CN112375007B - Treatment process of leftovers generated in preparation process of glycine ethyl ester hydrochloride - Google Patents
Treatment process of leftovers generated in preparation process of glycine ethyl ester hydrochloride Download PDFInfo
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- CN112375007B CN112375007B CN202011399244.3A CN202011399244A CN112375007B CN 112375007 B CN112375007 B CN 112375007B CN 202011399244 A CN202011399244 A CN 202011399244A CN 112375007 B CN112375007 B CN 112375007B
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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
- C07C227/14—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
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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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The scheme discloses a treatment process of leftovers generated in the process of preparing glycine ethyl ester hydrochloride, which comprises the steps of reacting glycine with absolute ethyl alcohol in the presence of hydrogen chloride, and carrying out alkali hydrolysis reaction on mother liquor obtained after crystallization and separation of reaction products. The method for treating the leftovers generated in the process of preparing the glycine ethyl ester hydrochloride is particularly suitable for treating the leftovers after multiple treatment and recovery. After treatment, the residual glycine ethyl ester hydrochloride, glycine hydrochloride and other byproducts which can be hydrolyzed are hydrolyzed into glycine and the like by adding alkali, the pH value is adjusted to be near the isoelectric point of the glycine, the glycine is separated out, the glycine is obtained by separation, and ethanol generated by hydrolysis is recovered by distillation. The production amount of solid waste of the leftovers can be greatly reduced through the scheme.
Description
Technical Field
The invention relates to the technical field of reaction waste recovery, in particular to a treatment process of leftovers generated in a glycine ethyl ester hydrochloride preparation process.
Background
The glycine ethyl ester hydrochloride is chemically named as glycine ethyl ester hydrochloride, is a pesticide and a medical intermediate which are widely applied, and can also be used for biochemical research and used 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 an anti-inflammatory drug such as gemifloxacin, such as Chinese patent CN104725294A, and an intelligence promoting drug oxiracetam is synthesized by taking glycine ethyl ester hydrochloride and 4-halogenated acetoacetate ester as raw materials, and is used for treating brain injury and nerve function deficiency, memory and intelligence disorder caused by the brain injury. The traditional glycine ethyl ester hydrochloride production process comprises the steps of heating glycine and acid ethanol (hydrogen chloride ethanol) for reflux reaction, cooling for crystallization, centrifugal separation, washing and drying to obtain the product. The optimized process is that glycine is added into absolute ethyl alcohol, hydrogen chloride gas is introduced when the temperature is raised until complete reaction is achieved, the temperature is reduced for crystallization, and the product is prepared after crystallization separation, washing and drying. In the process of synthesizing glycine ethyl ester hydrochloride, glycine ethyl ester hydrochloride is separated out by crystallization and centrifugation. Because one molecule of water is generated when one molecule of glycine ethyl ester hydrochloride is synthesized, the glycine ethyl ester hydrochloride has extremely high solubility in water and also has higher solubility in aqueous ethanol. After the synthesis solution is separated, a large amount of product still remains in the mother solution. In the currently commonly used production process, about 30% of the product remains in the mother liquor. The mother liquor contains water and can affect the next batch reaction by direct application, and the commonly adopted treatment process comprises the steps of distilling the mother liquor to recover ethanol, distilling the distillation residue under reduced pressure to distill out part of water, cooling and crystallizing, separating out leftovers, drying the leftovers, putting the leftovers into an esterification kettle, adding hydrogen chloride and ethanol to react the glycine hydrochloride with the ethanol and the hydrogen chloride to generate glycine ethyl ester hydrochloride, crystallizing and separating to obtain a glycine ethyl ester hydrochloride product, and merging the leftovers and distilling the mother liquor to separate the leftovers. After multiple treatments, the impurities of the leftover mother liquor are increased, the temperature is usually 140 ℃, the vacuum degree is-0.098 MPa, a large amount of water still can not be evaporated, and because glycine ethyl ester hydrochloride is very soluble in water, the leftover in the state is difficult to treat to obtain a product and can only be treated as solid waste.
