CN105017074A - Iminodiacetonitrile production mother liquor treatment recovery method and apparatus thereof - Google Patents
Iminodiacetonitrile production mother liquor treatment recovery method and apparatus thereof Download PDFInfo
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- CN105017074A CN105017074A CN201510331903.2A CN201510331903A CN105017074A CN 105017074 A CN105017074 A CN 105017074A CN 201510331903 A CN201510331903 A CN 201510331903A CN 105017074 A CN105017074 A CN 105017074A
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- iminodiacetonitrile
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Abstract
The present invention discloses an iminodiacetonitrile production mother liquor treatment recovery method and an apparatus thereof. According to the method, an iminodiacetonitrile production mother liquor is subjected to continuous chromatography separation, the separated solution containing iminodiacetonitrile, glycolonitrile and aminoacetonitrile is subjected to ammonification reaction, decolorization impurity removing and concentration crystallization to obtain the iminodiacetonitrile solid, and the separated solution containing sulfuric acid, ammonium bisulfate and ammonium sulfate is subjected to ammonification reaction and concentration crystallization to obtain the ammonium sulfate solid. According to the present invention, the method has characteristics of simple process, less investment, effective treatment on the iminodiacetonitrile production mother liquor, no requirement of expensive incinerator, prevention of secondary pollution of burning waste gas, efficient recycling of glycolonitrile, aminoacetonitrile, iminodiacetonitrile ammonium bisulfate and ammonium sulfate contained in the mother liquor, and easy production cost reducing.
Description
Technical field
The invention belongs to wastewater from chemical industry recycling field, relate to a kind of process recovery method and corollary apparatus thereof of Chemical Manufacture mother liquor.
Background technology
Iminodiacetonitrile (being called for short IDAN) production technique take prussic acid as starting raw material, synthesis of hydroxy acetonitrile solution is absorbed through formaldehyde solution, hydroxyl acetonitrile aqueous solution and ammonia effect continuous reaction obtain the reaction solution of imido-diacetonitrile, passed through repeatedly Crystallization Separation, obtained iminodiacetonitrile product and mother liquor respectively.Iminodiacetonitrile is produced containing a large amount of iminodiacetonitrile, hydroxyacetonitrile, aminoacetonitriles, sulfuric acid, monoammonium sulfate and ammonium sulfate in mother liquor, also has some other organic polymer, because of complicated component, usually by as liquid waste incineration process.But the saltiness of this mother liquor, water content are larger, burning is difficulty comparatively, and combustion heat value is very low, in mother liquor combustion processes, also can produce a large amount of acid gas, cause the corrosion of secondary pollution and hardware, the organic polymer produced in combustion processes very easily blocks incinerator.Therefore, existing iminodiacetonitrile produce mother liquor processing method exist serious waste of resources, intractability large, have secondary pollution, do not produce the shortcomings such as any economic worth.
Chinese patent CN 101391911A discloses a kind of method utilizing amino-nitrile production waste liquid to prepare organic fertilizer, the method produces in waste liquid at amino-nitrile to add catalyzer and dispersion agent obtains base manure, then base manure is inoculated biological bacteria, carry out the fermentation of 7 ~ 15 days, hydrolysis becomes material fertilizer again, and material fertilizer is produced into organic fertilizer through operations such as nutrient allotment, granulation, dryings.The method achieve the overall recycling to cyanide wastewater, but liquid waste disposal overlong time, and need large-scale compost place.
Chinese patent CN 101172743A discloses the combination process of a kind of high-cyanogen high-ammonia high-salt organic waste water process and reuse, adopt acidifying decyanation, ammonia blown in alkalization, add oxychlorination, biological treatment, precipitation clarification, deep oxidation, biologic active carbon filtration, salt solution primary purification, the combination process such as micro-filtrate membrane filtration, again through conventional chlor-alkali industry secondary refining process of brine, enter ion-exchange membrane electrolyzer and produce chlor-alkali.The method treatment effect is good, has significant environmental benefit and economic benefit, but its process combination link many, have high input, treatment cycle is longer, be more difficult to get and generally apply.
Chinese patent CN 103483031A discloses a kind of with the method for iminodiacetonitrile waste water for raw material Preparation of amino acid mixture.With the iminodiacetonitrile waste water produced in production iminodiacetonitrile process for raw material, add auxiliary agent, polyreaction is stirred 6 ~ 120 minutes under temperature 50-280 DEG C of condition, successively add two kinds of composite catalysts after completion of the polymerization reaction, amino acidification reaction is carried out 10 ~ 150 minutes under temperature 50-200 DEG C of condition, obtain a kind of Liquid amino acid mixture, this liquid again drying obtains a kind of solid amino acid complex.The method energy consumption is high, and the product composition obtained is complicated, applies limited.
