CN105017047B - The production method and device of a kind of iminodiacetic acid - Google Patents
The production method and device of a kind of iminodiacetic acid Download PDFInfo
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- CN105017047B CN105017047B CN201510332096.6A CN201510332096A CN105017047B CN 105017047 B CN105017047 B CN 105017047B CN 201510332096 A CN201510332096 A CN 201510332096A CN 105017047 B CN105017047 B CN 105017047B
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- iminodiacetonitrile
- iminodiacetic acid
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Abstract
The invention discloses a kind of production method of iminodiacetic acid and device, it is to add calcium oxide or calcium hydroxide reaction into iminodiacetonitrile production mother liquor, the hydroxyacetonitrile and aminoacetonitriles that contain in mother liquor is set to change into iminodiacetonitrile, sulfuric acid, ammonium hydrogen sulfate and ammonium sulfate change into calcium sulfate, and separation of solid and liquid obtains calcium sulphate solid and iminodiacetonitrile solution；Iminodiacetonitrile solution is generated into iminodiacetic acid and ammonium hydrogen sulfate with sulphuric acid hydrolysis, ammonification reaction makes ammonium hydrogen sulfate change into ammonium sulfate, and activated carbon decolorizing, destainer passes through the isolated iminodiacetic acid (salt) acid solution of continuous chromatography and ammonium sulfate；Two kinds of solution are distinguished into condensing crystallizing, that is, obtain iminodiacetic acid solid and ammonium sulfate solids.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 and iminodiacetonitrile, being made has the iminodiacetic acid of economic value.
Description
Technical field
The invention belongs to chemical field, it is related to a kind of production method of iminodiacetic acid and its device that forms a complete production network.
Background technology
Iminodiacetic acid is a kind of important fine chemical product, with very strong complexing, energy and various metals
Ion formation chelate, extensively should have in terms of agricultural chemicals, dyestuff, chemical industry, water process, medicine, functional polymer, electronics
With.
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, imino-diacetic is prepared using iminodiacetonitrile production mother liquor it is an object of the invention to provide one kind
The method and its corollary apparatus of acetic acid, can not only be effectively treated, and can return to iminodiacetonitrile production mother liquor
Receive using the hydroxyacetonitrile, aminoacetonitriles and iminodiacetonitrile contained in mother liquor, the iminodiacetic acid (salt) for having economic value is made
Acid.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1. a kind of production method of iminodiacetic acid, comprises the following steps：
（1）Calcium oxide or calcium hydroxide reaction are added into iminodiacetonitrile production mother liquor, makes the hydroxyl contained in mother liquor
Base acetonitrile and aminoacetonitriles change into iminodiacetonitrile, and sulfuric acid, ammonium hydrogen sulfate and ammonium sulfate change into calcium sulfate, separation of solid and liquid
Obtain calcium sulphate solid and iminodiacetonitrile solution；
（2）To step（1）Sulphuric acid hydrolysis, generation iminodiacetic acid and sulfuric acid are added in gained iminodiacetonitrile solution
Hydrogen ammonium；Then ammonification is reacted, and ammonium hydrogen sulfate is changed into ammonium sulfate；Gained reaction solution adds activated carbon decolorizing；
（3）By step（2）Gained destainer carries out continuous chromatography separation, respectively obtains iminodiacetic acid (salt) acid solution and sulfuric acid
Ammonium salt solution；
（4）By step（3）Gained iminodiacetic acid (salt) acid solution is concentrated, crystallization, and separation of solid and liquid obtains iminodiacetic acid and consolidated
Body and crystalline mother solution I；
（5）By step（3）Gained ammonium sulfate is concentrated, and crystallization, separation of solid and liquid obtains ammonium sulfate solids and crystalline mother solution
II。
With step（1）Add exemplified by calcium oxide, the chemical equation that this method is related to is as follows：
H2SO4 + CaO → CaSO4 + H2O
NH4HSO4 + CaO → CaSO4 + NH3 + H2O
(NH4)2SO4 + CaO → CaSO4 + 2 NH3 + H2O
2 HOCH2CN + NH3 → HN(CH2CN)2 + 2 H2O
HOCH2CN + NH2CH2CN → HN(CH2CN)2 + H2O
HN(CH2CN)2 + 4 H2O + 2 H2SO4 → HN(CH2COOH)2 + 2 NH4HSO4
NH4HSO4 + NH3 → (NH4)2SO4
It is preferred that, step（1）Middle addition calcium oxide or calcium hydroxide regulation pH value is heating response after 6 ~ 9.
