CN112010770A - Novel production method of glycine ethyl ester hydrochloride - Google Patents
Novel production method of glycine ethyl ester hydrochloride Download PDFInfo
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- CN112010770A CN112010770A CN202010931372.1A CN202010931372A CN112010770A CN 112010770 A CN112010770 A CN 112010770A CN 202010931372 A CN202010931372 A CN 202010931372A CN 112010770 A CN112010770 A CN 112010770A
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- hydrogen chloride
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- ethyl ester
- ester hydrochloride
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- TXTWXQXDMWILOF-UHFFFAOYSA-N (2-ethoxy-2-oxoethyl)azanium;chloride Chemical compound [Cl-].CCOC(=O)C[NH3+] TXTWXQXDMWILOF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 84
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 81
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 64
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 29
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 238000005886 esterification reaction Methods 0.000 claims abstract description 24
- 229960002449 glycine Drugs 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 235000013905 glycine and its sodium salt Nutrition 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 119
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 43
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 27
- 239000000460 chlorine Substances 0.000 claims description 24
- 238000003786 synthesis reaction Methods 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 239000012452 mother liquor Substances 0.000 claims description 16
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000004471 Glycine Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- GIUTUZDGHNZVIA-UHFFFAOYSA-N 2-(ethylamino)acetic acid;hydrochloride Chemical compound Cl.CCNCC(O)=O GIUTUZDGHNZVIA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 35
- 239000006227 byproduct Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- IVLXQGJVBGMLRR-UHFFFAOYSA-N 2-aminoacetic acid;hydron;chloride Chemical compound Cl.NCC(O)=O IVLXQGJVBGMLRR-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000575 pesticide Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- CUHRIRXNRTVEOH-UHFFFAOYSA-N 2-aminoacetic acid;chloroethane Chemical compound CCCl.NCC(O)=O CUHRIRXNRTVEOH-UHFFFAOYSA-N 0.000 description 2
- MBXNLDOJSJWJMN-UHFFFAOYSA-N Cl.C(C)(=O)O.NCC(=O)O Chemical compound Cl.C(C)(=O)O.NCC(=O)O MBXNLDOJSJWJMN-UHFFFAOYSA-N 0.000 description 2
- UDNAQLAFFVIMLM-UHFFFAOYSA-N amino acetate;hydrochloride Chemical compound Cl.CC(=O)ON UDNAQLAFFVIMLM-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ZCVAOQKBXKSDMS-AQYZNVCMSA-N (+)-trans-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-AQYZNVCMSA-N 0.000 description 1
- CXBMCYHAMVGWJQ-CABCVRRESA-N (1,3-dioxo-4,5,6,7-tetrahydroisoindol-2-yl)methyl (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCN1C(=O)C(CCCC2)=C2C1=O CXBMCYHAMVGWJQ-CABCVRRESA-N 0.000 description 1
- FMTFEIJHMMQUJI-NJAFHUGGSA-N 102130-98-3 Natural products CC=CCC1=C(C)[C@H](CC1=O)OC(=O)[C@@H]1[C@@H](C=C(C)C)C1(C)C FMTFEIJHMMQUJI-NJAFHUGGSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 239000005874 Bifenthrin Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- CRBDHJDPBLYJHY-UHFFFAOYSA-N Cl.C(C)(=O)OCC.NCC(=O)O Chemical compound Cl.C(C)(=O)OCC.NCC(=O)O CRBDHJDPBLYJHY-UHFFFAOYSA-N 0.000 description 1
- 239000005867 Iprodione Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GQNBIMLHUAWKHJ-UHFFFAOYSA-N [4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound C1=CC(COC)=CC=C1COC(=O)C1C(C)(C)C1C=C(C)C GQNBIMLHUAWKHJ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229940024113 allethrin Drugs 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- ZRCVYEYHRGVLOC-HYARGMPZSA-N gemifloxacin Chemical compound C1C(CN)C(=N/OC)/CN1C(C(=C1)F)=NC2=C1C(=O)C(C(O)=O)=CN2C1CC1 ZRCVYEYHRGVLOC-HYARGMPZSA-N 0.000 description 1
- 229960003170 gemifloxacin Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- ONUFESLQCSAYKA-UHFFFAOYSA-N iprodione Chemical compound O=C1N(C(=O)NC(C)C)CC(=O)N1C1=CC(Cl)=CC(Cl)=C1 ONUFESLQCSAYKA-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229940108410 resmethrin Drugs 0.000 description 1
- VEMKTZHHVJILDY-FIWHBWSRSA-N resmethrin Chemical compound CC1(C)[C@H](C=C(C)C)C1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-FIWHBWSRSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960005199 tetramethrin Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- 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
