CN103435441B - The method of dimethyl malonate production wastewater treatment and resource reclaim - Google Patents
The method of dimethyl malonate production wastewater treatment and resource reclaim Download PDFInfo
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- CN103435441B CN103435441B CN201310349611.2A CN201310349611A CN103435441B CN 103435441 B CN103435441 B CN 103435441B CN 201310349611 A CN201310349611 A CN 201310349611A CN 103435441 B CN103435441 B CN 103435441B
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- dimethyl malonate
- methyl alcohol
- ammonia
- wastewater treatment
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Abstract
Disclosed by the invention is the method for dimethyl malonate production wastewater treatment and resource reclaim, and its step is that methyl alcohol, ammonia neutralization and condensing crystal reclaim(ed) sulfuric acid ammonium are reclaimed in rectifying, or methyl alcohol and condensing crystal reclaim(ed) sulfuric acid ammonium are reclaimed in ammonia neutralization, rectifying; The rate of recovery of single batch of methyl alcohol of the present invention is greater than 85%, the methyl alcohol reclaimed can be applied mechanically in dimethyl malonate is produced, the rate of recovery of single batch of ammonium sulfate is greater than 70%, can be used as byproduct to sell, the raffinate reclaimed after methyl alcohol and ammonium sulfate can continue to apply mechanically in the malonic acid dimethyl ester production process extraction phase-splitting stage; After method process of the present invention, dimethyl malonate produce without high-concentration wastewater emission, useful resources is utilized effectively, and reduces environmental protection pressure and production cost, economy and environment protecting obvious.
Description
Technical field
The present invention relates to chemical production wastewater treatment process, be specifically related to the method for dimethyl malonate production wastewater treatment and resource reclaim.
Background technology
Dimethyl malonate is the intermediate of medicine, agricultural chemicals and dyestuff etc., the domestic and international more domestic main cyaniding esterification process of production method at present, namely be raw material with Mono Chloro Acetic Acid, sodium cyanide and methyl alcohol etc., through neutralization, cyaniding, acidifying, esterification process, last extracting and separating and obtain dimethyl malonate.Production process produces a certain amount of waste water, wherein containing a large amount of useful resources such as methyl alcohol, sulfuric acid, monoammonium sulfate, does not carry out reclaiming the significant wastage that not only can cause resource, also can serious environment pollution.
Often produce 1 ton of dimethyl malonate and approximately produce 2.5 tons of high-concentration waste waters, wherein containing methyl alcohol 200-220kg, sulfuric acid 580-600kg, monoammonium sulfate 800-900kg, carry out resource reclaim recycling and have economic worth.
Summary of the invention
The object of the present invention is to provide the method for dimethyl malonate production wastewater treatment and resource reclaim, the methyl alcohol in dimethyl malonate factory effluent, sulfuric acid and monoammonium sulfate can be recycled, and greatly reduce high-concentration wastewater emission.
The invention discloses a kind of method of dimethyl malonate production wastewater treatment and resource reclaim, comprise the following steps:
(1) Methanol Recovery: dimethyl malonate factory effluent is transferred to rectifying tower, methyl alcohol is reclaimed in rectifying;
(2) neutralize: neutralize having reclaimed the waste water ammonia after methyl alcohol;
(3) ammonium sulfate reclaims: the waste water after neutralization is steamed water and concentrates, then crystallisation by cooling, more centrifugally obtain ammonium sulfate solids, and centrifugate proceeds to malonic acid dimethyl ester production process extraction phase-splitting workshop section and uses.
As technique scheme further preferably, in described step (1), rectifying is atmospheric distillation, controls the methyl alcohol moisture content that rectifying goes out and is less than 1%.
As technique scheme further preferably, in described step (2), ammonia is ammonia or liquefied ammonia, and waste water ammonia is neutralized to pH=5.0-6.0.
As technique scheme further preferably, in described step (3), be cooled to 0-5 DEG C of crystallization.
