CN105001121B - The resource utilization method and device of iminodiacetonitrile production mother liquor - Google Patents
The resource utilization method and device of iminodiacetonitrile production mother liquor Download PDFInfo
- Publication number
- CN105001121B CN105001121B CN201510332150.7A CN201510332150A CN105001121B CN 105001121 B CN105001121 B CN 105001121B CN 201510332150 A CN201510332150 A CN 201510332150A CN 105001121 B CN105001121 B CN 105001121B
- Authority
- CN
- China
- Prior art keywords
- iminodiacetonitrile
- mother liquor
- ammonium sulfate
- solution
- resource utilization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of resource utilization method of iminodiacetonitrile production mother liquor and device, it is to make the hydroxyacetonitrile and aminoacetonitriles that contain in mother liquor change into iminodiacetonitrile, sulfuric acid and ammonium hydrogen sulfate iminodiacetonitrile production mother liquor ammonification reaction to change into ammonium sulfate, after decolouring removal of impurities, iminodiacetonitrile solution and ammonium sulfate are respectively obtained through continuous chromatography, two kinds of solution are distinguished into condensing crystallizing again, iminodiacetonitrile solid and ammonium sulfate solids are obtained；The inventive method technique is simple, small investment, iminodiacetonitrile production mother liquor can be not only effectively treated, the incinerator expensive without purchase, it also prevent the secondary pollution of waste gas from incinerator, and can be to contain in effective recycling mother liquor hydroxyacetonitrile, aminoacetonitriles, iminodiacetonitrile, ammonium hydrogen sulfate and ammonium sulfate, advantageously reduce production cost.
Description
Technical field
The invention belongs to wastewater from chemical industry recycling field, it is related to the recycling that a kind of iminodiacetonitrile produces mother liquor
Method and its corollary apparatus.
Background technology
Iminodiacetonitrile（Abbreviation IDAN）Production technology is, using hydrogen cyanide as initiation material, to absorb and synthesize through formalin
Hydroxyl acetonitrile aqueous solution, hydroxyl acetonitrile aqueous solution acts on the reaction solution that continuous reaction obtains imido- diacetonitrile with ammonia, will
It respectively obtains iminodiacetonitrile product and mother liquor by multiple Crystallization Separation.Contain in iminodiacetonitrile production mother liquor
Substantial amounts of iminodiacetonitrile, hydroxyacetonitrile, aminoacetonitriles, sulfuric acid, ammonium hydrogen sulfate and ammonium sulfate, it is also some other organic
Polymer, because of complicated component, is generally taken as liquid waste incineration processing.But salt content, the water content of the mother liquor are larger, burning is more
Difficulty, and combustion heat value is very low, and substantial amounts of acid gas can be also produced in mother liquor combustion process, causes secondary pollution and metal to set
The organic polymer produced in standby corrosion, combustion process easily blocks incinerator.Therefore, existing iminodiacetonitrile production
Mother liquor processing method has that serious waste of resources, intractability are big, have the shortcomings that secondary pollution, do not produce any economic value.
Chinese patent CN 101391911A disclose a kind of method that utilization amino nitrile production waste liquid prepares organic fertilizer,
This method is that catalyst and the obtained base manure of dispersant are added in amino nitrile production waste liquid, and base manure then is inoculated with into biological bacteria, entered
The row fermentation of 7 ~ 15 days, then hydrolyze as material fertilizer, material fertilizer is produced into organic by the process such as nutrient allotment, granulation, dry
Fertilizer.The overall recycling to cyanide wastewater, but liquid waste processing overlong time are the method achieve, and needs large-scale heap
Fertile place.
Chinese patent CN 101172743A disclose the combination of a kind of high-cyanogen high-ammonia high-salt organic waste water processing and reuse
Technique, ammonia, chlorination oxidation, biological treatment, precipitation clarification, deep oxidation, biological activated carbon mistake are blown using acidifying decyanation, alkalization
The group technology such as filter, salt solution primary purification, micro-filtrate membrane filtration, then through conventional chlor-alkali industry secondary refining process of brine, enter ion
Membrane electrolysis cells produce chlor-alkali.This method high treating effect, with significant environmental benefit and economic benefit, but its technique groups cyclization
Section is more, input is big, process cycle is longer, it is commonly used to be more difficult to get.
