CN114671772A - Production process of aminoacetic acid - Google Patents
Production process of aminoacetic acid Download PDFInfo
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- CN114671772A CN114671772A CN202210476969.0A CN202210476969A CN114671772A CN 114671772 A CN114671772 A CN 114671772A CN 202210476969 A CN202210476969 A CN 202210476969A CN 114671772 A CN114671772 A CN 114671772A
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229960002449 glycine Drugs 0.000 title claims abstract description 23
- 235000013905 glycine and its sodium salt Nutrition 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 141
- 239000007789 gas Substances 0.000 claims abstract description 68
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 66
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 54
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 34
- 239000012452 mother liquor Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 28
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 17
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 17
- 230000023556 desulfurization Effects 0.000 claims abstract description 17
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000010521 absorption reaction Methods 0.000 claims abstract description 7
- 239000010413 mother solution Substances 0.000 claims abstract description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 50
- 235000019270 ammonium chloride Nutrition 0.000 claims description 25
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 239000011593 sulfur Substances 0.000 description 6
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4561—Compounds containing sulfur, halogen and oxygen only
- C01B17/4592—Sulfuryl chloride (SO2Cl2)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
- C01B7/0725—Purification ; Separation of hydrogen chloride by adsorption by active carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production process of aminoacetic acid, belonging to the technical field of aminoacetic acid production. The method comprises the following steps: (1) adding acetic acid and chlorine into a chlorination reactor to react to generate chloroacetic acid and generate tail gas; (2) adding chloroacetic acid into an ammoniation reactor for reaction to generate ammoniation liquid, and purifying to obtain an aminoacetic acid product and a methanol mother solution; (3) the tail gas generated in the step (1) firstly passes through a cooler, so that acetic acid and acetyl chloride in the tail gas are condensed and recycled for chlorination reaction; (4) enabling the uncondensed tail gas to enter a desulfurization and dechlorination device to generate sulfuryl chloride, and condensing the sulfuryl chloride for chlorination reaction; simultaneously recovering hydrogen chloride gas; (5) the hydrogen chloride gas enters a hydrochloric acid absorption device to prepare a hydrochloric acid solution, and the unabsorbed hydrogen chloride gas is mixed with the methanol mother liquor to carry out a neutralization reaction. The invention has the characteristics of safety, reliability, energy conservation, emission reduction, low consumption of sulfur and acetic acid raw materials, high product quality and the like.
Description
Technical Field
The invention relates to the technical field of aminoacetic acid production, in particular to a production process of aminoacetic acid.
Background
At present, the domestic industrial aminoacetic acid is generally matched with a chloroacetic acid production device, chloroacetic acid products are prepared by reacting acetic acid and liquid chlorine at a certain temperature by taking sulfur as a catalyst to generate chloroacetic acid, tail gas mainly comprising hydrogen chloride gas, a small amount of chlorine gas, sulfur dioxide and sulfur trioxide is generated, and the tail gas is recovered to obtain hydrochloric acid solution. The aminoacetic acid production process adopts a chlorination method to produce chloroacetic acid as a raw material, the chloroacetic acid, ammonia gas and hexamethylenetetramine are subjected to ammoniation low-temperature reaction to generate aminoacetic acid reaction liquid, the ammoniation reaction liquid is dripped into a certain amount of industrial methanol to crystallize and separate out granular industrial aminoacetic acid, and then aminoacetic acid and methanol mother liquor are separated out by a centrifuge, wherein the methanol mother liquor contains about 33% of ammonium chloride and 10% of free ammonia, and the pH value is 7.5-8.5. Neutralizing the methanol mother liquor to a pH value of about 6.3, rectifying and purifying in a rectifying tower to separate out a methanol solution with the methanol content of 92% and an ammonium chloride aqueous solution with the methanol content of 33%, repeatedly recycling the methanol solution in an alcohol precipitation reaction system, evaporating and concentrating the ammonium chloride solution to generate a finished product of ammonium chloride, a high-concentration ammonium chloride concentrated solution and distilled water, and recycling the distilled water in an ammoniation reaction system.