The invention also discloses the method for another kind of dimethyl malonate production wastewater treatment and resource reclaim, comprise the following steps:
(1) neutralize: dimethyl malonate factory effluent ammonia is neutralized;
(2) Methanol Recovery: the waste water after neutralization is transferred to rectifying tower, methyl alcohol is reclaimed in rectifying;
(3) ammonium sulfate reclaims: steam having reclaimed the waste water after methyl alcohol water and concentrate, then crystallisation by cooling, more centrifugally obtain ammonium sulfate solids, centrifugate proceeds to the use of malonic acid dimethyl ester production process extraction phase-splitting workshop section.
As technique scheme further preferably, in described step (1), ammonia is ammonia or liquefied ammonia, and waste water ammonia is neutralized to pH=5.0-6.0.
As technique scheme further preferably, in described step (2), rectifying is atmospheric distillation, controls the methyl alcohol moisture content that rectifying goes out and is less than 1%.
As technique scheme further preferably, in described step (3), be cooled to 0-5 DEG C of crystallization.
Beneficial effect of the present invention is: the present invention reclaims methyl alcohol by rectifying, and the rate of recovery of single batch of methyl alcohol is greater than 85%, and the methyl alcohol of recovery can be applied mechanically in dimethyl malonate is produced; And sulfuric acid and monoammonium sulfate are changed into ammonium sulfate by the present invention's ammonia, and then condensing crystal reclaim(ed) sulfuric acid ammonium, the rate of recovery of single batch of ammonium sulfate is greater than 70%, can be used as byproduct and sells; The raffinate reclaimed after methyl alcohol and ammonium sulfate can continue to apply mechanically in the malonic acid dimethyl ester production process extraction phase-splitting stage; After method process of the present invention, dimethyl malonate produce without high-concentration wastewater emission, useful resources is utilized effectively, and reduces environmental protection pressure and production cost, economy and environment protecting obvious.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention 1;
Fig. 2 is the process flow sheet of the embodiment of the present invention 2.
Embodiment
Embodiment 1
Hereinafter with reference to Fig. 1, further illustrate the present invention by embodiment 1:
(1) Methanol Recovery: (methanol content 8.6%, amounts to 172kg by 2000kg dimethyl malonate factory effluent; Sulfuric acid content 23.5%, amounts to 470kg; Monoammonium sulfate content 32.4%, amounts to 640.8kg) be transferred to rectifying tower, atmospheric distillation obtains methyl alcohol 152kg, content 99.3%, moisture 0.2%, the rate of recovery 87.8%;
(2) neutralize: being transferred to neutralization reaction still by having reclaimed the waste water after methyl alcohol, being down to room temperature, maintenance temperature is no more than 60 DEG C and passes into ammonia and be neutralized to pH=5.5;
(3) ammonium sulfate reclaims: the waste water decompression after neutralization is steamed water 150kg, is then cooled to 0 DEG C of crystallization, more centrifugally obtains ammonium sulfate solids, use 100kg water washing, dry ammonium sulfate 978kg, content 98.5%, the rate of recovery 70.4%; Centrifugate proceeds to malonic acid dimethyl ester production process extraction phase-splitting workshop section and uses.
Embodiment 2
Hereinafter with reference to Fig. 2, further illustrate the present invention by embodiment 2:
(1) neutralize: by 2000kg dimethyl malonate factory effluent, (methanol content 8.6%, amounts to 172kg; Sulfuric acid content 23.5%, amounts to 470kg; Monoammonium sulfate content 32.4%, amounts to 640.8kg) be transferred to neutralization reaction still, keep temperature to be no more than 60 DEG C and pass into ammonia and be neutralized to pH=5.7;
(2) Methanol Recovery: the waste water after neutralization is transferred to rectifying tower, and atmospheric distillation obtains methyl alcohol 149kg, content 99.1%, moisture 0.3%, the rate of recovery 85.7%;
(3) ammonium sulfate reclaims: steaming water 150kg by having reclaimed the decompression of the waste water after methyl alcohol, being then cooled to 0 DEG C of crystallization, more centrifugally obtaining ammonium sulfate solids, using 100kg water washing, dry must ammonium sulfate 985kg, content 98.3%, the rate of recovery 70.8%; Centrifugate proceeds to malonic acid dimethyl ester production process extraction phase-splitting workshop section and uses.