Chinese patent CN 101503367A discloses a kind of method utilizing the raffinate synthetic ammonia nitrilotriacetic of prussic acid method production iminodiacetonitrile.Specifically comprise: 1) raffinate of iminodiacetonitrile is added alkali and be hydrolyzed at 30 ~ 100 DEG C, Mono Chloro Acetic Acid is added in hydrolyzed solution, 10 ~ 100 DEG C, react after 0.5 ~ 10 hour with adjusting PH with base=9 ~ 14, then to be acidified with acid in reaction solution, to separate out nitrilotriacetic acid(NTA) crude product.2) suspended in water by nitrilotriacetic acid(NTA) crude product, add in alkali and dissolve, activated carbon decolorizing under stirring, except gac, acidifying, filters, dry, obtains nitrilotriacetic acid(NTA) finished product.The shortcoming of the method effectively to utilize great amount of hydroxy group acetonitrile residual in mother liquor, and consume a large amount of alkali and acid, produce a large amount of inorganic salt, energy consumption is high, and wastewater flow rate can increase.
Chinese patent CN 101531676A discloses a kind of method preparing pmida98, and it for raw material, prepares pmida98 by alkaline hydrolysis, activated carbon decolorizing, acidifying, contracting phosphine formylation reaction with iminodiacetonitrile mother liquor.Although this method can utilize, and the iminodiacetonitrile in iminodiacetonitrile mother liquor is changed into pmida98, but a large amount of hydroxyacetonitriles and aminoacetonitriles are not utilized effectively, and generate glycine and oxyacetic acid after aminoacetonitriles in mother liquor and aminoacetonitriles alkaline hydrolysis, can affect the quality of pmida98 product, wastewater treatment difficulty also can strengthen.
Chinese patent CN 103408460A discloses a kind of recovery method and mother liquor processing method thereof of iminodiacetonitrile second product, iminodiacetonitrile mother liquor is passed into ammonia to regulate the pH value of feed liquid to alkalescence, stirring reaction, stratification, organic bed of material, through cooling, crystallization, centrifugal, obtains iminodiacetonitrile crude product; Sulfate solution layer, through activated carbon decolorizing, evaporation, centrifugal, obtains byproduct of ammonium sulfate.There is following problem in the method: phase separation temperature higher (80-100 DEG C), the solubleness of iminodiacetonitrile is greater than 100g/100mL at this temperature, this will inevitably reduce the rate of recovery of iminodiacetonitrile, and being at high temperature dissolved with more impurity in organic bed of material, gained iminodiacetonitrile crude product needs purification process.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of iminodiacetonitrile to produce process recovery method and the corollary apparatus thereof of mother liquor, simple to operate, economic environmental protection, and can certain economic benefit be produced.
For achieving the above object, the invention provides following technical scheme:
Iminodiacetonitrile produces the process recovery method of mother liquor, comprises the following steps:
(1) iminodiacetonitrile being produced mother liquor adopts continuous chromatography to be separated, and obtains the solution containing iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles and the solution containing sulfuric acid, monoammonium sulfate and ammonium sulfate respectively;
(2) solution containing iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles step (1) obtained adds ammonia react, makes hydroxyacetonitrile and aminoacetonitriles change into iminodiacetonitrile, obtains iminodiacetonitrile solution; After iminodiacetonitrile solution with activated carbon or hydrogen peroxide for decoloration, concentrated, crystallization, solid-liquid separation obtains iminodiacetonitrile solid and crystalline mother solution I;
(3) solution containing sulfuric acid, monoammonium sulfate and ammonium sulfate step (1) obtained adds ammonia react, makes sulfuric acid and monoammonium sulfate change into ammonium sulfate, obtains ammoniumsulphate soln; Concentrated by ammoniumsulphate soln, crystallization, solid-liquid separation obtains ammonium sulfate solids and crystalline mother solution II.
The chemical equation that present method relates to is as follows:
H
2SO
4 + NH
3→ (NH
4)
2SO
4
NH
4HSO
4 + NH
3→ (NH
4)
2SO
4
2 HOCH
2CN + NH
3→ HN(CH
2CN)
2 + 2 H
2O
HOCH
2CN + NH
2CH
2CN → HN(CH
2CN)
2 + H
2O
Preferably, in step (1) continuous chromatography be separated that the chromatograph packing material used is sodium form, potassium type, ammonium type or calcium type chromatographic separation resin.