Chinese patent CN 103483031A disclose a kind of amino acid that prepared by raw material of iminodiacetonitrile waste water and are combined
The method of thing.Iminodiacetonitrile waste water to be produced during production iminodiacetonitrile adds auxiliary agent, in temperature as raw material
Stirring polymerisation 6 ~ 120 minutes, successively add two kinds of composite catalysts after completion of the polymerization reaction under the conditions of 50-280 DEG C of degree,
Amino acidification reaction is carried out under the conditions of 50-200 DEG C of temperature 10 ~ 150 minutes, obtain a kind of Liquid amino acid compound, the liquid
Body is again through being dried to obtain a kind of solid amino acid complex.This method high energy consumption, obtained product form is complicated, using limited.
Chinese patent CN 101503367A disclose a kind of raffinate synthesis of utilization hydrogen cyanide method production iminodiacetonitrile
The method of nitrilotriacetic acid.Specifically include：1）Alkali is added to be hydrolyzed at 30 ~ 100 DEG C the raffinate of iminodiacetonitrile, in hydrolysis
Monoxone is added in liquid, at 10 ~ 100 DEG C, with after the reaction of adjusting PH with base=9 ~ 14 0.5 ~ 10 hour, then is acidified with acid in reaction solution,
Separate out nitrilotriacetic acid crude product.2）Nitrilotriacetic acid crude product is suspended in water, stirring is lower to be added in alkali and dissolve, activated carbon decolorizing, is removed
Activated carbon, is acidified, and filters, and dries, obtains nitrilotriacetic acid finished product.The shortcoming of this method can not effectively be utilized and remained in mother liquor
Great amount of hydroxy group acetonitrile, consumes substantial amounts of alkali and acid, and producing substantial amounts of inorganic salts, high energy consumption, and wastewater flow rate can increase.
Chinese patent CN 101531676A disclose a kind of method for preparing PMIDA, and it is with iminodiacetonitrile mother liquor
For raw material, PMIDA is prepared by alkaline hydrolysis, activated carbon decolorizing, acidifying, contracting phosphine formylation reaction.Although the method can be utilized Asia
Iminodiacetonitrile in aminoacetaldehyde diethyl nitrile mother liquor changes into PMIDA, but substantial amounts of hydroxyacetonitrile and aminoacetonitriles are not obtained
Utilized to effective, and generation glycine and hydroxyacetic acid after the aminoacetonitriles and aminoacetonitriles alkaline hydrolysis in mother liquor, it can influence double sweet
The quality of phosphine product, wastewater treatment difficulty can also be increased.
Chinese patent CN 103408460A disclose a kind of recovery method and its mother liquor of iminodiacetonitrile afterproduct
Processing method, is that iminodiacetonitrile mother liquor is passed through into the pH values of ammonia regulation feed liquid to alkalescence, stirring reaction, stratification,
Organic bed of material obtains iminodiacetonitrile crude product through cooling, crystallization, centrifugation；Sulfate solution layer is through activated carbon decolorizing, steaming
Hair, centrifugation, obtain byproduct of ammonium sulfate.There is problems with this method：Phase separation temperature is higher（80-100℃）, at this temperature
The solubility of iminodiacetonitrile is more than 100g/100mL, and this will necessarily reduce the rate of recovery of iminodiacetonitrile, and in high temperature
Under be dissolved with more impurity in organic bed of material, gained iminodiacetonitrile crude product needs purification process.
The content of the invention
In view of this, it is an object of the invention to provide a kind of iminodiacetonitrile production mother liquor recoverying and utilizing method and
Its corollary apparatus, it is simple to operate, economic and environment-friendly, and certain economic benefit can be produced.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1. iminodiacetonitrile produces the resource utilization method of mother liquor, comprise the following steps：
（1）By iminodiacetonitrile production mother liquor ammonification reaction, turn the hydroxyacetonitrile and aminoacetonitriles that contain in mother liquor
Chemical conversion iminodiacetonitrile, sulfuric acid and ammonium hydrogen sulfate change into ammonium sulfate, gained reaction solution activated carbon or hydrogen peroxide for decoloration, obtain
To imido- diacetonitrile and the mixed liquor of ammonium sulfate；
（2）By step（1）Obtained imido- diacetonitrile and the mixed liquor of ammonium sulfate is separated using continuous chromatography, respectively
Obtain iminodiacetonitrile solution and ammonium sulfate；
（3）By step（2）Obtained iminodiacetonitrile solution concentration, crystallization, separation of solid and liquid obtains iminodiacetonitrile
Solid and crystalline mother solution I；
（4）By step（2）Obtained ammonium sulfate concentration, crystallization, separation of solid and liquid obtains ammonium sulfate solids and crystallization is female
Liquid II.