Disclosure of Invention
One object of the present invention is to provide a process for treating the heel produced during the preparation of glycine ethyl ester hydrochloride.
In order to achieve the purpose, the scheme is as follows:
a treatment process of leftover materials generated in the process of preparing glycine ethyl ester hydrochloride comprises the following steps:
glycine and absolute ethyl alcohol react in the presence of hydrogen chloride, and mother liquor obtained after reaction products are crystallized and separated is subjected to alkali hydrolysis reaction.
Preferably, the process further comprises:
after the alkaline hydrolysis reaction is finished, the pH value of the solution is adjusted to be near the isoelectric point of glycine, so that the glycine can be separated out;
separating the separated glycine;
distilling the mixed liquid after separating the glycine, and recovering the ethanol in the liquid.
Preferably, the mother liquor is a mixed liquor obtained by carrying out a reaction between glycine and absolute ethyl alcohol in the presence of hydrogen chloride and carrying out multiple distillation crystallization treatment on a mixed liquor obtained after crystallization separation of a reaction product.
Preferably, the multiple distillation crystallization is performed for 5-10 times.
Preferably, the alkali-adding hydrolysis reaction further comprises adding ethanol into the mother liquor before alkali-adding hydrolysis is carried out, so that the mass ratio of ethanol to water in the mixed liquid is 1: 0.1-0.55, and filtering to remove insoluble impurities.
Preferably, the alkali-adding hydrolysis reaction is to introduce ammonia gas into the mother liquor, adjust the pH value of the mixed solution, and enable the alkali-adding hydrolysis reaction to be carried out under the condition that the pH value is 7.5-10.5, and the reaction time is 1-4 hours.
Preferably, the pH value of the mixed solution after the hydrolysis reaction is adjusted to 5.5-6.5, and the glycine is separated out by cooling and centrifuging.
Preferably, the liquid left after ethanol recovery is subjected to multi-effect evaporation, and the residue left after evaporation is treated as solid waste.
The scheme has the following beneficial effects:
the method for treating the leftovers generated in the process of preparing the glycine ethyl ester hydrochloride is particularly suitable for treating the leftovers after multiple treatment and recovery. The residual glycine ethyl ester hydrochloride, glycine hydrochloride and other byproducts which can be hydrolyzed are hydrolyzed into glycine and the like by adding alkali, the pH value is adjusted to be near the isoelectric point of the glycine, the glycine is separated out, the glycine is obtained by separation, and ethanol generated by hydrolysis is recovered by distillation. The production amount of solid waste of the leftovers can be greatly reduced through the scheme.
Detailed Description
Embodiments of the present solution are described in further detail below. It is clear that the described embodiments are only a part of the embodiments of the present solution, and not an exhaustive list of all embodiments. It should be noted that, in the present embodiment, features of the embodiment and the embodiment may be combined with each other without conflict.
After the waste mother liquor generated after the glycine ethyl ester hydrochloride product is separated in the process of synthesizing the glycine ethyl ester hydrochloride is treated for multiple times, impurities in the waste mother liquor are gradually increased, the waste mother liquor still contains a large amount of water and can not be evaporated when the vacuum degree is-0.098 MPa at 140 ℃, and the glycine ethyl ester hydrochloride is very easy to dissolve in water, so that the waste mother liquor after the waste mother liquor is treated by multiple times of distillation crystallization is difficult to treat and can only be treated as solid waste. In order to reduce the generation of solid waste and fully recover reaction raw material ethanol, the scheme provides a treatment process of leftovers generated in the process of preparing glycine ethyl ester hydrochloride for the purposes of simplicity and feasibility and maximally recovering the reaction raw materials.
The process comprises the following steps:
glycine and absolute ethyl alcohol react in the presence of hydrogen chloride, and mother liquor obtained after reaction products are crystallized and separated is subjected to alkali hydrolysis reaction.