It is preferred that, step（2）Middle hydrolysis temperature is 40 ~ 80 DEG C.
It is preferred that, step（2）Middle bleaching temperature is 60-100 DEG C.
It is preferred that, step（2）Middle activated carbon dosage is the 0.1 ~ 5% of reaction solution quality.
It is preferred that, step（3）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（3）The temperature of middle continuous chromatography separation is 20 ~ 90 DEG C.
It is preferred that, step（4）Middle gained crystalline mother solution I is when lower batch continuous chromatography is separated or lower batch iminodiacetic acid (salt)
Acid solution is applied mechanically when concentrating.
It is preferred that, step（5）Middle gained crystalline mother solution II is when lower batch continuous chromatography is separated or lower batch ammonium sulfate is molten
Liquid is applied mechanically when concentrating.
2. for realizing the device of the iminodiacetic acid production method, including reactor, the solid-liquid point being sequentially communicated
From device I, hydrolysis kettle, solid-liquid separator II and continuous chromatography piece-rate system, the outlet of the continuous chromatography piece-rate system respectively with
Condensing crystallizing kettle I and condensing crystallizing kettle II inlet communication, the outlet of the condensing crystallizing kettle I and entering for solid-liquid separator III
Mouth connection, the outlet of the condensing crystallizing kettle II and solid-liquid separator IV inlet communication.
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 and the iminodiacetonitrile contained in effective recycling mother liquor, is made the imido for having economic value
Base oxalic acid.
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, solid-liquid separator I, hydrolysis kettle, solid-liquid separator II and the continuous chromatography point being sequentially communicated
From system, the outlet of the continuous chromatography piece-rate system respectively with condensing crystallizing kettle I and condensing crystallizing kettle II inlet communication, institute
State condensing crystallizing kettle I outlet and solid-liquid separator III inlet communication, the outlet of the condensing crystallizing kettle II and separation of solid and liquid
Device IV inlet communication.
Specific method is as follows：
（1）Iminodiacetonitrile is taken to produce mother liquor 1kg（Containing 8.5wt% hydroxyacetonitriles, 6.2wt% iminodiacetonitriles,
4.7wt% aminoacetonitriles, 56.5wt% water, 17.5wt% (sulfuric acid+ammonium hydrogen sulfate+ammonium sulfate)）, add the calcium oxide that content is 97%
108g adjusts pH value to 8.5, and back flow reaction 1.5 hours, sampling analysis shows that the content of hydroxyacetonitrile and aminoacetonitriles is respectively less than
0.5%, calcium sulfate is separated by filtration while hot, and filtrate is stand-by；
（2）To step（1）98wt% sulfuric acid 260g is added in gained filtrate, 60 DEG C are reacted 2 hours, lead to ammonia by reaction solution
It is 2 to be neutralized to pH value, adds activated carbon 3g, 80 DEG C are stirred 1 hour, activated carbon are filtered to remove while hot, filtrate is stand-by；
（3）By step（2）Gained filtrate uses the continuous chromatography piece-rate system filled with ammonium type chromatographic isolation resin 80 ~ 85
Separated under the conditions of DEG C, respectively obtain iminodiacetic acid (salt) acid solution 1893g（Content 12.4%）With ammonium sulfate 2531g（Content
22.9%）；
（4）By step（3）The concentration of gained iminodiacetic acid (salt) acid solution steams water 1050g, is cooled to 10 DEG C of stirred crystallizations 2 small
When, filtering, Washing of Filter Cake is dried, obtains iminodiacetic acid 212.6g, content 98.3%；Filtrate is crystalline mother solution I in lower batch
Applied mechanically when continuous chromatography is separated or when lower batch iminodiacetic acid (salt) acid solution is concentrated；
（5）By step（3）The concentration of gained ammonium sulfate steams water 1600g, is cooled to 10 DEG C of stirred crystallizations 1 hour, mistake
Filter, Washing of Filter Cake is dried, obtains ammonium sulfate 323g, content 99.0%；Filtrate is that crystalline mother solution II is separated in lower batch continuous chromatography
When or lower batch ammonium sulfate concentration when apply mechanically.
