CN109354261B - Treatment process of p-hydroxyphenylglycine synthetic industrial wastewater - Google Patents
Treatment process of p-hydroxyphenylglycine synthetic industrial wastewater Download PDFInfo
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- CN109354261B CN109354261B CN201811504158.7A CN201811504158A CN109354261B CN 109354261 B CN109354261 B CN 109354261B CN 201811504158 A CN201811504158 A CN 201811504158A CN 109354261 B CN109354261 B CN 109354261B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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Abstract
The invention discloses a process for treating p-hydroxyphenylglycine synthetic industrial wastewater, which comprises the following steps: adding acid into industrial wastewater to adjust the pH value to acidity, then adding an extracting agent for extraction to obtain an organic phase and a water phase, concentrating the water phase, and filtering to obtain inorganic salt and mother liquor; and the organic phase adopts a distillation method to recover the extractant and the phenol. The method can realize the high-efficiency separation of organic matters and salts, and the recovered salts are dried and have high purity and can be sold directly; the recovered phenol can be directly used for production; the water generated by concentration directly enters into the environment protection, and the treatment process realizes the green and sustainable industrialized mass production of the DL-p-hydroxyphenylglycine.
Description
Technical Field
The invention relates to a treatment process of industrial wastewater generated in the synthesis of a medical intermediate, in particular to a treatment process of industrial wastewater generated in the synthesis of an antibiotic medical intermediate, and belongs to the field of pharmaceutical chemicals.
Background
DL-p-hydroxyphenylglycine is an important intermediate of antibiotics and has the function of synthesizing side chains of semi-synthetic beta-lactam antibiotics.
In the prior art, the method for synthesizing DL-p-hydroxyphenylglycine by industrial production is to prepare racemic p-hydroxyphenylglycine by reacting phenol, glyoxylic acid and sulfamic acid. The method has mature process and low cost, the post-treatment process is to add alkali for neutralization, filter and wash to obtain DL-p-hydroxyphenylglycine, but the method generates a large amount of industrial wastewater of high-salt and biologically refractory organic matters, and is environment-friendly and difficult to treat.
U.S. patent application No. US5336805 discloses a method for synthesizing DL-p-hydroxyphenylglycine, which comprises the following steps: under the condition of stirring at room temperature, sequentially adding sulfamic acid, phenol, sulfuric acid and glyoxylic acid aqueous solution into water, and then stirring for reaction at the temperature of 60-75 ℃ after the reaction is finished. At a temperature of 60 ℃ to 75 ℃, ammonia water is added to neutralize the solution to a pH of 4 to 5 while stirring. And cooling to room temperature, sequentially carrying out spin-filtration, water washing and methanol washing on the obtained p-hydroxyphenylglycine suspension, and drying to obtain the p-hydroxyphenylglycine. Wherein, the filtrate obtained by the spin filtration and the washing liquid obtained by the water washing and the methanol washing are combined to be the industrial wastewater to be treated by the invention, and the wastewater used in the embodiment is the same as the process wastewater.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a treatment process of p-hydroxyphenylglycine synthetic industrial wastewater, which can effectively separate salt and organic matters, and the treated wastewater meets the environmental protection requirement and can be discharged into the environment for further treatment.
The invention provides a treatment process of p-hydroxyphenylglycine synthetic industrial wastewater, which comprises the following steps: adding acid into industrial wastewater to adjust the pH value to acidity, then adding an extracting agent for extraction to obtain an organic phase and a water phase, concentrating the water phase, and filtering to obtain inorganic salt and mother liquor;
and distilling the organic phase to sequentially recover the extracting agent and the phenol.
According to the method, the industrial wastewater is adjusted to be acidic, then the extracting agent is added for extraction, so that organic matters and inorganic salts in the industrial wastewater can be efficiently separated, wherein the organic phase can be used for recycling phenol for reuse after being distilled, the aqueous phase can be used for recycling inorganic salts after being distilled, and meanwhile, the concentration of the organic matters in the mother liquor is greatly reduced, so that the environmental protection requirement is met.
