CN111689635A - Method for treating waste water containing ammonium acetate - Google Patents

Method for treating waste water containing ammonium acetate Download PDF

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Publication number
CN111689635A
CN111689635A CN202010525852.8A CN202010525852A CN111689635A CN 111689635 A CN111689635 A CN 111689635A CN 202010525852 A CN202010525852 A CN 202010525852A CN 111689635 A CN111689635 A CN 111689635A
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China
Prior art keywords
ammonium acetate
acetic acid
ammonium sulfate
waste water
treating
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CN202010525852.8A
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Chinese (zh)
Inventor
乔旭
崔咪芬
徐希化
陈献
刘清
周哲
齐敏
汤吉海
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Nanjing Zihuan Engineering Technology Research Institute Co ltd
Nanjing Tech University
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Nanjing Zihuan Engineering Technology Research Institute Co ltd
Nanjing Tech University
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Publication of CN111689635A publication Critical patent/CN111689635A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/24Sulfates of ammonium
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for treating waste water containing ammonium acetate, which comprises the steps of firstly, acidifying the waste water containing ammonium acetate by an acidifying agent to convert the ammonium acetate in the waste water into acetic acid and ammonium sulfate; distilling to remove acetic acid aqueous solution, producing acetic ester from the acetic acid aqueous solution by adopting an esterification reaction rectification method, and separating ammonium sulfate from organic matters remained in the water phase by adopting a self-salting-out method to obtain an ammonium sulfate product. The method adopts the method of firstly acidifying and then directly distilling, so that the acetic acid formed after acidification is separated from the ammonium sulfate in advance, the method is favorable for the subsequent esterification reaction of the acetic acid, and the content of organic matters in the obtained ammonium sulfate is less than or equal to 0.1 percent by utilizing the self-salting-out technology, so that the quality of the ammonium sulfate byproduct is greatly improved, the waste of the ammonium acetate wastewater is really changed into valuable, and the method has great environmental protection benefit and economic benefit.