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
-
- 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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Abstract
The invention discloses a novel production method of glycine ethyl ester hydrochloride, which comprises the following steps: purifying tail gas containing hydrogen chloride in the production process of the chloroacetic acid to prepare dry hydrogen chloride meeting the requirement of producing the glycine ethyl ester hydrochloride; after aminoacetic acid and absolute ethyl alcohol are added into the esterification kettle, the stirring speed and the heating voltage are controlled, so that the reaction liquid in the esterification kettle is stirred stably and flows back stably when the temperature is controlled, and the obtained dry hydrogen chloride is slowly and continuously introduced into the esterification kettle until the reaction is finished; and (3) cooling, crystallizing and filtering the solution after the reaction is finished, and drying the solid obtained by filtering to obtain a dry product, namely the glycine ethyl ester hydrochloride. The invention has simple process flow, and the product quality can reach the refining level without repeated crystallization. Meanwhile, the raw material hydrogen chloride is derived from tail gas in the production of monochloroacetic acid, so that the comprehensive utilization of resources is realized, the cost is saved, and the product of the glycine ethyl ester hydrochloride with high added value is produced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a novel production method of aminoacetic acid ethyl ester hydrochloride, which is a method for synthesizing aminoacetic acid ethyl ester hydrochloride by utilizing hydrogen chloride in tail gas generated in the production of chloroacetic acid.
Background
Glycine ethyl ester hydrochloride, also known as glycine ethyl ester hydrochloride, is a widely used pesticide and medical intermediate, and can also be used in biochemical research and as a feed additive. In the synthesis of pesticides, glycine ethyl ester hydrochloride is a key intermediate of various pyrethroid pesticides such as bifenthrin, allethrin, resmethrin, tetramethrin, methothrin and the like. Pyrethroid insecticides are the insecticides with the largest usage amount in the world at present and are widely used in the fields of agriculture, storage, life and sanitation and the like. Can also be used for synthesizing pesticide such as iprodione. In the aspect of medical synthesis, the compound can be used for synthesizing anti-inflammatory drugs such as gemifloxacin. Chinese patent (a production method of glycine ethyl ester hydrochloride, publication No. CN103864632A) discloses a method for producing glycine ethyl ester hydrochloride by using triethyl orthoformate, glycine, anhydrous ethanol and hydrogen chloride as raw materials, and by using the method, the triethyl orthoformate actually reacts with glycine, and no water is generated in the esterification process, but a byproduct of ethyl formate is generated, zinc chloride is used as a catalyst in the reaction, and after the solvent is removed after the reaction, the ethanol-diethyl ether mixed solvent is used for recrystallization and drying to obtain the product. In the synthesis process, triethyl orthoformate may also react with ethanol to generate products such as ethyl acetate and the like, the number of byproducts is large, the separation process is complex, the price of triethyl orthoformate is high, and the production cost is increased. Chinese patent (an improved method for preparing glycine ethyl ester hydrochloride, publication No. CN108484421A) comprises charging glycine, ethanol, and hydrogen chloride at a certain proportion, salt-forming and esterifying, adding water-carrying agent to evaporate water, cooling for crystallization, centrifuging, and oven drying to obtain product; adding a certain amount of water into a ternary system formed by the evaporated water-carrying agent, ethanol and water, standing for phase separation, and directly recycling a water-carrying agent phase layer; the water phase obtained by phase separation is recycled and reused; the centrifugal mother liquor is used for feeding. The reaction stage of the method has simple and convenient flow, but the finished product is not simple and convenient enough to process part of water.
