CN104892436A - Recycling method and device for iminodiacetonitrile production mother liquor - Google Patents
Recycling method and device for iminodiacetonitrile production mother liquor Download PDFInfo
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- CN104892436A CN104892436A CN201510332151.1A CN201510332151A CN104892436A CN 104892436 A CN104892436 A CN 104892436A CN 201510332151 A CN201510332151 A CN 201510332151A CN 104892436 A CN104892436 A CN 104892436A
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- iminodiacetonitrile
- mother liquor
- calcium
- recycling method
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Abstract
The invention discloses a recycling method and device for iminodiacetonitrile production mother liquor. Calcium oxide or calcium hydroxide is added to the iminodiacetonitrile production mother liquor for a reaction to enable glycolonitrile and aminoacetonitrile contained in the mother liquor to be converted into the iminodiacetonitrile and enable sulfuric acid, ammonium bisulfate and ammonium sulfate to be converted into calcium sulfate. According to the method, the process is simple, low investment is required, the iminodiacetonitrile production mother liquor can be treated effectively, an expensive incinerator is not required to purchase, secondary pollution due to waste gas incineration is prevented, the glycolonitrile, the aminoacetonitrile and the iminodiacetonitrile in the mother liquor can be recycled effectively, iminodiacetic acid with economic value is prepared, and the production cost can be reduced.
Description
Technical field
The invention belongs to wastewater from chemical industry recycling field, relate to recycling method and corollary apparatus thereof that a kind of iminodiacetonitrile produces 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 recycling 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:
1.iminodiacetonitrile produces the recycling method of mother liquor, produce in mother liquor to iminodiacetonitrile to add calcium oxide or calcium hydroxide reaction, make the hydroxyacetonitrile that contains in mother liquor and aminoacetonitriles change into iminodiacetonitrile, sulfuric acid, monoammonium sulfate and ammonium sulfate change into calcium sulfate.
To add calcium oxide, the chemical equation related to is as follows:
H
2SO
4 + CaO → CaSO
4 + H
2O
NH
4HSO
4 + CaO → CaSO
4 + NH
3+ H
2O
(NH
4)
2SO
4 + CaO → CaSO
4 + 2 NH
3+ H
2O
2 HOCH
2CN + NH
3→ HN(CH
2CN)
2 + 2 H
2O
HOCH
2CN + NH
2CH
2CN → HN(CH
2CN)
2 + H
2O
Preferably, the recycling method of iminodiacetonitrile production mother liquor comprises the following steps:
(1) produce in mother liquor to iminodiacetonitrile and add calcium oxide or calcium hydroxide reaction, make the hydroxyacetonitrile that contains in mother liquor and aminoacetonitriles change into iminodiacetonitrile, sulfuric acid, monoammonium sulfate and ammonium sulfate change into calcium sulfate;
(2) in step (1) gained reaction solution, add calcium oxide or calcium hydroxide hydrolysis, make iminodiacetonitrile change into iminodiethanoic acid calcium;
(3) in step (2) gained hydrolyzed solution, hydrogen peroxide for decoloration is added;
(4) step (3) gained destainer is carried out solid-liquid separation, obtain solid mixture and the mother liquor I of iminodiethanoic acid calcium and calcium sulfate;
(5) in the solid mixture of step (4) gained iminodiethanoic acid calcium and calcium sulfate, sulfuric acid acidation is added, iminodiethanoic acid calcium is made to change into iminodiethanoic acid, solid-liquid separation obtains calcium sulphate solid and iminodiacetic acid (salt) acid solution, by iminodiacetic acid (salt) acid solution crystallisation by cooling, solid-liquid separation obtains iminodiethanoic acid solid and mother liquor II.
To add calcium oxide in step (1) and (2), the chemical equation related to is as follows:
H
2SO
4 + CaO → CaSO
4 + H
2O
NH
4HSO
4 + CaO → CaSO
4 + NH
3+ H
2O
(NH
4)
2SO
4 + CaO → CaSO
4 + 2 NH
3+ H
2O
2 HOCH
2CN + NH
3→ HN(CH
2CN)
2 + 2 H
2O
HOCH
2CN + NH
2CH
2CN → HN(CH
2CN)
2 + H
2O
HN(CH
2CN)
2 + 3 H
2O + CaO → HN(CH
2COO)
2Ca + 2 NH
3
HN(CH
2COO)
2Ca
+ H
2SO
4→ HN(CH
2COOH)
2 + CaSO
4
Preferably, produce in mother liquor to iminodiacetonitrile and add calcium oxide or calcium hydroxide adjust ph is 6 ~ 9 post-heating reactions.