Claims (8)
1. a method for dimethyl malonate production wastewater treatment and resource reclaim, is characterized in that: comprise the following steps:
(1) Methanol Recovery: dimethyl malonate factory effluent is transferred to rectifying tower, methyl alcohol is reclaimed in rectifying;
(2) neutralize: neutralize having reclaimed the waste water ammonia after methyl alcohol;
(3) ammonium sulfate reclaims: the waste water after neutralization is steamed water and concentrates, then crystallisation by cooling, more centrifugally obtain ammonium sulfate solids, and centrifugate proceeds to malonic acid dimethyl ester production process extraction phase-splitting workshop section and uses.
2. the method for dimethyl malonate production wastewater treatment as claimed in claim 1 and resource reclaim, it is characterized in that: in described step (1), rectifying is atmospheric distillation, and the methyl alcohol moisture content that control rectifying goes out is less than 1%.
3. the method for dimethyl malonate production wastewater treatment as claimed in claim 1 and resource reclaim, it is characterized in that: in described step (2), ammonia is ammonia or liquefied ammonia, and waste water ammonia is neutralized to pH=5.0-6.0.
4. the method for dimethyl malonate production wastewater treatment as claimed in claim 1 and resource reclaim, is characterized in that: in described step (3), is cooled to 0-5 DEG C of crystallization.
5. a method for dimethyl malonate production wastewater treatment and resource reclaim, is characterized in that: comprise the following steps:
(1) neutralize: dimethyl malonate factory effluent ammonia is neutralized;
(2) Methanol Recovery: the waste water after neutralization is transferred to rectifying tower, methyl alcohol is reclaimed in rectifying;
(3) ammonium sulfate reclaims: steam having reclaimed the waste water after methyl alcohol water and concentrate, then crystallisation by cooling, more centrifugally obtain ammonium sulfate solids, centrifugate proceeds to the use of malonic acid dimethyl ester production process extraction phase-splitting workshop section.
6. the method for dimethyl malonate production wastewater treatment as claimed in claim 5 and resource reclaim, it is characterized in that: in described step (1), ammonia is ammonia or liquefied ammonia, and waste water ammonia is neutralized to pH=5.0-6.0.
7. the method for dimethyl malonate production wastewater treatment as claimed in claim 5 and resource reclaim, it is characterized in that: in described step (2), rectifying is atmospheric distillation, and the methyl alcohol moisture content that control rectifying goes out is less than 1%.
8. the method for dimethyl malonate production wastewater treatment as claimed in claim 5 and resource reclaim, is characterized in that: in described step (3), is cooled to 0-5 DEG C of crystallization.
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| CN201310349611.2A CN103435441B (en) | 2013-08-12 | 2013-08-12 | The method of dimethyl malonate production wastewater treatment and resource reclaim |
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| CN104528764B (en) * | 2015-01-26 | 2017-01-11 | 四川弘征科技有限公司 | Comprehensive recovery and utilization system and method for ammonia gas containing low-carbon alcohol |
| CN106365954A (en) * | 2016-08-31 | 2017-02-01 | 河北诚信有限责任公司 | Method for recycling alcohol from malonic ester rectified low-boiling-point substance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1850773A (en) * | 2006-05-23 | 2006-10-25 | 重庆紫光化工有限责任公司 | Method for preparing malonic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1850773A (en) * | 2006-05-23 | 2006-10-25 | 重庆紫光化工有限责任公司 | Method for preparing malonic ester |
Non-Patent Citations (2)
| Title |
|---|
| 丙二酸二甲酯合成工艺的改进;荆超等;《河南化工》;19991231(第7期);第18-19页 * |
| 改进的氰化酯化法合成丙二酸二甲酯;丁斌;《染料工业》;20011231;第38卷(第6期);第46页1.2 * |
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