CN114394607A - Process for recycling sodium sulfate in glycine production wastewater - Google Patents

Process for recycling sodium sulfate in glycine production wastewater Download PDF

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Publication number
CN114394607A
CN114394607A CN202210105176.8A CN202210105176A CN114394607A CN 114394607 A CN114394607 A CN 114394607A CN 202210105176 A CN202210105176 A CN 202210105176A CN 114394607 A CN114394607 A CN 114394607A
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sodium sulfate
glycine
wastewater
production wastewater
glycine production
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CN202210105176.8A
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Inventor
周焕东
刘宁
马跃辉
贾丹丹
滕东晓
傅玉倩
鄂生平
苑诚
赵锦书
张坤
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Shandong Tianda Taize Environmental Protection Technology Co ltd
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Shandong Tianda Taize Environmental Protection Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16Purification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/38Separation; Purification; Stabilisation; Use of additives
    • C07C227/40Separation; Purification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/38Separation; Purification; Stabilisation; Use of additives
    • C07C227/40Separation; Purification
    • C07C227/42Crystallisation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention belongs to the technical field of treatment and recovery of glycine production wastewater, and particularly relates to a process for recycling sodium sulfate in glycine production wastewater. The process for recycling sodium sulfate in the glycine production wastewater comprises the following steps: filtering the glycine production wastewater to remove solid impurities and suspended impurities in the wastewater to obtain the wastewater after impurity removal; adding absolute ethyl alcohol into the wastewater after impurity removal for mixing, then standing for layering, and separating an upper-layer water phase from a lower-layer organic phase to obtain a water phase and an organic phase; and (3) rectifying the water phase, distilling out ethanol to obtain a tower bottom liquid containing sodium sulfate, and performing evaporation concentration, washing and drying to obtain a final product sodium sulfate. According to the invention, the sodium sulfate in the wastewater from the glycine production is efficiently recovered, the whole recovery treatment process is green and environment-friendly, the yield of the product glycine is improved, the recovery rate and the purity of the sodium sulfate are high, and the production benefit is increased.