Preferably, in step (2), hydrolysis temperature is 50 ~ 110 DEG C.
Preferably, in step (3), hydrogen peroxide consumption is 0.1 ~ 5% of hydrolyzed solution quality.
Preferably, in step (3), bleaching temperature is 60-100 DEG C.
Preferably, in step (4), mother liquid obtained I applies mechanically in lower batch of step (2) hydrolysis reaction.
Preferably, in step (5), sulfuric acid acidation temperature is 60 ~ 100 DEG C.
Preferably, in step (5), the Tc of iminodiethanoic acid is 0 ~ 30 DEG C.
Preferably, in step (5), mother liquid obtained II applies mechanically in lower batch of step (5) sulfuric acid acidation reaction.
2.producing the device of the recycling method of mother liquor for realizing described iminodiacetonitrile, comprising the reactor, hydrolysis kettle, solid-liquid separator I, acidifying still, solid-liquid separator II, crystallization kettle and the solid-liquid separator III that are communicated with successively.
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 and the iminodiacetonitrile that can contain in effective recycling mother liquor, the obtained iminodiethanoic acid having economic worth, the obtained iminodiethanoic acid having economic worth, is 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 the reactor, hydrolysis kettle, solid-liquid separator I, acidifying still, solid-liquid separator II, crystallization kettle and the solid-liquid separator III that are communicated with successively.
Concrete grammar is as follows:
(1) get iminodiacetonitrile production mother liquor 1kg(and contain 8.2wt% hydroxyacetonitrile, 5.8wt% iminodiacetonitrile, 4.4wt% aminoacetonitriles, 59.5wt% water, 16.5wt% (sulfuric acid+monoammonium sulfate+ammonium sulfate)), add the calcium oxide 110g adjust ph to 8.5 that content is 97%, back flow reaction 1.5 hours, the content of sampling analysis display hydroxyacetonitrile and aminoacetonitriles is all less than 0.5%;
(2) in step (1) gained reaction solution, add the calcium oxide 115g that content is 97%, 55 ~ 60 DEG C of stirring reactions 2 hours, be then warming up to 95 ~ 100 DEG C and continue stirring reactions, until do not have ammonia to release in system;
(3) in step (2) gained hydrolyzed solution, add hydrogen peroxide 5.0g, reflux 1.0 hours, then steam water 400g, be cooled to 30 DEG C;
(4) step (3) gained destainer is cooled to 20 DEG C, filter, filter cake use water 100g washs, heavy 508.6g; Filtrate and mother liquor I apply mechanically in lower batch of hydrolysis reaction;
(5) step (4) gained filter cake is mixed with water 750g and 98wt% sulfuric acid 250g, be warming up to 90 ~ 95 DEG C and stir 1 hour, filtered while hot, filter cake hot water 100g washs, drying, obtains calcium sulfate (white solid) 458g, and wherein iminodiacetic acid content is 0.06%; Filtrate is cooled to 10 DEG C of stirred crystallization 4 hours, filters, filter cake washing, dry, obtains iminodiethanoic acid 201.8g, content 98.2%; Filtrate and mother liquor II apply mechanically in lower batch of sulfuric acid acidation reaction.
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 recycling method of mother liquor, it is characterized in that: produce in mother liquor to iminodiacetonitrile and add calcium oxide or calcium hydroxide reaction, make the hydroxyacetonitrile that contains in mother liquor and aminoacetonitriles changes into iminodiacetonitrile, sulfate ion changes into calcium sulfate.
2. iminodiacetonitrile as claimed in claim 1 produces the recycling method of mother liquor, it is characterized in that: comprise the following steps:
(1) produce in mother liquor to iminodiacetonitrile and add calcium oxide or calcium hydroxide reaction, make the hydroxyacetonitrile that contains in mother liquor and aminoacetonitriles changes into iminodiacetonitrile, sulfate ion changes into calcium sulfate;
(2) in step (1) gained reaction solution, add calcium oxide or calcium hydroxide hydrolysis, make iminodiacetonitrile change into iminodiethanoic acid calcium;
(3) in step (2) gained hydrolyzed solution, hydrogen peroxide for decoloration is added;
(4) step (3) gained destainer is carried out solid-liquid separation, obtain solid mixture and the mother liquor I of iminodiethanoic acid calcium and calcium sulfate;
(5) in the solid mixture of step (4) gained iminodiethanoic acid calcium and calcium sulfate, sulfuric acid acidation is added, iminodiethanoic acid calcium is made to change into iminodiethanoic acid, solid-liquid separation obtains calcium sulphate solid and iminodiacetic acid (salt) acid solution, by iminodiacetic acid (salt) acid solution crystallisation by cooling, solid-liquid separation obtains iminodiethanoic acid solid and mother liquor II.