The products in the market are mainly divided into industrial grade and refined grade, and the industrial grade products are generally prepared by esterifying glycine, ethanol and hydrogen chloride which are used as raw materials. Because the content of the low-carbon-content polyurethane resin is low, the content is generally about 96-97%, and the use of partial downstream products is influenced. To obtain glycine ethyl ester hydrochloride of 98% or more (purified grade), recrystallization must be performed twice. The hydrogen chloride gas adopted in the industrial production of the glycine ethyl hydrochloride needs hydrogen chloride produced by a synthesis method or hydrogen chloride obtained by high-temperature deep analysis of concentrated hydrochloric acid as a raw material, and generally has higher requirement on the purity of the hydrogen chloride gas. The byproduct hydrogen chloride generated in the organic chlorination synthesis process contains more organic impurities, so that the method is not reported to be used for synthesizing the glycine ethyl ester hydrochloride.
Most chloroacetic acid production enterprises in China adopt an acetic acid chlorination method, and the component of production tail gas is mainly hydrogen chloride. At present, hydrochloric acid as a byproduct is generated by water absorption and sold at low price, and the use of the hydrochloric acid is limited because the quantity of the byproduct is large and the byproduct contains organic impurities, so that the phenomenon of lost sales is often caused, and the further expansion of the production scale of chloroacetic acid is influenced. If the hydrochloric acid is directly digested on site, products with high added values are further produced, which is beneficial to the development of the chloroacetic acid industry and is also beneficial to eliminating the hidden trouble of environmental pollution caused by the existence of excessive hydrochloric acid. Sulfur powder is used as a catalyst in the production process of chloroacetic acid in China, and the byproduct hydrogen chloride tail gas generally contains the catalyst sulfur powder and impurities such as acetyl chloride, chloroacetyl chloride, sulfur-containing compounds and the like, and at present, chloroacetic acid is synthesized in the production processIn the production process, sulfur is mostly used as a catalyst, and hydrogen chloride (HCl) and sulfur dioxide (SO) are generated in the process of producing monochloroacetic acid from liquid chlorine and acetic acid2) Sulfur trioxide (SO)3) Acetic acid (CH)3COOH) and chlorine (Cl)2) And the like. The introduction of these substances affects the synthesis reaction of glycine ethyl ester hydrochloride and the quality of the product, and therefore the off-gas must be purified before the reaction.
The method adopts hydrogen chloride gas obtained after chloroacetic acid tail gas purification as a hydrogen chloride raw material, researches the two aspects of complex process flow and product water carrying phenomenon, and provides the production of the aminoacetic acid ethyl ester hydrochloride with high yield and low cost.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel production method of glycine ethyl ester hydrochloride so as to solve the problems in the technical background.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a novel production method of glycine ethyl ester hydrochloride comprises the following steps:
step one, purifying tail gas containing hydrogen chloride in the production process of chloroacetic acid to prepare dry hydrogen chloride meeting the requirement of producing glycine ethyl ester hydrochloride;
step two, after aminoacetic acid and absolute ethyl alcohol are added into the esterification kettle, the stirring speed and the heating voltage are controlled, so that the reaction liquid in the esterification kettle is stirred stably and flows back stably when the temperature is controlled, and the dry hydrogen chloride obtained in the step one is slowly and continuously introduced into the esterification kettle until the reaction is finished;
step three, cooling, crystallizing and filtering the solution obtained after the reaction in the step two is finished, and drying the solid obtained by filtering; and (3) carrying out rotary evaporation on the filtered mother liquor, then cooling, crystallizing and filtering again to obtain a solid, drying, and obtaining a dried product, namely the aminoacetic acid ethyl ester hydrochloride.