The chemical equation that this method is related to is as follows：
H2SO4+NH3→(NH4)2SO4
NH4HSO4+NH3→(NH4)2SO4
2 HOCH2CN+NH3→HN(CH2CN)2+2H2O
HOCH2CN+NH2CH2CN→HN(CH2CN)2+H2O
It is preferred that, step（1）The consumption of middle activated carbon or hydrogen peroxide is the 0.1 ~ 1% of reaction solution quality.
It is preferred that, step（1）Middle bleaching temperature is 60-100 DEG C.
It is preferred that, step（1）In before ammonification reaction, between ammonification reaction and decolorization or decolorization it
There is concentration afterwards.
It is preferred that, step（2）The chromatograph packing material that middle continuous chromatography separation is used is sodium form, potassium type, ammonium type or calcium type color
Compose separation resin.
It is preferred that, step（2）The temperature of middle continuous chromatography separation is 20 ~ 80 DEG C.
It is preferred that, step（3）It is middle that iminodiacetonitrile solution is concentrated into iminodiacetonitrile content for 30 ~ 50%, 0 ~ 30
DEG C crystallization.
It is preferred that, step（3）Middle gained crystalline mother solution I when lower batch ammonification is reacted or continuous chromatography separation when or
Iminodiacetonitrile solution is applied mechanically when concentrating.
It is preferred that, step（4）It is middle by ammonium sulfate be concentrated into ammonium sulphate content for 40 ~ 50%, 0 ~ 30 DEG C crystallization.
It is preferred that, step（4）Middle gained crystalline mother solution II is when lower batch continuous chromatography is separated or ammonium sulfate is dense
Applied mechanically during contracting.
2. the device of the resource utilization method for realizing the iminodiacetonitrile production mother liquor, including be sequentially communicated
Reactor, decolouring kettle and continuous chromatography piece-rate system, the outlet of the continuous chromatography piece-rate system respectively with condensing crystallizing kettle I
With condensing crystallizing kettle II inlet communication, the outlet of the condensing crystallizing kettle I and solid-liquid separator I inlet communication are described dense
Contracting crystallization kettle II outlet and solid-liquid separator II inlet communication.
It is preferred that, before reactor, between reactor and decolouring kettle or between decolouring kettle and continuous chromatography piece-rate system
It is additionally provided with the concentration kettle of connection.
The beneficial effects of the present invention are：The inventive method technique is simple, and small investment not only can be to iminodiacetonitrile
Production mother liquor is effectively treated, the incinerator expensive without purchase, also prevent the secondary pollution of waste gas from incinerator, and can be with
Hydroxyacetonitrile, aminoacetonitriles, iminodiacetonitrile, ammonium hydrogen sulfate and the ammonium sulfate contained in effective recycling mother liquor, favorably
In reduction production cost.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, below in conjunction with accompanying drawing to the present invention
It is described further：
Fig. 1 is the inventive method and schematic device.
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 is as shown in Figure 1.Device includes reactor, decolouring kettle, concentration kettle and the company being sequentially communicated
Continuous chromatographic fractionation system, the outlet of the continuous chromatography piece-rate system is entered with condensing crystallizing kettle I and condensing crystallizing kettle II respectively
Mouthful connection, the outlet of the condensing crystallizing kettle I and solid-liquid separator I inlet communication, the outlet of the condensing crystallizing kettle II with
Solid-liquid separator II inlet communication.