Description

Method for treating waste water containing ammonium acetate
Technical Field
The invention belongs to the field of wastewater treatment and resource recovery, relates to a method for treating wastewater containing ammonium acetate, and particularly relates to a method for treating wastewater containing ammonium acetate and recovering acetic ester and ammonium sulfate in a resource manner.
Background
In the production process of furfural and methylamine phosphine, a large amount of waste water containing ammonium acetate is produced, and acetate radicals in the waste water are wasted if the waste water is directly treated. Therefore, how to realize the waste water treatment of ammonium acetate and realize resource utilization is a problem for furfural and methylamine phosphine production enterprises.
The patent CN1327953A discloses a method for treating furfural wastewater containing ammonium acetate, which comprises the steps of firstly separating organic matters in the wastewater by adsorption, then concentrating ammonium acetate mother liquor, separating out part of ammonium acetate, dehydrating to prepare acetamide, returning the acetamide to a furfural production system, acidifying ammonium acetate saturated liquid by concentrated sulfuric acid, separating out ammonium sulfate, acidifying, crystallizing, filtering to remove ammonium sulfate, then carrying out esterification reaction on the mother liquor containing acetic acid and butanol to obtain butyl acetate. This method has the following disadvantages: because the solubility of the ammonium acetate is as high as 148g/100g, the mother liquor obtained after acidification and filtration of the saturated aqueous solution of the ammonium acetate still contains a large amount of ammonium acetate, and because of the existence of the ammonium acetate, in the subsequent esterification reaction, the pH value in the aqueous solution is gradually increased along with the complete consumption of the acetic acid, and the acetic ester generated in the esterification reaction generates hydrolysis reaction, thereby influencing the yield of the esterification reaction. Therefore, the ammonium acetate needs to be removed first, and then esterification reaction is carried out, so that reaction rectification is possible to improve the conversion rate of the acetic acid and the yield of the acetic ester.
Patent CN1313282A discloses a method for separating ammonium acetate and furfural from wastewater by adsorption, in which the adsorbed acetate ions are desorbed by alkaline desorption and then acidified to obtain acetic acid, and the acidified solution is filtered and then directly added with ethanol to perform esterification reaction to obtain ethyl acetate. This method also has the drawbacks related to patent CN 1327953A.
Patent CN108689541A discloses a method for treating ammonium acetate-containing wastewater, which comprises the steps of firstly carrying out reduced pressure distillation dehydration on ammonium acetate wastewater to obtain water and mother liquor containing high-concentration ammonium acetate, acidifying the high-concentration ammonium acetate aqueous solution by using sulfuric acid, then cooling and crystallizing to precipitate ammonium sulfate, and distilling the precipitated residual liquid to obtain an acid-acid aqueous solution. The main disadvantage of the method is that a large amount of acetic acid is inevitably carried in ammonium sulfate crystals generated by cooling and crystallizing after the ammonium acetate aqueous solution is acidified, so that the ammonium sulfate generates a strong sour taste and cannot be sold as a refined byproduct.
Disclosure of Invention
Aiming at various defects in the prior art, the invention aims to provide a method for treating waste water containing ammonium acetate, which realizes the reclamation of acetate and the refinement of ammonium sulfate.
The purpose of the invention is realized by the following technical scheme:
a method for treating waste water containing ammonium acetate comprises the following steps: firstly, acidifying the ammonium acetate wastewater by using an acidifying agent to convert ammonium acetate in the wastewater into acetic acid and ammonium sulfate; distilling to remove acetic acid aqueous solution, producing acetic ester from the acetic acid aqueous solution by esterification distillation, and separating ammonium sulfate from part of organic matters remained in the water phase by self-salting out method to obtain refined ammonium sulfate product.
The ammonium acetate wastewater is wastewater produced by furfural or methylamine phosphine, the mass fraction of ammonium acetate in the wastewater is 15-25%, the mass fraction of ammonium sulfate is 1-3%, and the mass fraction of organic matters is less than or equal to 0.5%. The organic matter in the furfural production wastewater is mainly furfural except acetic acid, and the organic matter in the methylamine phosphine production wastewater is mainly methylamine phosphine except acetic acid.
The acidifying agent is sulfuric acid with the mass fraction of more than or equal to 70%, preferably 98% concentrated sulfuric acid, and the adding amount of the sulfuric acid is calculated by the molar ratio of the sulfuric acid to the ammonium acetate being 0.5-0.55: 1.
The distillation is normal pressure distillation, the temperature is 130-150 ℃, part of water and most of acetic acid in the acidizing fluid are distilled out, the mass fraction of ammonium sulfate in the distillation residue is 45-50%, the content of organic matters except the acetic acid is 0.5-1.1%, the content of the acetic acid is less than or equal to 0.07%, and the organic matters in the ammonium sulfate product are further separated after salting out at the temperature of 25-40 ℃ by utilizing the electrostatic repulsion between high-concentration ammonium ions and organic matter molecules, so that the content of the organic matters in the ammonium sulfate product is less than or equal to 0.1%.
The esterification reaction rectification method adopts methanol as aliphatic alcohol, the esterification reaction temperature is 60-65 ℃, the number of theoretical plates of the reaction rectification tower is 35-50, and the feeding molar ratio of the methanol to the acetic acid in the reaction rectification tower is 1-2: 1.