In the above technical scheme, in the first step, the specific method for purifying the tail gas containing hydrogen chloride in the production process of chloroacetic acid comprises the following steps:
a. tail gas containing hydrogen chloride from the production process of chloroacetic acid enters the bottom of a first acetic acid washing tower, and the tail gas containing the hydrogen chloride in the first acetic acid washing tower is in countercurrent contact with an absorption liquid to remove acetic acid in the tail gas;
b. b, gas coming out of the top of the acetic acid washing tower I in the step a enters the bottom of an acetic acid washing tower II, and the gas is in countercurrent contact with absorption liquid in the acetic acid washing tower II to remove acetic acid in the gas;
c. the gas coming out of the top of the acetic acid washing tower II in the step b enters CaCl2Drying the bottom of the tower to remove water from the gas;
d. from said step c CaCl2Gas coming out of the top of the drying tower enters the bottom of a sulfuryl chloride synthesis tower, chlorine is introduced from the bottom of the sulfuryl chloride synthesis tower, the introduced chlorine and the chlorine in the gas react with sulfur dioxide and sulfur trioxide in the gas rapidly to generate sulfuryl chloride, the generated sulfuryl chloride and residual hydrogen chloride gas in the gas are condensed by a condenser above the sulfuryl chloride synthesis tower, and the condensed sulfuryl chloride flows into a sulfuryl chloride storage tank from the bottom of the sulfuryl chloride synthesis tower;
the gas coming out from the top of the sulfuryl chloride synthesis tower and condensed by a condenser is the dry hydrogen chloride meeting the requirement of producing the glycine ethyl ester hydrochloride.
In the technical scheme, the feeding mass ratio of the glycine to the absolute ethyl alcohol in the second step is 1: 3.
In the above technical scheme, in the second step, the esterification kettle is a glass reaction kettle or a glass lining reaction kettle.
In the technical scheme, in the second step, the flow of the dry hydrogen chloride obtained in the first step is 10-25 Nm3And h, controlling the temperature to be 70-78 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the hydrogen chloride gas in the tail gas generated in the production of the aminoacetic acid, the absolute ethyl alcohol and the chloroacetic acid as the raw materials to react to generate the aminoacetic acid ethyl ester hydrochloride, the process flow is simple, and the product quality can reach the refining level without repeated crystallization.
In the invention, the raw material hydrogen chloride is derived from the tail gas in the production of monochloroacetic acid, thereby realizing the comprehensive utilization of resource recovery, saving the cost and producing the product of the glycine ethyl ester hydrochloride with high added value.
Drawings
FIG. 1 is a flow chart of the present invention;
in the figure, 1, tail gas containing hydrogen chloride in the production process of chloroacetic acid; 2. acetic acid wash column one; 3. acetic acid scrubber II; 4. CaCl2A drying tower; 5. a sulfuryl chloride synthesis tower; 6. a condenser; 7. an esterification kettle; 8. a stirrer; 9. a reflux condenser; (ii) a 10. A heater; 11. a suction filter; 12. an oven; 13. an evaporator; 14. and (4) a sulfuryl chloride storage tank.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
Referring to fig. 1, a novel method for producing glycine ethyl ester hydrochloride comprises the following steps:
step one, purifying tail gas 1 containing hydrogen chloride in the production process of chloroacetic acid to prepare dry hydrogen chloride meeting the requirement of producing glycine ethyl ester hydrochloride; the specific method comprises the following steps:
a. tail gas 1 containing hydrogen chloride from the production process of chloroacetic acid enters the bottom of a first acetic acid washing tower 2, and the tail gas 1 containing the hydrogen chloride in the first acetic acid washing tower 2 is in countercurrent contact with an absorption liquid to remove acetic acid in the tail gas;
b. b, gas coming out of the top of the first acetic acid washing tower 2 in the step a enters the bottom of a second acetic acid washing tower 3, and the gas is in countercurrent contact with absorption liquid in the second acetic acid washing tower 3 to remove acetic acid in the gas;
c. the gas coming out of the top of the second acetic acid washing tower 3 in the step b enters CaCl2Drying the bottom of the tower 4 to remove water from the gas;
d. from said step c CaCl2The gas from the top of the drying tower 4 enters the bottom of the sulfuryl chloride synthesis tower 5, and chlorine (Cl) is introduced from the bottom of the sulfuryl chloride synthesis tower 52) And tail gas (i.e., CaCl)2Gas coming out of the top of the drying column 4) of a small amount of chlorine (Cl)2) With sulfur dioxide (SO) in the gas2) Sulfur trioxide (SO)3) Quickly react to generate sulfuryl chloride, generated sulfuryl chloride and gas (CaCl)2Gas from the top of the drying tower 4) is condensed by a condenser 6, and the condensed sulfuryl chloride flows into a sulfuryl chloride storage tank 14 from the bottom of a sulfuryl chloride synthesis tower 5;
the gas coming out of the top of the sulfuryl chloride synthesis tower 5 and condensed by the condenser 6 is the dry hydrogen chloride (with the water content of 0) meeting the requirement of producing the glycine ethyl ester hydrochloride.