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 (6)
1. a kind of production method of iminodiacetic acid, it is characterised in that：Comprise the following steps：
（1）Calcium oxide or calcium hydroxide reaction are added into iminodiacetonitrile production mother liquor, makes the hydroxyl second contained in mother liquor
Nitrile and aminoacetonitriles change into iminodiacetonitrile, and sulfuric acid, ammonium hydrogen sulfate and ammonium sulfate change into calcium sulfate, and separation of solid and liquid is obtained
Calcium sulphate solid and iminodiacetonitrile solution；
（2）To step（1）Sulphuric acid hydrolysis are added in gained iminodiacetonitrile solution, hydrolysis temperature is 40 ~ 80 DEG C, generates imido
Base oxalic acid and ammonium hydrogen sulfate；Then ammonification is reacted, and ammonium hydrogen sulfate is changed into ammonium sulfate；Gained reaction solution adds activated carbon
Decolourize；
（3）By step（2）Gained destainer carries out continuous chromatography separation, respectively obtains iminodiacetic acid (salt) acid solution and ammonium sulfate is molten
Liquid；
（4）By step（3）Gained iminodiacetic acid (salt) acid solution concentrate, crystallization, separation of solid and liquid obtain iminodiacetic acid solid and
Crystalline mother solution I, gained crystalline mother solution I cover when lower batch continuous chromatography is separated or when lower batch iminodiacetic acid (salt) acid solution is concentrated
With；
（5）By step（3）Gained ammonium sulfate is concentrated, and crystallization, separation of solid and liquid obtains ammonium sulfate solids and crystalline mother solution II, institute
Crystalline mother solution II is obtained to apply mechanically when lower batch continuous chromatography is separated or when lower batch ammonium sulfate is concentrated.
2. the production method of iminodiacetic acid as claimed in claim 1, it is characterised in that：Step（1）Middle addition calcium oxide
Or calcium hydroxide regulation pH value is heating response after 6 ~ 9.
3. the production method of iminodiacetic acid as claimed in claim 1, it is characterised in that：Step（2）Middle bleaching temperature is
60-100℃。
4. the production method of iminodiacetic acid as claimed in claim 1, it is characterised in that：Step（2）Middle activated carbon dosage
For the 0.1 ~ 5% of reaction solution quality.
5. the production method of iminodiacetic acid as claimed in claim 1, it is characterised in that：Step（3）Middle continuous chromatography point
It is sodium form, potassium type, ammonium type or calcium type chromatographic isolation resin from the chromatograph packing material used.
6. the production method of iminodiacetic acid as claimed in claim 1, it is characterised in that：Step（3）Middle continuous chromatography point
From temperature be 20 ~ 90 DEG C.
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1075138B (en) * | 1976-03-29 | 1985-04-22 | Grace W R & Co | PROCESS FOR THE RECOVERY OF GLYCINE AND IMINODIACETIC ACID |
| CN1594281A (en) * | 2004-07-05 | 2005-03-16 | 四川省天然气化工研究院 | Process for preparing iminodiacetic acid |
| CN102432478B (en) * | 2011-11-09 | 2013-11-13 | 重庆紫光化工股份有限公司 | Preparation process of glycine |
| CN103232355B (en) * | 2013-04-25 | 2015-06-17 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN103319359A (en) * | 2013-07-22 | 2013-09-25 | 重庆紫光化工股份有限公司 | Production method of iminodiacetic acid |
| 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 |
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