The hydrogen chloride gas generated in the chloroacetic acid production section contains a certain amount of Cl2(chlorine gas), once the chlorine gas contacts with free ammonia in the methanol mother liquor, violent strong oxidation reaction is instantly generated, so that explosion occurs, and therefore, hydrogen chloride gas generated in a chloroacetic acid production section cannot be directly used for neutralizing the methanol mother liquor. At present, hydrochloric acid aqueous solution produced by an HCI gas dissolution absorption working section of a chloroacetic acid production working section is conveyed to methanol mother liquor to adjust the pH value, and the hydrochloric acid and alkaline methanol mother liquor are mixed into a standard pH value by utilizing the centrifugal force of a methanol mother liquor conveying pump, wherein the pH value is 5.8-6.5 (the specific process is shown in figure 1). The hydrochloric acid solution has low concentration and large water amount, so that the water amount of mother liquor is increased, the rectification load is increased, steam is consumed, the extraction amount of the ammonium chloride solution is large, the relative load of a concentration working section is increased, and the evaporation efficiency water amount is increased.
No removal S, CI in the prior art2The device does not recover sulfuryl chloride, thereby causing the consumption of raw materials of sulfur and acetic acid to be increased.
Disclosure of Invention
The present invention is directed to a process for producing glycine, which solves the above problems of the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a process for the production of aminoacetic acid, said process comprising the following steps:
(1) adding acetic acid and chlorine into a chlorination reactor to react to generate chloroacetic acid and generate tail gas;
(2) adding chloroacetic acid obtained by the reaction in the step (1), ammonia gas and hexamethylenetetramine into an ammoniation reactor for reaction to generate ammoniated liquid, adding the ammoniated liquid into a methanol-alcohol precipitation kettle for extraction by using a methanol solution, and performing centrifugal separation after the extraction is finished to obtain an aminoacetic acid product and a methanol mother solution;
(3) cooling the tail gas generated in the step (1) in a cooler to condense acetic acid and acetyl chloride in the tail gas and recycle the condensed acetic acid and acetyl chloride for chlorination reaction;
(4) heating the uncondensed tail gas, then feeding the heated tail gas into a desulfurization and dechlorination device, simultaneously introducing chlorine gas to ensure that sulfur dioxide in the tail gas generates sulfuryl chloride, and condensing the sulfuryl chloride for the chlorination reaction; meanwhile, hydrogen chloride gas with the purity of more than 99.9 percent is obtained by recovery;
(5) part of the hydrogen chloride gas obtained in the step (4) enters a hydrochloric acid absorption device to prepare a hydrochloric acid solution, the rest hydrogen chloride gas is mixed with the methanol mother liquor to carry out neutralization reaction, the pH value of the methanol mother liquor is adjusted to 6.0-6.5, and the neutralized mother liquor enters a rectifying tower to be rectified and purified;
(6) separating by a rectifying tower to obtain a 92% concentrated methanol solution and an ammonium chloride aqueous solution with the mass content of ammonium chloride being more than or equal to 33%, and feeding the methanol solution into an alcohol precipitation kettle for alcohol precipitation reaction; and (3) allowing the ammonium chloride aqueous solution to enter an evaporation concentration device, separating to obtain an ammonium chloride finished product, high-concentration ammonium chloride concentrated solution and evaporation water, and reusing the evaporation water for ammoniation reaction.
The cooler temperature in step (3) is from-18 to-15 ℃.
And (4) heating the uncondensed tail gas in the step (4) to 68-75 ℃.
And (4) carrying out neutralization reaction on the methanol mother liquor and the hydrogen chloride gas in the step (4) through a gas-liquid mixer.
And (3) carrying out neutralization reaction on the methanol mother liquor and the hydrogen chloride gas through a siphon mixer.
And (4) the desulfurization and dechlorination device in the step (4) is an active carbon catalytic desulfurization and dechlorination device. The active carbon catalytic desulfurization and dechlorination device is an active carbon catalytic reactor, and utilizes the principle that sulfur dioxide and chlorine react to generate sulfuryl chloride in the presence of an active carbon catalyst to ensure that the sulfur dioxide in tail gas reacts with the chlorine, thereby not only removing and recovering the sulfur chloride, but also removing the chlorine in hydrogen chloride gas, and ensuring that the recovered hydrogen chloride gas can be directly used for neutralizing methanol.
The mol ratio of the chlorine gas introduced in the step (4) to the sulfur dioxide in the tail gas is 1.1: 1.