In particular, from CaCl2The tail gas from the drying tower 4 enters from the lower part of the bottom part of the sulfuryl chloride synthesis tower 5, and chlorine (Cl) gas enters at the same time2) Introducing chlorine (Cl) from the lower part of the other side of the bottom of the sulfuryl chloride synthesis tower 52) And tail gas (i.e., CaCl)2Gas coming out of the top of the drying column 4) of a small amount of chlorine (Cl)2) With sulfur dioxide (SO) in the gas2) Sulfur trioxide (SO)3) Rapidly reacting to generate sulfuryl chloride; the residual dry hydrogen chloride in the gas rises with the sulfuryl chloride formed, since the boiling point of hydrogen chloride (HCl) is very lowWhen the sulfuryl chloride and the sulfuryl chloride are at a temperature of about-85 ℃ and 70 ℃, dry hydrogen chloride (HCl) enters a reaction (such as a raw material enters an esterification kettle 7 or is collected) when the sulfuryl chloride and the sulfuryl chloride pass through a condenser 6 above a sulfuryl chloride synthesis tower 5, and the sulfuryl chloride condensed from the condenser flows into a sulfuryl chloride storage tank 14 from the bottom of the tower together with the sulfuryl chloride condensed in the rising process.
Wherein, the first acetic acid washing tower 2 and the second acetic acid washing tower 3 both contain absorption liquid, and the absorption liquid is over 31 percent concentrated hydrochloric acid and is used for absorbing acetic acid in tail gas; the first acetic acid washing tower 2 and the second acetic acid washing tower 3 have the same effect, and the two acetic acid washing towers are used because one tower is not used for completely absorbing acetic acid. CaCl2The filling in the drying tower 4 is CaCl2The function is to absorb water in the tail gas. Acetic acid washing tower 2, acetic acid washing tower 3 and CaCl2Drying column 4 the three column set conditions were atmospheric columns. The sulfuryl chloride synthesizing tower 5 is used for synthesizing sulfuryl chloride and removing sulfur dioxide (SO) in tail gas2) Sulfur trioxide (SO)3) And chlorine (Cl)2)。
Step two, after the aminoacetic acid and the absolute ethyl alcohol are added into an esterification kettle 7 (the esterification kettle 7 is provided with a stirrer 8 and a reflux condenser 9; the esterification kettle 7 is also matched with a heater 10 for heating the esterification kettle and controlling heating voltage and reaction temperature, such as an electric heating jacket; the esterification kettle is also provided with a feed inlet for adding the aminoacetic acid, the absolute ethyl alcohol and hydrogen chloride gas), the stirring speed and the heating voltage are controlled, so that the reaction liquid in the esterification kettle is stirred stably, and after the temperature is controlled and the reaction liquid flows back stably, the dry hydrogen chloride obtained in the step one is slowly and continuously introduced into the esterification kettle 7 until the reaction is finished; wherein the feeding mass ratio of the aminoacetic acid to the absolute ethyl alcohol is 1: 3; the esterification kettle is a glass reaction kettle or a glass lining reaction kettle, and preferably a four-port glass reaction kettle or a four-port glass reaction kettle; the flow rate of the dry hydrogen chloride obtained in the step one is 10-25 Nm3And h, controlling the temperature to be 70-78 ℃.