The reaction formula of the alkaline hydrolysis reaction is shown as the following formula (1):
specifically, when ammonia gas is introduced into the mother liquor, the reaction equation is as follows (2):
after the alkaline hydrolysis reaction is completed, the method also comprises the following steps:
after the alkaline hydrolysis reaction is finished, the pH value of the solution is adjusted to be near the isoelectric point of glycine, so that the glycine can be separated out;
separating the separated glycine;
distilling the mixed liquid after separating the glycine, and recovering the ethanol in the liquid.
In one embodiment, the leftover mother liquor subjected to distillation and crystallization treatment for 5-10 times or more or the mother liquor difficult to distill is added into a reaction kettle; preferably, the medium for carrying out the alkaline hydrolysis reaction is an ethanol-water mixture, ethanol is added into a reaction kettle for adding the leftover mother liquor, and the adding amount of the ethanol is that the mass ratio of the ethanol to the water in the reaction system is 1: 0.1-0.55 percent of ethanol water with the mass percentage concentration of 65-91 percent is formed, the solubility of glycine is low in the ethanol water with the concentration range, inorganic salts such as ammonium chloride have certain solubility, and insoluble impurities are removed by filtration after uniform stirring.
In one embodiment, under the stirring state, an alkaline substance is slowly added into the kettle, the best choice is ammonia with smaller molecular weight, and less salt is generated after treatment; adjusting the flow rate of ammonia gas or other addition amount, and finally controlling the pH value of the materials in the kettle to be 7.5-10.5; preserving the heat for 1 to 4 hours under the condition of the pH value; cooling and centrifugally separating glycine after heat preservation; or dripping acid into the kettle, adjusting the pH value to 5.5-6.5, cooling the material to normal temperature, centrifugally drying, sampling and detecting, if the material is unqualified, rinsing the material with a small amount of ethanol until the material is qualified, and drying the filter cake to obtain the glycine.
In one embodiment, the centrifugal mother liquor after separating glycine is distilled, ethanol is recovered, and after the residual liquid is subjected to multiple-effect evaporation, the residue is treated as solid waste.
The present invention will be described in detail with reference to examples.
Example 1
(1) Pumping 800L of mother liquor obtained after ethanol is distilled and recovered into a glass lining kettle a with stirring capacity of 3000L, stirring, pumping 1600L of absolute ethanol, stirring for half an hour, and performing pressure filtration to a glass lining kettle b with stirring and backflow capacity of 3000L;
(2) slowly introducing ammonia gas into the glass lining kettle b, and controlling the aeration speed to be 1.5-2.0 m 3 Min, after the pH value is 8, keeping the pH value at about 8, keeping the temperature at 55-65 ℃ for 2 hours, and observing that a large amount of white crystals appear in the kettle;
(3) and (3) introducing cooling water into a jacket of the glass lining kettle b, cooling to normal temperature, preserving heat for 2 hours, carrying out centrifugal separation, carrying out spin-drying, sampling, detecting the content of chloride ions in the filter cake to be 0.9%, washing the filter cake once by using 95% ethanol in percentage by mass, and detecting the content of chloride ions in the filter cake to be 0.4%. And (3) drying the filter cake in vacuum to obtain 342.9kg of crystalline powder, wherein the glycine content in the dried filter cake is detected to be 98.1%, and the chloride ion content is detected to be 0.45%, so that the first-class standard in HG/T2029-2004 industrial grade glycine industry standard is met.
(4) And (3) distilling the centrifugal mother liquor obtained in the step (3) to recover ethanol to obtain 475kg of residual liquid, 268kg of evaporation residues obtained after triple effect evaporation dehydration, and detecting that the glycine content is 4.9%.
Example 2
(1) Pumping 800L of mother liquor obtained after ethanol is distilled and recovered into a glass lining kettle a with stirring capacity of 3000L, stirring, pumping 1600L of 95% ethanol, stirring for half an hour, and performing pressure filtration to a glass lining kettle b with stirring and backflow capacity of 3000L.