Preferably, the temperature that in step (1), continuous chromatography is separated is 20 ~ 80 DEG C.
Preferably, in step (2), the consumption of gac or hydrogen peroxide is 0.1 ~ 1% of iminodiacetonitrile solution quality.
Preferably, in step (2), bleaching temperature is 60-100 DEG C.
Preferably, in step (2), iminodiacetonitrile solution being concentrated into iminodiacetonitrile content is 30 ~ 50%, 0 ~ 30 DEG C of crystallization.
Preferably, in step (2), gained crystalline mother solution I applies mechanically when the solution that lower batch contains iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles adds ammonia react or when lower batch of iminodiacetonitrile solution decolours.
Preferably, in step (3), ammoniumsulphate soln being concentrated into ammonium sulphate content is 40 ~ 50%, 0 ~ 30 DEG C of crystallization.
Preferably, in step (3) gained crystalline mother solution II when lower batch of continuous chromatography is separated or apply mechanically when lower batch of ammoniumsulphate soln concentrates.
The device of the process recovery method of mother liquor is produced for realizing described iminodiacetonitrile, comprise continuous chromatography separation system, decolouring still, reactor I and II, condensing crystal still I and II and solid-liquid separator I and II, the outlet of described continuous chromatography separation system respectively with the inlet communication of reactor I and reactor II, described reactor I, decolouring still, condensing crystal still I are communicated with successively with solid-liquid separator I, and described reactor II, condensing crystal still II are communicated with successively with solid-liquid separator II.
Beneficial effect of the present invention is: the inventive method technique is simple, less investment, not only can produce mother liquor to iminodiacetonitrile effectively to process, without the need to buying expensive incinerator, also prevent the secondary pollution of waste gas from incinerator, and hydroxyacetonitrile, aminoacetonitriles, iminodiacetonitrile, monoammonium sulfate and the ammonium sulfate that can contain in effective recycling mother liquor, be conducive to reducing production cost.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, below in conjunction with accompanying drawing, the invention will be further described:
Fig. 1 is the inventive method and device schematic diagram.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
Method and device schematic diagram are as shown in Figure 1.Device comprises continuous chromatography separation system, decolouring still, reactor I and II, condensing crystal still I and II and solid-liquid separator I and II, the outlet of described continuous chromatography separation system respectively with the inlet communication of reactor I and reactor II, described reactor I, decolouring still, condensing crystal still I are communicated with successively with solid-liquid separator I, and described reactor II, condensing crystal still II are communicated with successively with solid-liquid separator II.
Concrete grammar is as follows:
(1) get iminodiacetonitrile production mother liquor 1kg(and contain 7.8wt% hydroxyacetonitrile, 5.4wt% iminodiacetonitrile, 4.6wt% aminoacetonitriles, 59.5wt% water, 20.7wt% (sulfuric acid+monoammonium sulfate+ammonium sulfate)), be separated at 30 DEG C by the continuous chromatography separation system being filled with ammonium type chromatographic separation resin, obtain the solution 958g of imido-diacetonitrile, hydroxyacetonitrile and aminoacetonitriles respectively, and the solution 996g of sulfur acid, monoammonium sulfate and ammonium sulfate;
(2) in the solution of the imido-diacetonitrile of step (1) gained, hydroxyacetonitrile and aminoacetonitriles, ammonia adjust ph to 8.5 is passed into, back flow reaction 1.5 hours, the content of sampling analysis display hydroxyacetonitrile and aminoacetonitriles is all less than 0.5%, obtains iminodiacetonitrile solution; In iminodiacetonitrile solution, add hydrogen peroxide 5.0g, continue backflow 1.0 hours, being then concentrated into iminodiacetonitrile content is 50%, is cooled to 10 DEG C of crystallizations, and filter, filtration cakes torrefaction, obtains iminodiacetonitrile 120.6g, content 95.3%; Filtrate and crystalline mother solution I apply mechanically when the solution that lower batch contains iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles adds ammonia react or when lower batch of iminodiacetonitrile solution decolours;
(3) in the solution of the sulfur acid of step (1) gained, monoammonium sulfate and ammonium sulfate, passing into ammonia to pH value is 5, obtains ammoniumsulphate soln; Ammoniumsulphate soln being concentrated into ammonium sulphate content is 48.5%, is cooled to 10 DEG C of crystallizations, and filter, filtration cakes torrefaction, obtains ammonium sulfate 60.5g, content 99.3%; Filtrate and crystalline mother solution II apply mechanically when lower batch of continuous chromatography is separated or when ammoniumsulphate soln concentrates.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (10)
1. iminodiacetonitrile produces the process recovery method of mother liquor, it is characterized in that: comprise the following steps:
(1) iminodiacetonitrile being produced mother liquor adopts continuous chromatography to be separated, and obtains the solution containing iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles and the solution containing sulfuric acid, monoammonium sulfate and ammonium sulfate respectively;
(2) solution containing iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles step (1) obtained adds ammonia react, makes hydroxyacetonitrile and aminoacetonitriles change into iminodiacetonitrile, obtains iminodiacetonitrile solution; After iminodiacetonitrile solution with activated carbon or hydrogen peroxide for decoloration, concentrated, crystallization, solid-liquid separation obtains iminodiacetonitrile solid and crystalline mother solution I;
(3) solution containing sulfuric acid, monoammonium sulfate and ammonium sulfate step (1) obtained adds ammonia react, makes sulfuric acid and monoammonium sulfate change into ammonium sulfate, obtains ammoniumsulphate soln; Concentrated by ammoniumsulphate soln, crystallization, solid-liquid separation obtains ammonium sulfate solids and crystalline mother solution II.
2. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: in step (1) continuous chromatography be separated that the chromatograph packing material used is sodium form, potassium type, ammonium type or calcium type chromatographic separation resin.
3. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: the temperature that in step (1), continuous chromatography is separated is 20 ~ 80 DEG C.
4. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: in step (2), the consumption of gac or hydrogen peroxide is 0.1 ~ 1% of iminodiacetonitrile solution quality.
5. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: in step (2), bleaching temperature is 60-100 DEG C.
6. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: the content in step (2), iminodiacetonitrile solution being concentrated into iminodiacetonitrile is 30 ~ 50%, 0 ~ 30 DEG C of crystallization.
7. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: in step (2), gained crystalline mother solution I applies mechanically when the solution that lower batch contains iminodiacetonitrile, hydroxyacetonitrile and aminoacetonitriles adds ammonia react or when lower batch of iminodiacetonitrile solution decolours.
8. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: the content in step (3), ammoniumsulphate soln being concentrated into ammonium sulfate is 40 ~ 50%, 0 ~ 30 DEG C of crystallization.
9. iminodiacetonitrile as claimed in claim 1 produces the process recovery method of mother liquor, it is characterized in that: the middle gained crystalline mother solution II of step (3) is when lower batch of continuous chromatography is separated or apply mechanically when lower batch of ammoniumsulphate soln concentrates.
10. the device of the process recovery method of mother liquor is produced for realizing iminodiacetonitrile described in claim 1, it is characterized in that: comprise continuous chromatography separation system, decolouring still, reactor I and II, condensing crystal still I and II and solid-liquid separator I and II, the outlet of described continuous chromatography separation system respectively with the inlet communication of reactor I and reactor II, described reactor I, decolouring still, condensing crystal still I are communicated with successively with solid-liquid separator I, and described reactor II, condensing crystal still II are communicated with successively with solid-liquid separator II.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156096A (en) * | 1978-03-15 | 1979-05-22 | W. R. Grace & Co. | Process for recovering dissolved iminodiacetonitrile from effluent liquors |
| EP0367364A1 (en) * | 1988-10-31 | 1990-05-09 | Hampshire Chemical Corporation | Integrated process for the production of aminoacetonitriles |
| CN103274954A (en) * | 2013-05-22 | 2013-09-04 | 厦门世达膜科技有限公司 | Production process of Gly |
| CN103408460A (en) * | 2013-08-22 | 2013-11-27 | 河北诚信有限责任公司 | Recovery method of secondary products of iminodiacetonitrile and mother liquid treatment method |
-
2015
- 2015-06-16 CN CN201510331903.2A patent/CN105017074B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156096A (en) * | 1978-03-15 | 1979-05-22 | W. R. Grace & Co. | Process for recovering dissolved iminodiacetonitrile from effluent liquors |
| EP0367364A1 (en) * | 1988-10-31 | 1990-05-09 | Hampshire Chemical Corporation | Integrated process for the production of aminoacetonitriles |
| CN103274954A (en) * | 2013-05-22 | 2013-09-04 | 厦门世达膜科技有限公司 | Production process of Gly |
| CN103408460A (en) * | 2013-08-22 | 2013-11-27 | 河北诚信有限责任公司 | Recovery method of secondary products of iminodiacetonitrile and mother liquid treatment method |
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