Step three, cooling, crystallizing and filtering the solution obtained after the reaction in the step two is finished, and drying the solid obtained by filtering; and (3) carrying out rotary evaporation on the filtered mother liquor, then cooling, crystallizing and filtering again to obtain a solid, drying, and obtaining a dried product, namely the aminoacetic acid ethyl ester hydrochloride.
Specifically, after the reaction in the second step is finished, the solution is cooled to 18 ℃ under stirring, then is filtered by a suction filter 11, and the solid obtained by suction filtration is collected and put into an oven 12 to be dried for 3 hours at 100 ℃; and meanwhile, carrying out rotary evaporation on the obtained suction filtration mother liquor by an evaporator 13 to obtain a secondary mother liquor with most of the solvent, cooling to 20 ℃, carrying out suction filtration again to obtain a solid, putting the solid into an oven 12, and drying for 3 hours at 100 ℃, wherein a dried product obtained by drying is glycine ethyl hydrochloride.
Example 1
The first experiment is repeated,
100g of aminoacetic acid and 300g of absolute ethyl alcohol are added into a 1000ml four-mouth bottle, and are respectively connected with an electric stirrer, a thermometer and a condenser, and the stirring speed and the heating voltage are adjusted to ensure that the reaction bottle is stirred stably and the temperature is controlled to reflux stably. And (3) purifying the tail gas containing hydrogen chloride in the chloroacetic acid production process to obtain dry hydrogen chloride, and slowly and stably introducing the dry hydrogen chloride into the reaction flask at the flow rate of 10-25 Nm3/h until the reaction is finished. Cooling the reaction solution to 18 ℃ under stirring, pouring the reaction solution into a Buchner funnel, carrying out vacuum filtration and pumping drying, pouring the reaction solution into a tray, weighing 220.3g of the reaction solution, putting the tray into an oven, drying the tray for 3 hours at the temperature of 100 ℃, taking out 175.2g of a weighed dried product, and carrying out sampling detection on the amino ethyl acetate hydrochloride and the amino acetate hydrochloride by 98.74 percent and 0.69 percent.
Most of the solvent is evaporated by the mother liquor after being dried, the secondary mother liquor is cooled to 20 ℃, poured into a Buchner funnel for vacuum filtration and drying to obtain 6.4g of solid, put into an oven for drying at 100 ℃ for 3 hours, and then 4.4g of weighed dry product is taken out, and sampling detection shows that the glycine ethyl acetate hydrochloride accounts for 97.3 percent and the glycine acetate hydrochloride accounts for 2.0 percent. 91.4 percent of ethanol is recycled.
The yield of ethyl glycinate hydrochloride was calculated as follows:
the reaction formula is as follows: NH (NH)2CH2COOH+HCl+C2H5OH→NH2CH2COOC2H5·HC1+H2O。
Given that 100g of glycine is fed, if the glycine is completely reacted, the formula can calculate that 186g of glycine ethyl ester hydrochloride can be obtained; and then 175.2g of weighed dry product is taken out, sampling detection shows that 98.74% of aminoacetic acid ethyl ester hydrochloride actually obtains 173g of aminoacetic acid ethyl ester hydrochloride, namely the yield of the aminoacetic acid ethyl ester hydrochloride is as follows: 173g/186 g-94.19%
The second experiment is repeated,
100g of aminoacetic acid and 300g of absolute ethyl alcohol are added into a 1000ml four-mouth bottle, and are respectively connected with an electric stirrer, a thermometer and a condenser, and the stirring speed and the heating voltage are adjusted to ensure that the reaction bottle is stirred stably and the temperature is controlled to reflux stably. And (3) purifying the tail gas containing hydrogen chloride in the chloroacetic acid production process to obtain dry hydrogen chloride, and slowly and stably introducing the dry hydrogen chloride into the reaction flask at the flow rate of 10-25 Nm3/h until the reaction is finished. Cooling the reaction solution to 18 ℃ under stirring, pouring the reaction solution into a Buchner funnel, performing vacuum filtration and pumping drying, pouring a tray, weighing 210.8g, putting the tray into an oven, drying the tray for 3 hours at 100 ℃, taking out 179.2g of a weighed dry product, sampling and detecting, and obtaining glycine ethyl ester hydrochloride: 99.08 percent and 0.63 percent of amino acetate hydrochloride.