One part of the hydrogen chloride gas after desulfurization and dechlorination enters a hydrochloric acid absorption system through a pipeline, and the rest part of the hydrogen chloride gas is used for the neutralization reaction of the methanol mother liquor, and the flow of the hydrogen chloride gas can be controlled through a valve.
The production process of chloroacetic acid comprises the following steps: the method comprises the following steps of (1) using sulfur as a catalyst, firstly, generating acyl chloride, reacting the sulfur with introduced chlorine to generate sulfur dichloride, and reacting the sulfur dichloride with acetic acid to generate acetyl chloride:
2S+Cl2→S2Cl2
2S2Cl2+3CH3COOH → HCl+H2SO3+3C2H3OCl
then reacting active acetyl chloride with chlorine to generate 2-chloroacetyl chloride, and finally carrying out acidolysis on the 2-chloroacetyl chloride to obtain chloroacetic acid.
Sulfur dichloride is generated in the reaction process, the sulfur dichloride is oxidized into sulfur dioxide, sulfur trioxide and the like, and chlorine and acetic acid which are not completely reacted and byproducts of hydrogen chloride gas and acetyl chloride (C)2H3ClO), and the like,
the tail gas passes through a cooler, so that acetyl chloride, acetic acid, sulfur trioxide and the like are condensed and recovered, and then the sulfur dioxide and chlorine are fully reacted to generate sulfuryl chloride under the catalytic action of activated carbon through a desulfurization and dechlorination device, and the sulfuryl chloride is recovered for chlorination reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adds a desulfurization and dechlorination device in the tail gas recovery of the chlorination reaction to convert the sulfur and chlorine in the tail gas into sulfuryl chloride for recycling, thereby reducing the consumption of sulfur and chlorine and greatly reducing the cost. According to the experimental result, the recoverable Cl of the generated one ton of chloroacetic acid is calculated2O23-5kg of S (sulfuryl chloride), and simultaneously saving the input amount of 3-5kg of sulfur catalyst.
(2) The produced hydrogen chloride gas has no chlorine gas, can be directly used for neutralizing the methanol mother liquor, has no explosion risk and has high safety coefficient; the mass concentration of the produced hydrochloric acid product reaches 37 percent, and the quality of the hydrochloric acid product is improved.
(3) The hydrogen chloride is adopted to directly carry out neutralization reaction on the methanol mother liquor, so that the water quantity is reduced, the rectification load is reduced by 0.18 percent, and the steam consumption is saved by 0.1t/t of the product; the HCI and the water in the methanol are dissolved to form an exothermic reaction, the methanol mother liquor is autonomously heated by the neutralization reaction, the temperature is raised by 15 ℃, and the use amount of the rectification steam is reduced by 0.2t/t of the product; the extraction amount of the ammonium chloride solution in the rectification section is reduced by 0.8 percent, so that the steam energy consumption is saved by 0.05t/t of the product, the steam efficiency water is reduced by 15 percent, and the reuse rate is reduced.
(4) The invention uses the siphon mixer to carry out neutralization reaction, directly mixes and neutralizes through the pipeline, and has uniform reaction and high speed.
(5) The invention has the characteristics of safety, reliability, energy conservation, emission reduction, low consumption of sulfur and acetic acid raw materials, high product quality and the like.
Drawings
FIG. 1 is a flow diagram of a current process for producing glycine;
FIG. 2 is a process flow diagram of the present invention.
Detailed Description
The technical solution of the present patent will be described in further detail with reference to the following embodiments.