Description

Process for recycling sodium sulfate in glycine production wastewater
Technical Field
The invention belongs to the technical field of treatment and recovery of glycine production wastewater, and particularly relates to a process for recycling sodium sulfate in glycine production wastewater.
Background
Glycine of the formula C2H5NO2The amino acid is white solid at normal temperature and normal pressure, and is one of amino acids in amino acid series, which has the simplest structure and is unnecessary for human body. In the event of a severe emergency in the organism, glycine serves as an exogenous supplement, also known as a semi-essential amino acid. The food can be used as biochemical reagent, nutritional supplement, and flavoring agent. The medicine is used for treating myasthenia gravis and progressive muscular atrophy, and can reduce irritation to stomach and treat hyperprolinemia in children when being combined with aspirin. Can be used as edible feed for poultry, livestock and the like in agriculture, and is added with amino acid additives and attractants.
The current industrial processes for the production of glycine are: the hydroxyacetonitrile reacts with ammonia water to generate aminoacetonitrile, the aminoacetonitrile is hydrolyzed with liquid alkali to generate aminoacetic sodium, the aminoacetic sodium is acidified by sulfuric acid to generate aminoacetic acid (glycine) and sodium sulfate, and the product glycine is obtained through separation and purification.
The wastewater generated in the production process mainly comprises the following components: 10-20% of glycine, 5-10% of iminodiacetic acid and 10-15% of sulfate radical. The wastewater has high glycine and sulfate radicals, and if the wastewater is directly discharged to a sewage treatment system for sewage treatment, the yield of products is low, and the economic benefit is low. Therefore, a wastewater treatment process for increasing the yield of glycine and simultaneously producing anhydrous sodium sulfate needs to be designed, and the solvent used in the treatment process is recycled, so that the total production value of the whole process flow is increased.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the process for recycling the sodium sulfate in the wastewater from the glycine production has the advantages that the sodium sulfate in the wastewater from the glycine production is efficiently recycled, the whole recycling process is green and environment-friendly, the yield of the product glycine is improved, the recovery rate and the purity of the sodium sulfate are high, and the production benefit is increased.
The process for recycling sodium sulfate in the glycine production wastewater comprises the following steps:
(1) removing impurities: filtering the glycine production wastewater to remove solid impurities and suspended impurities in the wastewater to obtain the wastewater after impurity removal;
(2) layering: adding absolute ethyl alcohol into the wastewater after impurity removal for mixing, then standing for layering, and separating an upper-layer water phase from a lower-layer organic phase to obtain a water phase and an organic phase;
(3) and (3) rectification: rectifying the separated water phase, and distilling out ethanol to obtain a tower bottom liquid containing sodium sulfate;
(4) concentrating and drying: and (4) evaporating and concentrating the tower bottom liquid containing sodium sulfate, washing and drying to obtain the final product sodium sulfate.
In the step (1) of the invention, 500-1000 mesh self-cleaning filters are adopted for filtering.
The wastewater from the production of glycine contains 10-20% of glycine, 5-10% of iminodiacetic acid and 10-15% of sulfate radical.
In the step (2) of the present invention, the mixing volume ratio of the anhydrous ethanol to the wastewater is (100-: 100.
the main components of the wastewater are as follows: 10-20% of glycine, 5-10% of iminodiacetic acid and 10-15% of sulfate radical.
Adding absolute ethyl alcohol into the waste water after impurity removal for mixing, wherein glycine is insoluble in ethyl alcohol, water and the absolute ethyl alcohol can be mutually soluble in any proportion, adding the absolute ethyl alcohol, dissolving sulfate radicals in the waste water in water and mixing with the ethyl alcohol, and neither glycine nor iminodiacetic acid in an organic phase is soluble in the ethyl alcohol, so that the ethanol can be used for separating the three, and further the sulfate radicals can be recycled.
During mixing, a magnetic stirrer is adopted for stirring, the stirring speed is 300-500r/min, and the stirring time is 15-20 min.
Mixing, stirring, standing for 30-60min for layering, and separating the upper aqueous phase and the lower organic phase by an oil-water separator. The separated water phase mainly comprises water, ethanol and sodium sulfate, and sodium sulfate is extracted in the next step; the separated organic phase components mainly comprise glycine and iminodiacetic acid, and the organic phase components return to a glycine concentration and crystallization system to recover the glycine, so that the yield of the glycine is improved.
In the step (3), the rectification temperature is 75-85 ℃. And (3) recycling the ethanol obtained by distillation for the step (2).
In the step (4) of the invention, the evaporation concentration temperature is 110-.
Washing with deionized water at 70-90 deg.C for 480 min.
The purity of the sodium sulfate product recovered by the method is more than 95%, and the recovery rate reaches 95-99%.
Compared with the prior art, the invention has the following beneficial effects:
according to the process for recycling sodium sulfate in the glycine production wastewater, the sodium sulfate in the glycine production wastewater is efficiently recycled, the whole recycling treatment process is green and environment-friendly, the yield of the product glycine is improved, the recovery rate and the purity of the sodium sulfate are high, the purity of the recycled sodium sulfate product is over 95%, the recovery rate reaches 95-99%, and the production benefit is increased.
Drawings
FIG. 1 is a process flow diagram for recycling sodium sulfate in wastewater from glycine production.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
A process for recycling sodium sulfate in glycine production wastewater comprises the following steps:
(1) removing impurities: filtering glycine production wastewater by using a 500-mesh self-cleaning filter, removing solid impurities and suspended impurities in the wastewater to obtain impurity-removed wastewater, and detecting that the impurity-removed wastewater contains 19.77% of glycine, 7.66% of iminodiacetic acid and 10.00% of sulfate radicals;
(2) layering: mixing absolute ethyl alcohol and waste water according to a volume ratio of 100: 100, adding absolute ethyl alcohol into the wastewater after impurity removal, stirring and mixing by using a magnetic stirrer, wherein the stirring speed is 400r/min, the stirring time is 15min, standing for 40min for layering, separating an upper-layer water phase from a lower-layer organic phase by using an oil-water separator after layering, and extracting sodium sulfate from the separated water phase in the next step, wherein the components of the separated water phase mainly comprise water, ethyl alcohol and sodium sulfate; the separated organic phase components mainly comprise glycine and iminodiacetic acid, and the organic phase components return to a glycine concentration and crystallization system to recover the glycine, so that the yield of the glycine is improved;