3. iminodiacetonitrile as claimed in claim 1 or 2 produces the recycling method of mother liquor, it is characterized in that: produce in mother liquor to iminodiacetonitrile and add calcium oxide or calcium hydroxide reaction adjust ph is 6 ~ 9 post-heating reactions.
4. iminodiacetonitrile as claimed in claim 2 produces the recycling method of mother liquor, it is characterized in that: in step (2), hydrolysis temperature is 50 ~ 110 DEG C.
5. iminodiacetonitrile as claimed in claim 2 produces the recycling method of mother liquor, it is characterized in that: in step (3), hydrogen peroxide consumption is 0.1 ~ 5% of hydrolyzed solution quality; Bleaching temperature is 60-100 DEG C.
6. iminodiacetonitrile as claimed in claim 2 produces the recycling method of mother liquor, it is characterized in that: in step (4), mother liquid obtained I applies mechanically in lower batch of step (2) hydrolysis reaction.
7. iminodiacetonitrile as claimed in claim 2 produces the recycling method of mother liquor, it is characterized in that: in step (5), sulfuric acid acidation temperature is 60 ~ 100 DEG C.
8. iminodiacetonitrile as claimed in claim 2 produces the recycling method of mother liquor, it is characterized in that: in step (5), the Tc of iminodiethanoic acid is 0 ~ 30 DEG C.
9. iminodiacetonitrile as claimed in claim 2 produces the recycling method of mother liquor, it is characterized in that: in step (5), mother liquid obtained II applies mechanically in lower batch of step (5) sulfuric acid acidation reaction.
10. producing the device of the recycling method of mother liquor for realizing iminodiacetonitrile described in claim 2, it is characterized in that: comprise the reactor, hydrolysis kettle, solid-liquid separator I, acidifying still, solid-liquid separator II, crystallization kettle and the solid-liquid separator III that are communicated with successively.
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|---|---|---|---|
| CN201510332151.1A CN104892436B (en) | 2015-06-16 | 2015-06-16 | Iminodiacetonitrile produces the recycling method and device of mother liquor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020087024A1 (en) * | 2000-10-16 | 2002-07-04 | Basf Aktiengesellschaft | Continuous process for the cyanoalkylation of compounds having one or more NH functions |
| WO2009079861A1 (en) * | 2007-12-25 | 2009-07-02 | Beijing Unis Insight Chemical Technology Co., Ltd. | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile |
| CN101619077A (en) * | 2009-07-27 | 2010-01-06 | 重庆紫光化工股份有限公司 | Method for preparing N-Phosphonomethyl iminodiacetic acid through hydrolyzing iminodiacetonitrile |
| 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 |
| CN103833563A (en) * | 2014-02-21 | 2014-06-04 | 重庆紫光化工股份有限公司 | Method for increasing yield of iminodiacetic acid |
-
2015
- 2015-06-16 CN CN201510332151.1A patent/CN104892436B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020087024A1 (en) * | 2000-10-16 | 2002-07-04 | Basf Aktiengesellschaft | Continuous process for the cyanoalkylation of compounds having one or more NH functions |
| WO2009079861A1 (en) * | 2007-12-25 | 2009-07-02 | Beijing Unis Insight Chemical Technology Co., Ltd. | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile |
| CN101619077A (en) * | 2009-07-27 | 2010-01-06 | 重庆紫光化工股份有限公司 | Method for preparing N-Phosphonomethyl iminodiacetic acid through hydrolyzing iminodiacetonitrile |
| 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 |
| CN103833563A (en) * | 2014-02-21 | 2014-06-04 | 重庆紫光化工股份有限公司 | Method for increasing yield of iminodiacetic acid |
Non-Patent Citations (2)
| Title |
|---|
| 奈普 等: "《氮·磷》", 31 May 2006, 山东教育出版社 * |
| 陈伟庆: "《冶金工程实验技术》", 31 October 2004, 冶金工业出版社 * |
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