As a further preferable technical scheme of the invention, the water phase obtained by the esterification reaction rectification method and the water phase obtained by the self-salting-out method adopt biochemical further purification treatment, thereby realizing the recovery of acetic acid resources and the standard discharge of waste water.
The invention has the beneficial effects that:
the method adopts the method of firstly acidifying and then directly distilling, so that the acetic acid formed after acidification is separated from the ammonium sulfate in advance, the method is favorable for the subsequent esterification reaction of the acetic acid, the ammonium sulfate is separated from part of organic matters remained in a water phase by utilizing a self-salting-out technology, the content of the organic matters in the obtained ammonium sulfate is lower than 0.1 percent, the quality of the ammonium sulfate by-product is greatly improved, the waste of ammonium acetate wastewater is really changed into valuable, and the method has great environmental protection benefit and economic benefit.
Drawings
FIG. 1 is a flow chart of the method for treating waste water containing ammonium acetate according to the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The ammonium acetate wastewater to be treated is wastewater from furfural production, wherein the mass fraction of ammonium acetate is 25%, the mass fraction of ammonium sulfate is 2.9%, the organic impurities mainly comprise acetic acid and furfural, and the total mass fraction of the organic impurities is 0.5%.
As shown in figure 1, 1000kg of ammonium acetate wastewater is added into an acidification kettle, 178.6kg of 98% concentrated sulfuric acid is slowly dropped into the acidification kettle, and the mixture is stirred for half an hour, so that the ammonium acetate in the wastewater is converted into acetic acid and ammonium sulfate. The temperature of the jacket of the acidification kettle is increased to 150 ℃ for atmospheric distillation, 637.9kg of materials containing 194.4kg of acetic acid are distilled out, the distilled materials are introduced into a reaction rectification system to react with methanol to generate methyl acetate, the theoretical plate number of the adopted reaction rectification tower is 50, the esterification reaction temperature is 65 ℃, the final methanol consumption is 207.4kg, and the conversion rate of the acetic acid reaches 99.5%.
The distillation residue in the acidification kettle contains 243.3kg of ammonium sulfate, the content of furfural and other organic impurities (without acetic acid) in the distillation residue is 0.92 percent, the content of acetic acid is about 0.07 percent, the temperature is reduced to 25 ℃, self-salting-out action is generated, ammonium sulfate solid is separated out, most organic matters of the distillation residue are separated from the ammonium sulfate, and the organic matter content in the ammonium sulfate solid obtained after filtration and separation is 0.08 percent.
Example 2
The ammonium acetate wastewater to be treated is wastewater from furfural production, wherein the mass fraction of ammonium acetate is 20%, the mass fraction of ammonium sulfate is 2.1%, the organic impurities mainly comprise acetic acid and furfural, and the total mass fraction of the organic impurities is 0.2%.
2000kg of ammonium acetate wastewater is added into an acidification kettle, 259.7kg of 98% concentrated sulfuric acid is slowly dropped into the acidification kettle, and the mixture is stirred for half an hour, so that the ammonium acetate in the wastewater is converted into acetic acid and ammonium sulfate. The temperature of the jacket of the acidification kettle is increased to 150 ℃ for atmospheric distillation, 1458.0kg of materials containing 311.4kg of acetic acid are distilled out, the distilled materials are introduced into a reaction rectification system to react with methanol to generate methyl acetate, the theoretical plate of the adopted reaction rectification tower is 35, the esterification reaction temperature is 60 ℃, the final methanol consumption is 166.1kg, and the conversion rate of the acetic acid reaches 98.2%.
The distillation residue in the acidification kettle contains 384.9kg of ammonium sulfate, the content of furfural and other organic impurities (without acetic acid) in the distillation residue is 0.5 percent, the content of acetic acid is about 0.04 percent, the temperature is reduced to 30 ℃, self-salting-out is generated, ammonium sulfate solid is separated out, most organic matters of the distillation residue are separated from the ammonium sulfate, and the organic matter content in the ammonium sulfate solid obtained after filtration and separation is 0.1 percent.
Example 3
The ammonium acetate wastewater to be treated is wastewater from methamidophos production, wherein the mass fraction of ammonium acetate is 15%, the mass fraction of ammonium sulfate is 1.4%, the organic impurities mainly comprise acetic acid and methamidophos, and the total mass fraction of the organic impurities is 0.3%.
5000kg of ammonium acetate wastewater is added into an acidification kettle, 487.0kg of 98% concentrated sulfuric acid is slowly dropped into the acidification kettle, and the mixture is stirred for half an hour, so that the ammonium acetate in the wastewater is converted into acetic acid and ammonium sulfate. The temperature of an acidification kettle jacket is increased to 150 ℃ for atmospheric distillation, 4061.3kg of materials containing 583.7kg of acetic acid are distilled out, the distilled materials are introduced into a reaction rectification system to react with methanol to generate methyl acetate, the adopted reaction rectification tower has a theoretical plate of 50, the esterification reaction temperature is 65 ℃, the final methanol consumption is 467.0kg, and the conversion rate of the acetic acid reaches 99.3%.
The residue in the acidification kettle contains 712.9kg of ammonium sulfate, the content of furfural and other organic impurities (not containing acetic acid) in the residue is 1.1%, the content of acetic acid is about 0.05%, the temperature is reduced to 40 ℃, self-salting-out action is generated, ammonium sulfate solid is separated out, most of organic matters in the residue are separated from ammonium sulfate, and the organic matter content in the ammonium sulfate solid obtained after filtration and separation is 0.05%.