(3) and (3) rectification: rectifying the separated water phase in a rectifying tower at the rectifying temperature of 78 ℃, distilling out ethanol, and recycling the distilled out ethanol in the step (2) to obtain tower bottom liquid containing sodium sulfate;
(4) concentrating and drying: and (3) carrying out evaporation concentration on the tower bottom liquid containing the sodium sulfate, wherein the evaporation concentration temperature is 120 ℃, the evaporation concentration time is 20min, washing the concentrate by using deionized water, and then drying at 80 ℃ for 7h to obtain the final product sodium sulfate.
The purity of the recovered sodium sulfate product was 95.5% and the recovery rate was 97.6%.
Example 2
A process for recycling sodium sulfate in glycine production wastewater comprises the following steps:
(1) removing impurities: filtering glycine production wastewater by a 1000-mesh self-cleaning filter, removing solid impurities and suspended impurities in the wastewater to obtain impurity-removed wastewater, wherein the impurity-removed wastewater contains 16.25% of glycine, 8.42% of iminodiacetic acid and 11.70% of sulfate radical through detection;
(2) layering: according to the mixing volume ratio of the absolute ethyl alcohol to the waste water of 150: 100, adding absolute ethyl alcohol into the wastewater after impurity removal, stirring and mixing by using a magnetic stirrer, wherein the stirring speed is 300r/min, the stirring time is 20min, standing for 60min for layering, separating an upper-layer water phase from a lower-layer organic phase by using an oil-water separator after layering, and extracting sodium sulfate in the separated water phase in the next step; the separated organic phase is recycled and reused in the glycine production step;
(3) and (3) rectification: rectifying the separated water phase in a rectifying tower at 75 ℃, distilling out ethanol, and recycling the distilled out ethanol in the step (2) to obtain tower bottom liquid containing sodium sulfate;
(4) concentrating and drying: and (3) carrying out evaporation concentration on the tower bottom liquid containing the sodium sulfate, wherein the evaporation concentration temperature is 125 ℃, the evaporation concentration time is 20min, washing the concentrate by using deionized water, and then drying at 70 ℃ for 8h to obtain the final product sodium sulfate.
The purity of the recovered sodium sulfate product was 96.2%, and the recovery rate was 96.3%.
Example 3
A process for recycling sodium sulfate in glycine production wastewater comprises the following steps:
(1) removing impurities: filtering glycine production wastewater by using a 500-mesh self-cleaning filter, removing solid impurities and suspended impurities in the wastewater to obtain impurity-removed wastewater, and detecting that the impurity-removed wastewater contains 17.68% of glycine, 8.92% of iminodiacetic acid and 13.24% of sulfate radicals;
(2) layering: according to the mixing volume ratio of the absolute ethyl alcohol to the waste water of 120: 100, adding absolute ethyl alcohol into the wastewater after impurity removal, heating, stirring and mixing by using a magnetic stirrer, wherein the stirring speed is 500r/min, the stirring time is 15min, standing for 30min for layering, separating an upper-layer water phase from a lower-layer organic phase by using an oil-water separator after layering, wherein the separated water phase contains sodium sulfate, and performing next step of sodium sulfate extraction; the separated organic phase is recycled and reused in the glycine production step;
(3) and (3) rectification: rectifying the separated water phase in a rectifying tower at the rectifying temperature of 80 ℃, distilling out ethanol, and recycling the distilled out ethanol in the step (2) to obtain tower bottom liquid containing sodium sulfate;
(4) concentrating and drying: and (3) carrying out evaporation concentration on the tower bottom liquid containing the sodium sulfate, wherein the evaporation concentration temperature is 110 ℃, the time is 30min, washing the concentrate by using deionized water, and then drying at 90 ℃ for 6h to obtain the final product sodium sulfate.
The purity of the recovered sodium sulfate product was 95.7% and the recovery rate was 98.5%.
Comparative example 1
A process for recycling sodium sulfate in glycine production wastewater comprises the following steps:
(1) removing impurities: filtering glycine production wastewater by using a 500-mesh self-cleaning filter, removing solid impurities and suspended impurities in the wastewater to obtain impurity-removed wastewater, wherein the impurity-removed wastewater contains 18.58% of glycine, 8.69% of iminodiacetic acid and 11.38% of sulfate radical through detection;
(2) and (3) evaporation and concentration: adopting MVR or multi-effect evaporation at 90 ℃, evaporating and concentrating the glycine production wastewater to improve the sulfate radical content to be between 20 and 30 percent;
(3) freezing and crystallizing: freezing and cooling the evaporated and concentrated wastewater to lower the temperature to below 5 ℃, and crystallizing and separating out sodium sulfate in a mirabilite form; the frozen mother liquor enters the glycine production step again;
(4) centrifugal drying: and (3) putting the mirabilite separated out by crystallization into a centrifugal dehydrator, centrifugally dehydrating the mirabilite, washing the mirabilite with deionized water, and drying at 120 ℃ for 8 hours to obtain the final product sodium sulfate.
The purity of the recovered sodium sulfate product is 85.4%, the recovery rate is 88.4%, and both the purity and the recovery rate are lower; and is firstly evaporated at high temperatureThe sodium sulfate (Na) produced by freezing is greatly consumed by condensation, freezing and crystallization2SO4.10H2O) contains a large amount of crystal water, and needs to be dried at a higher temperature, and the drying energy consumption is also larger.
Comparative example 2
A process for recycling sodium sulfate in glycine production wastewater comprises the following steps:
(1) removing impurities: filtering glycine production wastewater by using a 500-mesh self-cleaning filter, removing solid impurities and suspended impurities in the wastewater to obtain impurity-removed wastewater, wherein the impurity-removed wastewater contains 19.52% of glycine, 8.35% of iminodiacetic acid and 11.21% of sulfate radical through detection;
(2) layering: mixing anhydrous methanol and wastewater according to a volume ratio of 100: 100, adding absolute ethyl alcohol into the wastewater after impurity removal, stirring and mixing by using a magnetic stirrer, wherein the stirring speed is 400r/min, the stirring time is 15min, standing for 40min for layering, separating an upper-layer water phase from a lower-layer organic phase by using an oil-water separator after layering, and carrying out next-step extraction of sodium sulfate;
(3) and (3) rectification: rectifying the separated water phase in a rectifying tower at the rectifying temperature of 78 ℃ to evaporate methanol to obtain tower bottom liquid;
(4) concentrating and drying: and (3) carrying out evaporation concentration on the tower bottom liquid containing the sodium sulfate, wherein the evaporation concentration temperature is 120 ℃, the evaporation concentration time is 20min, washing the concentrate by using deionized water, and then drying at 80 ℃ for 7h to obtain the final product sodium sulfate.
The purity of the recovered sodium sulfate product was 60.2%, and glycine was not completely separated.