As can be seen from fig. 2, the present invention comprises the following steps:
(1) adding acetic acid and chlorine into a chlorination reactor to react to generate chloroacetic acid and generate tail gas;
(2) adding chloroacetic acid obtained by the reaction in the step (1), ammonia gas and hexamethylenetetramine into an ammoniation reactor for reaction to generate ammoniated liquid, adding the ammoniated liquid into a methanol-alcohol precipitation kettle for extraction by using a methanol solution, and performing centrifugal separation after the extraction is finished to obtain an aminoacetic acid product and a methanol mother solution;
(3) cooling the tail gas generated in the step (1) in a cooler to condense acetic acid and acetyl chloride in the tail gas and recycle the condensed acetic acid and acetyl chloride for chlorination reaction;
(4) heating the uncondensed tail gas, then feeding the heated tail gas into a desulfurization and dechlorination device, simultaneously introducing chlorine gas to ensure that sulfur dioxide in the tail gas generates sulfuryl chloride, and condensing the sulfuryl chloride for the chlorination reaction; meanwhile, hydrogen chloride gas with the purity of more than 99.9 percent is obtained by recovery;
(5) part of the hydrogen chloride gas obtained in the step (4) enters a hydrochloric acid absorption device to prepare a hydrochloric acid solution, the rest hydrogen chloride gas is mixed with the methanol mother liquor to carry out neutralization reaction, the pH value of the methanol mother liquor is adjusted to 6.0-6.5, and the neutralized mother liquor enters a rectifying tower to be rectified and purified;
(6) separating by a rectifying tower to obtain a 92% concentrated methanol solution and an ammonium chloride aqueous solution with the mass content of ammonium chloride being more than or equal to 33%, and feeding the methanol solution into an alcohol precipitation kettle for alcohol precipitation reaction; and (3) allowing the ammonium chloride aqueous solution to enter an evaporation concentration device, separating to obtain an ammonium chloride finished product, high-concentration ammonium chloride concentrated solution and evaporation water, and reusing the evaporation water for ammoniation reaction.
One part of the hydrogen chloride gas after desulfurization and dechlorination enters a hydrochloric acid absorption system through a pipeline, and the rest part of the hydrogen chloride gas is used for the neutralization reaction of the methanol mother liquor, and the flow of the hydrogen chloride gas can be controlled through a valve.
The cooler temperature in step (3) is from-18 to-15 ℃.
And (4) heating the uncondensed tail gas in the step (4) to 68-75 ℃.
And (4) carrying out neutralization reaction on the methanol mother liquor and the hydrogen chloride gas in the step (4) through a gas-liquid mixer.
And (3) carrying out neutralization reaction on the methanol mother liquor and the hydrogen chloride gas through a siphon mixer.
And (4) the desulfurization and dechlorination device in the step (4) is an active carbon catalytic desulfurization and dechlorination device.
The mol ratio of the chlorine gas introduced in the step (4) to the sulfur dioxide in the tail gas is 1.1: 1.
Compared with the figure 1 and the figure 2, the chloroacetic acid tail gas treatment is added with a desulfurization and dechlorination device, and the hydrogen chloride gas after desulfurization and dechlorination can be directly used for neutralizing methanol mother liquor, so that the water quantity is reduced, the rectification load is reduced by 0.18 percent, and the steam consumption energy consumption is saved by 0.1t/t product; and the ammonium chloride solution in the rectification section is reduced, and the extraction amount of the ammonium chloride solution is reduced by 0.8 percent, so that the steam energy consumption is saved by 0.05t/t of the product, the steam efficiency water is reduced by 15 percent, and the reuse rate is reduced.
Compared with the prior art, the invention has the advantages that the safety, the energy consumption and the like are compared, and the comparison data is as follows:
the operation time and the daily process index verify that the process requirements are met, the production cost is reduced, the safety and environmental protection requirements are ensured, and the formation of ammonium chloride solution is reduced.
Claims (7)
1. A process for the production of aminoacetic acid, characterized in that it comprises the following steps:
(1) adding acetic acid and chlorine into a chlorination reactor to react to generate chloroacetic acid and generate tail gas;
(2) adding chloroacetic acid obtained by the reaction in the step (1), ammonia gas and hexamethylenetetramine into an ammoniation reactor for reaction to generate ammoniated liquid, adding the ammoniated liquid into a methanol-alcohol precipitation kettle for extraction by using a methanol solution, and performing centrifugal separation after the extraction is finished to obtain an aminoacetic acid product and a methanol mother solution;
(3) cooling the tail gas generated in the step (1) in a cooler to condense acetic acid and acetyl chloride in the tail gas and recycle the condensed acetic acid and acetyl chloride for chlorination reaction;
(4) heating the uncondensed tail gas, then feeding the heated tail gas into a desulfurization and dechlorination device, introducing chlorine gas, enabling sulfur dioxide in the tail gas to generate sulfuryl chloride, and condensing the sulfuryl chloride for use in chlorination reaction; meanwhile, hydrogen chloride gas with the purity of more than 99.9 percent is obtained by recovery;
(5) part of the hydrogen chloride gas obtained in the step (4) enters a hydrochloric acid absorption device to prepare a hydrochloric acid solution, the rest hydrogen chloride gas is mixed with the methanol mother liquor to carry out neutralization reaction, the pH value of the methanol mother liquor is adjusted to 6.0-6.5, and the neutralized mother liquor enters a rectifying tower to be rectified and purified;
(6) separating by a rectifying tower to obtain a 92% concentrated methanol solution and an ammonium chloride aqueous solution with the mass content of ammonium chloride being more than or equal to 33%, and feeding the methanol solution into an alcohol precipitation kettle for alcohol precipitation reaction; and (3) allowing the ammonium chloride aqueous solution to enter an evaporation concentration device, separating to obtain an ammonium chloride finished product, high-concentration ammonium chloride concentrated solution and evaporation water, and reusing the evaporation water for ammoniation reaction.