Most of the solvent is evaporated by the mother liquor after being dried, the secondary mother liquor is cooled to 20 ℃, poured into a Buchner funnel for vacuum filtration and drying to obtain 3.3g of solid, put into an oven for drying at 100 ℃ for 3 hours, 2.6g of weighed dry product is taken out, and sampling detection shows that the glycine ethyl ester hydrochloride accounts for 97.55 percent and the glycine acetate hydrochloride accounts for 2.31 percent. 91.8 percent of ethanol is recycled.
Statistics of product testing data from two replicates are shown in table 1:
TABLE 1
Remarking: the product is a solid obtained by directly cooling, crystallizing and filtering reaction liquid; the mother liquor product is a solid obtained by filtering reaction liquid, filtering mother liquor, evaporating, cooling and crystallizing and then filtering.
As can be seen from Table 1, the product quality in the two repeated experiments is above 98.74, which indicates that the color and quality of the main product (glycine ethyl ester hydrochloride) of the invention meet the requirements of refined products.
Example 2
The production method of the embodiment is similar to that of the embodiment 1, except that the feeding mass ratio of the aminoacetic acid and the absolute ethyl alcohol in the esterification kettle is 1:2.5, namely 100g of the aminoacetic acid and 250g of the absolute ethyl alcohol, and the sampling detection shows that the product quality (solid obtained by directly cooling, crystallizing and filtering the reaction liquid), the aminoacetic acid ethyl ester hydrochloride is 97.02 percent, and the aminoacetic acid hydrochloride is 2.49 percent.
The product quality of the mother liquor (the reaction liquid is filtered, the mother liquor is evaporated, cooled and crystallized, and then the solid is filtered), 95.48 percent of aminoacetic acid ethyl ester hydrochloride and 4.33 percent of aminoacetic acid hydrochloride.
Example 3
The production method of the embodiment is similar to that of the embodiment 1, except that the feeding mass ratio of the aminoacetic acid and the absolute ethyl alcohol in the esterification kettle is 1:4, namely 100g of the aminoacetic acid and 400g of the absolute ethyl alcohol, and the sampling detection shows that the product quality (solid obtained by directly cooling, crystallizing and filtering the reaction liquid) is 97.28 percent of aminoacetic acid ethyl ester hydrochloride and 2.24 percent of aminoacetic acid hydrochloride.
The product quality of the mother liquor (the reaction liquor is filtered, the mother liquor is evaporated, cooled and crystallized, and then the solid is filtered), the aminoacetic acid ethyl ester hydrochloride is 96.03 percent, and the aminoacetic acid hydrochloride is 3.57 percent.
Compared with the embodiment 2 and the embodiment 3, the product quality of the embodiment 1 reaches the requirement of a refined product, and the mass ratio of the amino acetic acid to the absolute ethyl alcohol is 1:3, which is beneficial to improving the product quality.
Compared with the prior art, the method has the advantages of easy operation, simple flow and high yield; the hydrogen chloride is initially pretreated into the anhydrous chloroacetic acid, so that the process is simpler, the problem of air pollution possibly generated by the hydrogen chloride of the company is solved, and the waste is changed into valuable; the glycine and the hydrogen chloride used in the invention are mature products produced by the company, and are directly put into raw materials without modification, so that the production cost is effectively reduced.