Claims (10)

1. A process for recycling sodium sulfate in glycine production wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) removing impurities: filtering the glycine production wastewater to remove solid impurities and suspended impurities in the wastewater to obtain the wastewater after impurity removal;
(2) layering: adding absolute ethyl alcohol into the wastewater after impurity removal for mixing, then standing for layering, and separating an upper-layer water phase from a lower-layer organic phase to obtain a water phase and an organic phase;
(3) and (3) rectification: rectifying the separated water phase, and distilling out ethanol to obtain a tower bottom liquid containing sodium sulfate;
(4) concentrating and drying: and (4) evaporating and concentrating the tower bottom liquid containing sodium sulfate, washing and drying to obtain the final product sodium sulfate.
2. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: the wastewater from the production of glycine contains 10-20% of glycine, 5-10% of iminodiacetic acid and 10-15% of sulfate radical.
3. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (1), 500-1000 mesh self-cleaning filters are adopted for filtering.
4. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (2), the mixing volume ratio of the absolute ethyl alcohol to the wastewater is (50-150): 100.
5. the process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (2), a magnetic stirrer is adopted for stirring during mixing, the stirring speed is 300- & lt 500 & gt r/min, and the stirring time is 15-20 min.
6. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: and (2) mixing, stirring, standing for 30-60min for layering, and separating an upper aqueous phase from a lower organic phase by an oil-water separator.
7. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (3), the rectification temperature is 75-85 ℃.
8. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (3), the ethanol obtained by distillation is recycled for use in the step (2).
9. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (4), the evaporation concentration temperature is 110-.
10. The process for recycling sodium sulfate in glycine production wastewater according to claim 1, characterized in that: in the step (4), the drying temperature after washing is 70-90 ℃, and the drying time is 360-480 min.
CN202210105176.8A 2022-01-28 2022-01-28 Process for recycling sodium sulfate in glycine production wastewater Pending CN114394607A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116143240A (en) * 2023-04-19 2023-05-23 元氏鑫宏升医药科技有限公司 Clean treatment method for glycine production wastewater

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116143240A (en) * 2023-04-19 2023-05-23 元氏鑫宏升医药科技有限公司 Clean treatment method for glycine production wastewater
CN116143240B (en) * 2023-04-19 2023-07-25 元氏鑫宏升医药科技有限公司 Clean treatment method for glycine production wastewater

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Application publication date: 20220426