(2) Slowly introducing ammonia gas into the glass lining kettle b, and controlling the aeration speed to be 1.5-2.0 m 3 Min, after the pH value is 8, keeping the pH value at about 8, keeping the temperature at 55-65 ℃ for 2 hours, and observing that a large amount of white crystals appear in the kettle;
(3) and (3) introducing cooling water into a jacket of the glass lining kettle b, cooling to normal temperature, preserving heat for 2 hours, carrying out centrifugal separation, carrying out spin-drying, sampling, detecting the content of chloride ions in the filter cake to be 0.6%, washing the filter cake once by using 95% ethanol in percentage by mass, and detecting the content of chloride ions in the filter cake to be 0.35%. And drying the filter cake in vacuum to obtain 316.3kg of crystalline powder, wherein the content of glycine is 98.4 percent and the content of chloride ions is 0.40 percent according with the first-class standard in HG/T2029-2004 industrial grade glycine industry standard.
(4) And (4) distilling the centrifugal mother liquor obtained in the step (3) to recover ethanol to obtain 525kg of residual liquid, and detecting that the glycine content is 10.2% in 304kg of evaporation residues obtained after triple effect evaporation dehydration.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (5)
1. A treatment process of leftovers generated in a process of preparing glycine ethyl ester hydrochloride is characterized by comprising the following steps:
reacting glycine with absolute ethyl alcohol in the presence of hydrogen chloride, and carrying out alkaline hydrolysis reaction on mother liquor obtained after crystallization and separation of a reaction product;
wherein the alkali-adding hydrolysis reaction further comprises the steps of adding ethanol into the mother liquor before alkali-adding hydrolysis is carried out, so that the mass ratio of the ethanol to the water in the mixed liquid is 1: 0.1-0.55, and filtering to remove insoluble impurities;
after the alkaline hydrolysis reaction is finished, the pH value of the solution is adjusted to be near the isoelectric point of glycine, so that the glycine can be separated out;
separating the separated glycine;
distilling the mixed liquid after separating the glycine, and recovering ethanol in the liquid;
and the alkali-adding hydrolysis reaction is to introduce ammonia gas into the mother liquor, adjust the pH value of the mixed solution, and carry out the alkali-adding hydrolysis reaction under the condition that the pH value is 7.5-10.5, wherein the reaction time is 1-4 hours.
2. The treatment process according to claim 1, wherein the mother liquor is a mixed liquor obtained by subjecting a mixed liquor obtained by reacting glycine with absolute ethanol in the presence of hydrogen chloride and carrying out crystallization separation on a reaction product to a multiple distillation crystallization treatment.
3. The process according to claim 2, wherein the multiple distillation crystallization is performed 5 to 10 times.
4. The treatment process according to claim 1, wherein the pH value of the mixed solution after the hydrolysis reaction is adjusted to 5.5-6.5, and the glycine is separated by cooling and centrifuging.
5. The process of claim 1, wherein the liquid remaining after ethanol recovery is subjected to multi-effect evaporation, and the residue remaining after evaporation is treated as solid waste.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891637A (en) * | 2009-05-19 | 2010-11-24 | 李其奎 | Method for synthesizing glycine ester hydrochloride and processing mother liquid thereof |
| CN102234239A (en) * | 2010-04-30 | 2011-11-09 | 山东大成农药股份有限公司 | Optimization process of glycine ethyl ester hydrochloride |
| CN108484421A (en) * | 2018-04-27 | 2018-09-04 | 江苏优普生物化学科技股份有限公司 | The improved method for preparing glycine ethyl ester hydrochloride |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891637A (en) * | 2009-05-19 | 2010-11-24 | 李其奎 | Method for synthesizing glycine ester hydrochloride and processing mother liquid thereof |
| CN102234239A (en) * | 2010-04-30 | 2011-11-09 | 山东大成农药股份有限公司 | Optimization process of glycine ethyl ester hydrochloride |
| CN108484421A (en) * | 2018-04-27 | 2018-09-04 | 江苏优普生物化学科技股份有限公司 | The improved method for preparing glycine ethyl ester hydrochloride |
| 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 |
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