Claims (10)

1. A method for treating waste water containing ammonium acetate is characterized in that firstly, acidifying agent is adopted to acidify the waste water containing ammonium acetate so as to convert the ammonium acetate in the waste water into acetic acid and ammonium sulfate; distilling to remove acetic acid aqueous solution, producing acetic ester from the acetic acid aqueous solution by adopting an esterification reaction rectification method, and separating ammonium sulfate from organic matters remained in the water phase by adopting a self-salting-out method to obtain an ammonium sulfate product.
2. The method for treating the waste water containing the ammonium acetate according to claim 1, wherein the mass fraction of the ammonium acetate in the ammonium acetate waste water is 15 to 25%, the mass fraction of the ammonium sulfate is 1 to 3%, and the mass fraction of the organic matter is less than or equal to 0.5%.
3. The method for treating wastewater containing ammonium acetate according to claim 1, wherein the acidifying agent is sulfuric acid with a mass fraction of 70% or more, preferably 98% concentrated sulfuric acid.
4. The method for treating ammonium acetate-containing wastewater according to claim 3, wherein the amount of sulfuric acid added is 0.5 to 0.55:1 in terms of the molar ratio of sulfuric acid to ammonium acetate.
5. The method for treating the waste water containing the ammonium acetate according to claim 1, wherein the distillation is atmospheric distillation and the temperature is 130-150 ℃.
6. The method for treating wastewater containing ammonium acetate according to claim 1, wherein the mass fraction of ammonium sulfate in the residue is 45 to 50%, and the content of organic substances other than acetic acid is 0.5 to 1.1%.
7. The method for treating ammonium acetate-containing wastewater as claimed in claim 1, wherein the self-salting-out temperature is 25 to 40 ℃.
8. The method for treating waste water containing ammonium acetate according to claim 1, wherein the content of organic substances in the ammonium sulfate product is less than or equal to 0.1%.
9. The method for treating wastewater containing ammonium acetate according to claim 1, wherein the aliphatic alcohol used in the rectification by the esterification reaction is methanol; the esterification reaction temperature is 60-65 ℃.
10. The method for treating ammonium acetate-containing wastewater as claimed in claim 1, wherein the aqueous phase obtained by the rectification method of the esterification reaction and the aqueous phase obtained by the self-salting out are subjected to biochemical purification treatment to achieve standard discharge of wastewater.
CN202010525852.8A 2020-06-10 2020-06-10 Method for treating waste water containing ammonium acetate Pending CN111689635A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113754170A (en) * 2021-09-27 2021-12-07 高密银鹰新材料股份有限公司 Method for treating evaporation waste liquid in cellulose production

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB445108A (en) * 1934-10-02 1936-04-02 British Celanese Improvements in the recovery of acidic and basic reagents
CN1313282A (en) * 2001-03-08 2001-09-19 水志良 Process for treating waste water containing furaldehyde and recovering furaldehyde and acetic acid
CN1354165A (en) * 2001-11-15 2002-06-19 孙世勇 Control of waste water produced in furfural industry and preparation process of butyl acetate
CN201400612Y (en) * 2009-04-21 2010-02-10 南通维立科化工有限公司 Acephate ammonium acetate wastewater treatment system
CN108689541A (en) * 2018-04-24 2018-10-23 江苏蓝丰生物化工股份有限公司 The processing method of the waste water containing ammonium acetate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB445108A (en) * 1934-10-02 1936-04-02 British Celanese Improvements in the recovery of acidic and basic reagents
CN1313282A (en) * 2001-03-08 2001-09-19 水志良 Process for treating waste water containing furaldehyde and recovering furaldehyde and acetic acid
CN1354165A (en) * 2001-11-15 2002-06-19 孙世勇 Control of waste water produced in furfural industry and preparation process of butyl acetate
CN201400612Y (en) * 2009-04-21 2010-02-10 南通维立科化工有限公司 Acephate ammonium acetate wastewater treatment system
CN108689541A (en) * 2018-04-24 2018-10-23 江苏蓝丰生物化工股份有限公司 The processing method of the waste water containing ammonium acetate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113754170A (en) * 2021-09-27 2021-12-07 高密银鹰新材料股份有限公司 Method for treating evaporation waste liquid in cellulose production

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