The mixed gas of hydrogen chloride obtained by passing tail gas produced by monochloroacetic acid of the company (applicant) through a first acetic acid washing tower and a second acetic acid washing tower also contains chlorine (Cl)2) Sulfur dioxide (SO)2) Sulfur trioxide (SO)3) After the hydrogen chloride mixed gas is dewatered by a drying agent, the hydrogen chloride mixed gas is removed by a sulfuryl chloride synthesis tower to containWith chlorine (Cl)2) Sulfur dioxide (SO)2) Sulfur trioxide (SO)3) The obtained dry hydrogen chloride gas (with zero water content) can meet the requirement of producing the glycine ethyl ester hydrochloride. The method for synthesizing the glycine ethyl ester hydrochloride reduces the hydrochloric acid which has extremely low profit or even does not generate profit in tail gas absorption production, and simultaneously, hydrogen chloride in the tail gas is made into a product glycine ethyl ester hydrochloride with high added value for sale, thereby increasing the profit of companies, reducing environmental pollution and turning waste into wealth. The glycine ethyl ester hydrochloride is produced by using the hydrogen chloride gas purified by the chloroacetic acid tail gas, and the hydrogen chloride gas is not required to be purchased and stored, so that the cost of a storage site and a transportation link can be saved, and the glycine ethyl ester hydrochloride synthesized by the method has great competitive advantage in price and can generate considerable economic benefit for a company.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (5)
1. A novel production method of glycine ethyl ester hydrochloride is characterized by comprising the following steps:
step one, purifying tail gas (1) containing hydrogen chloride in the production process of chloroacetic acid to prepare dry hydrogen chloride meeting the requirement of producing glycine ethyl ester hydrochloride;
step two, after aminoacetic acid and absolute ethyl alcohol are added into the esterification kettle (7), the stirring speed and the heating voltage are controlled, so that the reaction liquid in the esterification kettle is stirred stably and flows back stably when the temperature is controlled, and the dry hydrogen chloride obtained in the step one is slowly and continuously introduced into the esterification kettle (7) until the reaction is finished;
step three, cooling, crystallizing and filtering the solution obtained after the reaction in the step two is finished, and drying the solid obtained by filtering; and (3) carrying out rotary evaporation on the filtered mother liquor, then cooling, crystallizing and filtering again to obtain a solid, drying, and obtaining a dried product, namely the aminoacetic acid ethyl ester hydrochloride.
2. A novel production method of ethyl glycinate hydrochloride according to claim 1, characterized in that in the first step, the specific method for purifying the tail gas (1) containing hydrogen chloride in the production process of the chloroacetic acid is as follows:
a. tail gas (1) containing hydrogen chloride from the production process of chloroacetic acid enters the bottom of a first acetic acid washing tower (2), and the tail gas (1) containing the hydrogen chloride in the first acetic acid washing tower (2) is in countercurrent contact with an absorption liquid to remove acetic acid in the tail gas;
b. b, gas coming out of the top of the first acetic acid washing tower (2) in the step a enters the bottom of a second acetic acid washing tower (3), and the gas is in countercurrent contact with absorption liquid in the second acetic acid washing tower (3) to remove acetic acid in the gas;
c. the gas coming out of the top of the second acetic acid washing tower (3) in the step b enters CaCl2Drying the bottom of the tower (4) to remove water from the gas;
d. from said step c CaCl2Gas coming out of the top of the drying tower (4) enters the bottom of a sulfuryl chloride synthesis tower (5), chlorine is introduced from the bottom of the sulfuryl chloride synthesis tower (5), the introduced chlorine and the chlorine in the gas react with sulfur dioxide and sulfur trioxide in the gas together to generate sulfuryl chloride, the generated sulfuryl chloride and residual hydrogen chloride gas in the gas are condensed by a condenser (6) above the sulfuryl chloride synthesis tower (5), and the condensed sulfuryl chloride flows into a sulfuryl chloride storage tank (14) from the bottom of the sulfuryl chloride synthesis tower (5);
the gas which comes out from the top of the sulfuryl chloride synthetic tower (5) and is condensed by the condenser (6) is the dry hydrogen chloride which meets the requirement of producing the glycine ethyl ester hydrochloride.
3. A novel production method of glycine ethyl ester hydrochloride according to claim 1, wherein the feeding mass ratio of glycine to absolute ethyl alcohol in the second step is 1: 3.
4. The novel production method of glycine ethyl ester hydrochloride according to claim 1, wherein in step two, the esterification kettle is a glass reaction kettle or a glass lining reaction kettle.
5. A novel production method of ethyl glycinate hydrochloride according to claim 1, wherein in the second step, the flow of the dry hydrogen chloride obtained in the first step is 10-25 Nm3And h, controlling the temperature to be 70-78 ℃.
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