Specific method is as follows：
（1）Iminodiacetonitrile is taken to produce mother liquor 1kg（Containing 7.8wt% hydroxyacetonitriles, 5.4wt% iminodiacetonitriles,
4.6wt% aminoacetonitriles, 59.5wt% water, 20.7wt% (sulfuric acid+ammonium hydrogen sulfate+ammonium sulfate)）, add 28wt% ammoniacal liquor 80g regulations
PH value is to 8.0, and back flow reaction 1.5 hours, sampling analysis shows that the content of hydroxyacetonitrile and aminoacetonitriles is respectively less than 0.5%；To institute
Obtain and hydrogen peroxide 5.0g is added in reaction solution, continue to flow back 1.0 hours, then steam water 400g, be cooled to 60 DEG C；
（2）By step（1）Obtained solution uses the continuous chromatography piece-rate system filled with ammonium type chromatographic isolation resin 60
Separated under the conditions of DEG C, respectively obtain iminodiacetonitrile solution 636g（Content is 21.9%）With ammonium sulfate 760g（Contain
Measure as 27.6%）；
（3）By step（2）It is 50% that obtained iminodiacetonitrile solution, which is concentrated into iminodiacetonitrile content, is cooled to
10 DEG C of crystallizations, filtering, filtration cakes torrefaction obtains iminodiacetonitrile 122.5g, content 95.7%；Filtrate is crystalline mother solution I in lower batch
Applied mechanically when ammonification is reacted or when continuous chromatography is separated or when iminodiacetonitrile solution is concentrated；
（4）By step（2）It is 48.5% that obtained ammonium sulfate, which is concentrated into ammonium sulphate content, is cooled to 10 DEG C of crystallizations, mistake
Filter, filtration cakes torrefaction obtains ammonium sulfate 62.9g, content 99.1%；Filtrate be crystalline mother solution II when lower batch continuous chromatography is separated or
Person's ammonium sulfate is applied mechanically when concentrating.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (8)
1. iminodiacetonitrile produces the resource utilization method of mother liquor, it is characterised in that：Comprise the following steps：
（1）By iminodiacetonitrile production mother liquor ammonification reaction, change into the hydroxyacetonitrile and aminoacetonitriles that contain in mother liquor
Iminodiacetonitrile, sulfuric acid and ammonium hydrogen sulfate change into ammonium sulfate, gained reaction solution activated carbon or hydrogen peroxide for decoloration, are contained
The mixed liquor of iminodiacetonitrile and ammonium sulfate；
（2）By step（1）Obtained imido- diacetonitrile and the mixed liquor of ammonium sulfate is separated using continuous chromatography, is respectively obtained
Iminodiacetonitrile solution and ammonium sulfate；
（3）By step（2）Obtained iminodiacetonitrile solution concentration, crystallization, separation of solid and liquid obtains iminodiacetonitrile solid
With crystalline mother solution I；Gained crystalline mother solution I when lower batch ammonification is reacted or continuous chromatography separation when or iminodiacetonitrile
Solution is applied mechanically when concentrating；
（4）By step（2）Obtained ammonium sulfate concentration, crystallization, separation of solid and liquid obtains ammonium sulfate solids and crystalline mother solution II；
Gained crystalline mother solution II is applied mechanically when lower batch continuous chromatography is separated or when ammonium sulfate is concentrated.
2. iminodiacetonitrile as claimed in claim 1 produces the resource utilization method of mother liquor, it is characterised in that：Step
（1）Middle bleaching temperature is 60-100 DEG C, and the consumption of activated carbon or hydrogen peroxide is the 0.1 ~ 1% of reaction solution quality.
3. iminodiacetonitrile as claimed in claim 1 produces the resource utilization method of mother liquor, it is characterised in that：Step
（1）In also have concentration before ammonification reaction, between ammonification reaction and decolorization or after decolorization.
4. iminodiacetonitrile as claimed in claim 1 produces the resource utilization method of mother liquor, it is characterised in that：Step
（2）The chromatograph packing material that middle continuous chromatography separation is used is sodium form, potassium type, ammonium type or calcium type chromatographic isolation resin；Continuous chromatography
The temperature of separation is 20 ~ 80 DEG C.
5. iminodiacetonitrile as claimed in claim 1 produces the resource utilization method of mother liquor, it is characterised in that：Step
（3）The middle content that iminodiacetonitrile solution is concentrated into iminodiacetonitrile is 30 ~ 50%, 0 ~ 30 DEG C of crystallization.