The type and the amount of the added acid can influence the efficiency of subsequent extraction, preferably, the acid is sulfuric acid or hydrochloric acid, the pH value is adjusted to 1-6, preferably 1.5-4 by adding the acid, and at the moment, organic matters and salts in the wastewater can be more fully separated in the subsequent extraction process.
The kind of the extracting agent can greatly influence the extraction efficiency, and preferably, the extracting agent is one of ketone and alcohol or a mixture thereof;
ketones are butanone, pentanone and isomers thereof (including n-pentanone, i-pentanone, etc.), cyclohexanone;
the alcohols are butanol and isomers thereof (including n-butanol, isobutanol, etc.), pentanol and isomers thereof (including n-pentanol, isopentanol, etc.), cyclohexanol, octanol and isomers thereof.
Preferably, the dosage of the extracting agent is 1% -30%, preferably 5% -15% of the wastewater amount, and at the moment, the higher extraction efficiency can be ensured, and meanwhile, the cost can be reduced.
In the invention, organic matters in the water phase after the wastewater is treated can not cause organic matter accumulation through degradation and extraction, and can be directly sleeved in next batch of wastewater, and organic residual liquid obtained by organic phase through a recovery link is burnt in an incinerator. Preferably, the auxiliary agent is added into the mother liquor for degradation, and the obtained degradation liquid is merged into the acid-regulated industrial wastewater for extraction.
Preferably, the auxiliary agent is selected from one of aromatic aldehydes or a mixture thereof;
the aromatic aldehyde comprises benzaldehyde, o-chlorobenzaldehyde, p-chlorobenzaldehyde, salicylaldehyde or p-nitrobenzaldehyde.
Preferably, the amount of the used auxiliary agent is 0.1-5%, preferably 0.2-2% of the mass of the mother liquor.
Preferably, the temperature for degrading by adding the auxiliary agent is 90-150 ℃, and preferably 110-130 ℃.
Preferably, the recovered extractant is used for extracting the next batch of industrial wastewater, the recovered phenol is used for synthesizing p-hydroxyphenylglycine, and the residual organic matters are incinerated.
In the invention, the inorganic salt is obtained by using the spin filtration, the temperature of the spin filtration is 10-40 ℃, preferably 20-30 ℃, and the obtained inorganic salt can be directly sold for the outside.
Compared with the prior art, the invention has the beneficial effects that:
(1) the whole wastewater treatment process is simple, and the high-efficiency separation of organic matters and salts is realized. The recovered salt is dried and has high purity, and can be directly sold; the recovered phenol can be directly used for production.
(2) Mother liquor generated by concentration can be combined for treatment after degradation, so that zero discharge of wastewater is basically realized, and green and sustainable industrial mass production of DL-p-hydroxyphenylglycine is realized.
Detailed Description
For better understanding of the technical solutions of the present invention, the following embodiments are further described, but those skilled in the art should recognize that the present invention is not limited to these embodiments.
Example 1
Adding 1000g of industrial wastewater (COD:12 ten thousand) in sequence, adding concentrated sulfuric acid to adjust the pH value to 3, adding 100g of n-butanol, stirring for half an hour, standing and layering to obtain a water layer and an organic phase, concentrating 60% of the water layer (the concentration of 60% refers to that the mass of the concentrated solution is 40% of the original mass, the same applies below), separating out solids, performing filter filtration to recover 200g of white ammonium sulfate with the purity of 98%, draining off 95%, adding 2g of benzaldehyde (used for degrading aromatic ring amino acid fragment-containing organic matters which are difficult to extract in the wastewater into aromatic aldehyde substances which are easy to extract), heating to 120 ℃, keeping the temperature for 8 hours, cooling, and adding into the next batch of acid-adjusted wastewater for extraction (the COD of the treated mother solution is 6 ten thousand); the organic phase was concentrated to 60% and 85g of n-butanol was recovered with a purity of 98.5%, and further concentrated to 50% and 20g of phenol was recovered with a purity of 98%. And (4) burning the residual organic residual liquid, recycling the n-butyl alcohol to be used in the next batch of extraction, and recycling the phenol to be used in the next batch of production.
The continuous production of the wastewater is realized by repeating the operation procedure.
Example 2
Adding 1000g of industrial wastewater (COD:12 ten thousand) in sequence, adding sulfuric acid to adjust the pH value to 2, adding 120g of n-butyl ketone, stirring for half an hour, standing for layering, concentrating a water layer to 60%, separating out solids, performing filter filtration to recover 205g of white-like ammonium sulfate with the purity of 97.5%, draining to 95%, adding 1.5g of salicylaldehyde into 190g of mother liquor, heating to 130 ℃, keeping the temperature for 8 hours, cooling, and adding into the next batch of acid-adjusted wastewater for extraction (COD of the treated mother liquor: 5.6 ten thousand); the organic phase was concentrated to 66% to recover 110g of n-butanone with a purity of 98.5%, and further concentrated to 50% to recover 22g of phenol with a purity of 98.5%. And burning the residual organic residual liquid, recycling the n-butyl ketone for the next batch of extraction, and recycling the phenol for the next batch of production.
The continuous production of the wastewater is realized by repeating the operation procedure.
Comparative example 1
Sequentially adding 1000g of industrial wastewater (COD:12 ten thousand), adding 100g of n-butanol, stirring for half an hour, standing for layering to obtain a water layer and an organic phase, concentrating 60% of the water layer, recovering 200g of yellow ammonium sulfate, keeping the purity at 94.5%, drying to 85%, adding 2g of benzaldehyde (used for degrading organic matters which contain aromatic ring amino acid fragments and are not easy to extract in the wastewater and are aromatic aldehyde substances easy to extract) into 230g of mother liquor, heating to 120 ℃, keeping the temperature for 8 hours, cooling, and adding into the next batch of acid-regulated wastewater for extraction (COD of the treated mother liquor: 14 ten thousand); the organic phase was concentrated to 60% to recover 80g of n-butanol with a purity of 98%, and further concentrated to 50% to recover 21g of phenol with a purity of 98%. And (4) burning the residual organic residual liquid, recycling the n-butyl alcohol to be used in the next batch of extraction, and recycling the phenol to be used in the next batch of production.
It should be noted that, because the pH is not adjusted, the organic matter in the aqueous phase and the organic matter in ammonium sulfate are accumulated, and the aqueous phase cannot be continuously used.
Comparative example 2
Adding 1000g of industrial wastewater (COD:12 ten thousand) in sequence, adding concentrated sulfuric acid to adjust the pH value to 3, adding 100g of n-butanol, stirring for half an hour, standing and layering to obtain a water layer and an organic phase, recovering 200g of white-like ammonium sulfate after the water layer is concentrated by 60%, wherein the purity is 98%, drying is performed by 90%, and the obtained 200g of mother liquor is merged into the next batch of acid-adjusted wastewater for extraction (the COD of the treated mother liquor is 16 ten thousand); the organic phase was concentrated to 60% to recover 80g of n-butanol with a purity of 98%, and further concentrated to 70% to recover 20g of phenol with a purity of 98%. And (4) burning the residual organic residual liquid, recycling the n-butyl alcohol to be used in the next batch of extraction, and recycling the phenol to be used in the next batch of production.
It should be noted that, because of no degradation, the aqueous phase organic matter and ammonium sulfate organic matter are accumulated, and further, the aqueous phase cannot be continuously reused.
It is noted that all references mentioned in this application are incorporated herein by reference as if each reference were individually incorporated by reference; it should be understood, moreover, that the foregoing is illustrative of specific embodiments of the invention and that numerous changes may be made therein by those skilled in the art without departing from the spirit and scope of the invention, which equivalents are encompassed within the scope of the invention.
Claims (5)
1. A treatment process of p-hydroxyphenylglycine synthetic industrial wastewater is characterized by comprising the following steps: adding acid into industrial wastewater to adjust the pH value to acidity, then adding an extracting agent for extraction to obtain an organic phase and a water phase, concentrating the water phase, and filtering to obtain inorganic salt and mother liquor;
distilling the organic phase to sequentially recover the extracting agent and the phenol;
the acid is sulfuric acid or hydrochloric acid, and the pH value is adjusted to 1.5-4 by adding the acid;
adding an auxiliary agent into the mother liquor for degradation, and merging the obtained degradation liquid into the acid-regulated industrial wastewater for merging treatment;
the auxiliary agent is selected from one of aromatic aldehydes or a mixture thereof;
the aromatic aldehyde is benzaldehyde, o-chlorobenzaldehyde, p-chlorobenzaldehyde, salicylaldehyde or p-nitrobenzaldehyde;
the extracting agent is one of ketone or alcohol;
the ketone is butanone, n-pentanone, iso-pentanone or cyclohexanone;
the alcohol is n-butanol, isobutanol, n-pentanol, isoamylol, cyclohexanol or octanol;
the temperature for adding the auxiliary agent for degradation is 90-150 ℃.
2. The process for treating p-hydroxyphenylglycine synthetic industrial wastewater according to claim 1, wherein the amount of the extractant used is 1 to 30 percent of the amount of wastewater.
3. The process for treating p-hydroxyphenylglycine synthetic industrial wastewater according to claim 1, wherein the amount of the used auxiliary agent is 0.1-5% by mass of the mother liquor.
4. The process for treating p-hydroxyphenylglycine synthetic industrial wastewater according to claim 1, wherein the temperature for degradation by adding the auxiliary agent is 110-130 ℃.
5. The process for treating p-hydroxyphenylglycine synthetic industrial wastewater according to claim 1, wherein the recovered extractant is used for extraction of the next batch of industrial wastewater, and the recovered phenol is used for synthesis of p-hydroxyphenylglycine.
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| CN111574457A (en) * | 2020-05-26 | 2020-08-25 | 联邦制药(内蒙古)有限公司 | Method for recovering hydrochloric acid and phenol in p-hydroxy-phenyl-hydantoin mother liquor |
| CN113636948B (en) * | 2021-08-20 | 2024-04-09 | 湖北省宏源药业科技股份有限公司 | DL-p-hydroxyphenylglycine asymmetric conversion resolution waste liquid treatment method |
| CN115254054B (en) * | 2022-07-25 | 2024-01-23 | 浙江云涛生物技术股份有限公司 | Production process of copper ion adsorption resin |
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| CN104609640A (en) * | 2013-11-05 | 2015-05-13 | 中蓝连海设计研究院 | Comprehensive treatment method of sebacic acid production wastewater |
| CN104787955A (en) * | 2015-04-17 | 2015-07-22 | 青岛科技大学 | Method for removing organic matters in phenolic wastewater |
| CN107089750A (en) * | 2017-04-28 | 2017-08-25 | 广东工业大学 | A kind of processing method containing high-concentration phenolic wastewater |
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| CN105084656B (en) * | 2015-08-10 | 2017-05-31 | 蓝星（北京）技术中心有限公司 | Methionine produces the processing method of waste water |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003070639A1 (en) * | 2002-02-22 | 2003-08-28 | Bayer Materialscience Ag | Preparation of waste water containing sodium chloride for use in chlor-alkali electrolysis |
| CN102503034A (en) * | 2011-11-08 | 2012-06-20 | 中蓝连海设计研究院 | Treatment method of phenol-containing liquid waste in sebacic acid production |
| CN104609640A (en) * | 2013-11-05 | 2015-05-13 | 中蓝连海设计研究院 | Comprehensive treatment method of sebacic acid production wastewater |
| CN104787955A (en) * | 2015-04-17 | 2015-07-22 | 青岛科技大学 | Method for removing organic matters in phenolic wastewater |
| CN107089750A (en) * | 2017-04-28 | 2017-08-25 | 广东工业大学 | A kind of processing method containing high-concentration phenolic wastewater |
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