2. A process for producing glycine as claimed in claim 1, wherein the cooler temperature in step (3) is from-18 to-15 ℃.
3. A process for producing glycine as claimed in claim 1, wherein the temperature of the uncondensed off-gas in step (4) is raised to 68-75 ℃.
4. The process according to claim 1, wherein the methanol mother liquor and the hydrogen chloride gas in the step (4) are subjected to neutralization reaction by a gas-liquid mixer.
5. A process for producing glycine as claimed in claim 4, wherein the methanol mother liquor and hydrogen chloride gas are subjected to neutralization reaction by means of a siphon mixer.
6. The process for producing glycine as claimed in claim 1, wherein the desulfurization and dechlorination device in step (4) is an activated carbon catalytic desulfurization and dechlorination device.
7. The process for producing glycine as claimed in claim 1, wherein the molar ratio of the chlorine gas introduced in step (4) to the sulfur dioxide in the tail gas is 1.1: 1.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803763A (en) * | 2006-01-19 | 2006-07-19 | 刘荣富 | Amino acetic acid preparation process |
| CN104193751A (en) * | 2014-07-25 | 2014-12-10 | 沈美忠 | Method for treating mother liquid discharged in glycine production |
| CN109231168A (en) * | 2018-09-27 | 2019-01-18 | 河北东华舰化工有限公司 | A kind of production of chloroacetic acid reduce hydrochloric acid, in acetic acid by-product sulfuric acid content method and apparatus |
| CN109851490A (en) * | 2019-03-01 | 2019-06-07 | 湖北泰盛化工有限公司 | The chloroacetic technique of acetic anhydride catalyst method continuous production |
| CN210751328U (en) * | 2019-09-20 | 2020-06-16 | 河南红东方化工股份有限公司 | Aminoacetic acid by-product ammonium chloride recovery device |
| CN112010770A (en) * | 2020-09-07 | 2020-12-01 | 河北东华舰化工有限公司 | Novel production method of glycine ethyl ester hydrochloride |
| CN112592285A (en) * | 2021-01-13 | 2021-04-02 | 河南红东方化工股份有限公司 | Continuous ammoniation production method of aminoacetic acid |
-
2022
- 2022-05-02 CN CN202210476969.0A patent/CN114671772A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803763A (en) * | 2006-01-19 | 2006-07-19 | 刘荣富 | Amino acetic acid preparation process |
| CN104193751A (en) * | 2014-07-25 | 2014-12-10 | 沈美忠 | Method for treating mother liquid discharged in glycine production |
| CN109231168A (en) * | 2018-09-27 | 2019-01-18 | 河北东华舰化工有限公司 | A kind of production of chloroacetic acid reduce hydrochloric acid, in acetic acid by-product sulfuric acid content method and apparatus |
| CN109851490A (en) * | 2019-03-01 | 2019-06-07 | 湖北泰盛化工有限公司 | The chloroacetic technique of acetic anhydride catalyst method continuous production |
| CN210751328U (en) * | 2019-09-20 | 2020-06-16 | 河南红东方化工股份有限公司 | Aminoacetic acid by-product ammonium chloride recovery device |
| CN112010770A (en) * | 2020-09-07 | 2020-12-01 | 河北东华舰化工有限公司 | Novel production method of glycine ethyl ester hydrochloride |
| CN112592285A (en) * | 2021-01-13 | 2021-04-02 | 河南红东方化工股份有限公司 | Continuous ammoniation production method of aminoacetic acid |
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