. The method according to claim 1 , in which the solution comprises between 10 and 99 wt. % of amine, between 1 and 90 wt. % of water and between 5 ppm and 5 wt. % of degradation-inhibiting compound.
3. The method according to claim 1 , in which the degradation-inhibiting compound is selected from the group containing: 2-thiouracil, a salt of 2-thiouracil, 4-thiouracil, a salt of 4-thiouracil, 2-thiobarbituric, a salt of 2-thiobarbituric, 2-mercaptopyrimidine, a salt of 2-mercaptopyrimidine, 3,4,5,6-tetrahydropyrimidine-2-thiol, a salt of 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-dihydro-4,4,6-trimethyl-2-pyrimidinethiol, a salt of 4,5-dihydro-4,4,6-trimethyl-2-pyrimidinethiol, 4-hydroxy-2-mercapto-6-methylpyrimidine, a salt of 4-hydroxy-2-mercapto-6-methylpyrimidine, 2-mercapto-4-methylpyrimidine, a salt of 2-mercapto -4-methylpyrimidine, 1,3,5-triazine-2,4,6-trithiol, a salt of 1,3,5-triazine-2,4,6-trithiol, and 4-methyl-2-(methylthio)pyrimidine.
4. The method according to claim 1 , in which the amine is monoethanolamine and in which the degradation-inhibiting compound is selected from 2-thiobarbituric acid, 2-thiouracil, 3,4,5,6-tetrahydro-2-pyrimidinethiol and the sodium triple salt of 1,3,5-triazine-2,4,6-trithiol.
5. The method according to claim 1 , wherein the solution comprises at least 39 wt. % of monoethanolamine.
6. The method according to claim 1 , wherein the gaseous effluent containing acidic compounds is selected from the group consisting of natural gas, flue gas, synthesis gases, refinery gases, gases obtained at the end of the Claus process, gases from fermentation of biomass, gases from cement works and incinerator flue gas.
7. The method according to claim 6 , in which the gaseous effluent containing acidic compounds comprises at least 500 ppm by volume of oxygen.
8. The method according to claim 1 , in which the degradation-inhibiting compound is selected from the group containing: 2-thiouracil, a salt of 2-thiouracil, 2-thiobarbituric acid, a salt of 2-thiobarbituric acid, 2-mercaptopyrimidine, a salt of 2-mercaptopyrimidine, 4-hydroxy-2-mercapto-6-methylpyrimidine, a salt of 4-hydroxy-2-mercapto-6-methylpyrimidine, 2-mercapto-4-methylpyrimidine, a salt of 2-mercapto-4-methylpyrimidine, and 4-methyl-2-(methylthio)pyrimidine.
9. The method according to claim 1 , in which the amine is monoethanolamine and in which the degradation-inhibiting compound is selected from 2-thiobarbituric acid, and 2-thiouracil.
10. The method according to claim 1 , in which the degradation-inhibiting compound corresponds to one of the following general formulas:
11. The method according to claim 9 , in which the solution comprises between 10 and 99 wt. % of amine, between 1 and 90 wt. % of water and between 5 ppm and 5 wt. % of degradation-inhibiting compound.
12. The method according to claim 9 , wherein the solution at least 39 wt. % of monoethanolamine.
13. The method according to claim 9 , wherein the gaseous effluent containing acidic compounds is selected from the group consisting of natural gas, flue gas, synthesis gases, refinery gases, gases obtained at the end of the Claus process, gases from fermentation of biomass, gases from cement works and incinerator flue gas.
14. The method to claim 13 , in which the gaseous effluent containing acidic compounds comprises at least 500 ppm by volume of oxygen.
15. A method of absorbing acidic compounds contained in a gaseous effluent, comprising:
bringing a gaseous effluent containing acidic compounds into contact with a solution comprising:
a) at least one amine selected from the group consisting of N.N,N′,N′,N″-pentamethyldiethylenetriamine, piperazine, monoethanolamine, diethanolamine, methyldiethanolamine, diisopropanolamine, diglycolamine, a glycine salt and a taurine salt,
b) water,
c) at least one degradation-inhibiting compound for limiting the degradation of said amine, said degradation-inhibiting compound corresponding to one of the following general formulas:
in which X is selected from
a hydrogen atom,
an alkali or alkaline-earth element,
a monovalent or multivalent metal,
NH 4 + or an ammonium cation resulting from the protonation of an amine function,
a phosphonium cation,
in which each of the radicals R 1 , R 2 and R 3 is selected independently from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms
a radical
in which W is selected from a sulfur atom and an oxygen atom and Y is selected from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms,
an alkali or alkaline-earth element,
a monovalent or multivalent metal,
NH 4 + or an ammonium cation resulting from the protonation of an amine function,
a phosphonium cation, in which at least one of the radicals R 1 , R 2 , R 3 , X and Y is a hydrocarbon group containing between 1 and 12 carbon atoms or a hydrocarbon group containing between 1 and 12 carbon atoms joined to at least one selected from the group consisting of a heteroatom and a halogen,
and in which each of the radicals R 4 and R 5 is selected independently from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms.
16. A method of absorbing acidic compounds contained in a gaseous effluent, comprising:
bringing a gaseous effluent containing acidic compounds into contact with a solution comprising:
a) at least one amine selected from the group consisting of N,N,N′,N′,N″-pentamethyldiethylenetriamine, piperazine, monoethanolamine, diethanolamine, methyldiethanolamine, diisopropanolamine, diglycolamine, a glycine salt and a taurine salt,
b) water,
c) at least one degradation-inhibiting compound for limiting the degradation of said amine, said degradation-inhibiting compound corresponding to one of the following general formulas:
in which X is selected from
a hydrogen atom,
an alkali or alkaline-earth element,
a monovalent or multivalent metal,
NH 4 + or an ammonium cation resulting from the protonation of an amine function,
a phosphonium cation,
in which each of the radicals R 1 R 2 and R 3 is selected independently from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms
a radical
in which W is selected from a sulfur atom and an oxygen atom and Y is selected from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms,
an alkali or alkaline-earth element,
a monovalent or multivalent metal,
NH 4 + or an ammonium cation resulting from the protonation of an amine function,
a phosphonium cation, in which at least one of the radicals R 1 , R 2 , R 3 , X and Y is a substituted hydrocarbon group containing between 1 and 12 carbon atoms and further comprises by substitution at least one function selected from the group: a hydroxyl function, a ketone function, a carboxyl function and a nitrile function,
and in which each of the radicals R 4 and R 5 is selected independently from:
a hydrogen atom,
a hydrocarbon radical comprising 1 to 12 carbon atoms.