6. iminodiacetonitrile as claimed in claim 1 produces the resource utilization method of mother liquor, it is characterised in that：Step
（4）The middle content that ammonium sulfate is concentrated into ammonium sulfate is 40 ~ 50%, 0 ~ 30 DEG C of crystallization.
7. the device for realizing the resource utilization method of iminodiacetonitrile production mother liquor described in claim 1, its feature
It is：Including the reactor, decolouring kettle and continuous chromatography piece-rate system being sequentially communicated, the outlet of the continuous chromatography piece-rate system
Respectively with condensing crystallizing kettle I and condensing crystallizing kettle II inlet communication, outlet and the solid-liquid separator I of the condensing crystallizing kettle I
Inlet communication, the outlet of the condensing crystallizing kettle II and solid-liquid separator II inlet communication.
8. being used for the device for realizing the resource utilization method of iminodiacetonitrile production mother liquor as claimed in claim 7, it is special
Levy and be：It is additionally provided with before reactor, between reactor and decolouring kettle or between decolouring kettle and continuous chromatography piece-rate system
The concentration kettle of connection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510332150.7A CN105001121B (en) | 2015-06-16 | 2015-06-16 | The resource utilization method and device of iminodiacetonitrile production mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510332150.7A CN105001121B (en) | 2015-06-16 | 2015-06-16 | The resource utilization method and device of iminodiacetonitrile production mother liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105001121A CN105001121A (en) | 2015-10-28 |
| CN105001121B true CN105001121B (en) | 2017-09-22 |
Family
ID=54374035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510332150.7A Active CN105001121B (en) | 2015-06-16 | 2015-06-16 | The resource utilization method and device of iminodiacetonitrile production mother liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001121B (en) |
Family Cites Families (3)
| 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 |
| US4895971A (en) * | 1988-10-31 | 1990-01-23 | W. R. Grace & Co.-Conn. | Process for the production of iminodiacetonitrile |
| CN103408460B (en) * | 2013-08-22 | 2014-12-10 | 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 CN201510332150.7A patent/CN105001121B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105001121A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111269107B (en) | L-lactic acid purification and refining method | |
| CN101491323B (en) | New production technique of sodium glutamate | |
| CN1318387C (en) | Cleaning production process of extracting L-isoleucine from fermented liquor using ion-exchange | |
| CN101323614B (en) | Acidum folicum production method without sewerage discharge | |
| CN102923776B (en) | Method for producing high-purity vanadium pentoxide | |
| CN101648864A (en) | Purification method of citric acid fermentation broth | |
| CN102028179B (en) | Method for refining gourmet powder mother liquor | |
| CN103570569B (en) | Method for preparing glycine betaine by using beet ethyl alcohol waste liquor | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN101103800A (en) | Green making technology for monosodium glutanmate | |
| CN103058877B (en) | A kind of method of utilizing chromatographic isolation GABA and glutamic acid | |
| CN104817468B (en) | A kind of preparation method of glycine | |
| CN101665428B (en) | Method for extracting succinic acid from succinic acid fermentation liquor | |
| CN104974054B (en) | The method and device of iminodiacetic acid is prepared using iminodiacetonitrile production mother liquor | |
| CN101857212B (en) | Method for preparing food-grade monoammonium phosphate from wet-process phosphoric acid | |
| CN105017047B (en) | The production method and device of a kind of iminodiacetic acid | |
| CN111718370A (en) | Preparation method of O, O' -dimethyl thiophosphoryl amide | |
| CN105001121B (en) | The resource utilization method and device of iminodiacetonitrile production mother liquor | |
| CN102875401B (en) | Method for producing DL-aspartic acid from waste radix asparagi | |
| CN106349108B (en) | A kind of isolation and purification method of cyanoacetic acid | |
| CN105017074B (en) | Iminodiacetonitrile produces the processing recovery method and device of mother liquor | |
| CN108117190B (en) | Process for treating low-concentration ammonia nitrogen wastewater of phosphate fertilizer plant | |
| CN104892436B (en) | Iminodiacetonitrile produces the recycling method and device of mother liquor | |
| CN111960958A (en) | Method for preparing glycine from ethanol-water solvent solid chloroacetic acid | |
| CN108913726A (en) | A kind of technique that biochemical method prepares acrylamide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |