CN109369429A - The device and method of iminodiacetic acid is prepared using iminodiacetonitrile feed liquid - Google Patents
The device and method of iminodiacetic acid is prepared using iminodiacetonitrile feed liquid Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/26—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing carboxyl groups by reaction with HCN, or a salt thereof, and amines, or from aminonitriles
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
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- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
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Abstract
The invention belongs to chemical industry synthesis fields, and in particular to a kind of device and method for preparing iminodiacetic acid using iminodiacetonitrile feed liquid.The device includes sequentially connected complex acid device, ammonium hydroxide preparing device, reaction system, decoloration system, solid-liquid separation system I, evaporation and crystallization system, solid-liquid separation system II.Wherein, the liquid outlet of solid-liquid separation system II is connected with decoloration system；The feed inlet of reaction system is connected with complex acid device；There is ammonium hydroxide feed inlet on solid-liquid separation system I.The present invention also provides a kind of methods for preparing iminodiacetic acid using apparatus above.Production process of the present invention simplifies, and IDA total recovery greatly improves, and has preferable economic benefit；And present invention process process is short, waste water is few, environment-friendly advantage is obvious, can be carried out large-scale production.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of to prepare iminodiacetic acid (salt) using iminodiacetonitrile feed liquid
The device and method of acid.
Background technique
Iminodiacetic acid also known as Diglycocol, aminodiacetic acid, abbreviation IDA, molecular formula are NH (CH2COOH)2, it is one
Kind important fine chemical product has very strong complexing, can and various metals ion form chelate, pesticide,
Dyestuff, chemical industry, water process, medicine, functional polymer, electronics etc. extensive application are pesticide, pharmacy, rubber, surface
Activating agent, complexing agent, food additives, electroplating industry, synthesis metal conditioner and its ion exchange resin etc. it is important
Raw material and intermediate.
Domestic industry metaplasia produces there are mainly four types of the methods of iminodiacetic acid: domestic industry metaplasia produces iminodiacetic acid
Method there are mainly four types of, iminodiacetonitrile alkali hydrolysis method, iminodiacetonitrile acid-hydrolysis method, chloroactic acid method and diethanol amine
Oxidizing process.Wherein, chloroactic acid method is to be acidified with hydrochloric acid by after monoxone and ammonium hydroxide, calcium hydroxide reaction, generate iminodiacetic acid (salt)
Acid hydrochloride is stood still for crystals, and is filtered, pickling, and hot water is dissolved in, and sodium hydroxide solution is added, and generates iminodiacetic acid, knot
Brilliant, separation, it is dry after obtain product, this method technical maturity, but have that long flow path, product purity is low, at high cost, " three wastes " are tight
The disadvantages of weight；Iminodiacetonitrile acid-hydrolysis method is that iminodiacetonitrile and hydrochloric acid or sulphuric acid hydrolysis are directly obtained imino group
Oxalic acid and ammonium chloride or ammonium sulfate；Diethanol amine oxidizing process and iminodiacetonitrile alkali hydrolysis method are all first to become raw material
Then iminodiacetic acid disodium salt is acidified to obtain the mixed of iminodiacetic acid and sodium chloride or sodium sulphate with hydrochloric acid or sulfuric acid
Close object, then isolated iminodiacetic acid.
Currently, iminodiacetonitrile is first with the system for after basic hydrolysis using acidization being again the most commonly used iminodiacetic acid
Preparation Method, common separation method be by iminodiacetic acid disodium salt hydrochloric acid or sulfuric acid acidification at iminodiacetic acid and
Corresponding inorganic salts, using iminodiacetic acid solubility is small in water and inorganic salts in water the big characteristic of solubility by the two
It separates, mother liquor is continuously applied；Or iminodiacetic acid disodium salt is acidified into one sodium salt of iminodiacetic acid and sodium chloride
Or sodium sulphate, recycle the dissolubility property of one sodium salt of iminodiacetic acid and inorganic salts first to isolate inorganic salts, then be acidified
Isolated iminodiacetic acid, mother liquid recycle.
Contain a large amount of iminodiacetonitrile, hydroxyacetonitrile, aminoacetonitriles, sulfuric acid, sulfuric acid in iminodiacetonitrile mother liquor
Hydrogen ammonium and ammonium sulfate, there are also some other organic polymers usually to be handled as liquid waste incineration because of complicated component.But mother liquor
Salt content, water content it is larger, burning is more difficult, and combustion heat value is very low, and can also generate in mother liquor combustion process big
The acid gas of amount causes secondary pollution and the corrosion of metal equipment, and there are also the organic polymers generated in combustion process easily to block
Incinerator.Therefore, existing iminodiacetonitrile mother liquor processing method there are serious waste of resources, processing difficulty is big, there have to be secondary
Pollution does not generate the disadvantages of any economic value.In addition, being influenced after impurities hydrolysis acidification in iminodiacetonitrile mother liquor sub-
The yield of aminodiacetic acid and the recycled number of mother liquor, and increase waste water yield and processing difficulty.
Chinese patent CN101391911A discloses a kind of method for preparing organic fertilizer using amino nitrile production waste liquid, should
Method is that catalyst and the obtained base manure of dispersing agent are added in amino nitrile production waste liquid, and base manure is then inoculated with biological bacteria, carries out 7
Fermentation in~15 days, then hydrolyze as material fertilizer, material fertilizer is produced into organic fertilizer by the processes such as nutrient allotment, granulation, dry
Material.The method achieve the whole resource utilization to cyanide wastewater, but liquid waste processing overlong time, and need large-scale compost
Place, and this kind of trans-utilization value is lower.
Chinese patent CN103483031A discloses one kind, and using iminodiacetonitrile waste water as raw material to prepare amino acid compound
The method of object.Using the iminodiacetonitrile waste water generated during producing iminodiacetonitrile as raw material, auxiliary agent is added, in temperature
It is stirred under the conditions of 50-280 DEG C of degree polymerization reaction 6~120 minutes, two kinds of composite catalyzings is successively added after completion of the polymerization reaction
Agent carries out amino acidification reaction 10~150 minutes under the conditions of 50-200 DEG C of temperature, obtains a kind of Liquid amino acid compound,
The liquid is dried to obtain a kind of solid amino acid complex again.This method energy consumption is high, and obtained product form is complicated, using by
Limit.
Chinese patent CN101503367A discloses a kind of raffinate synthesis using hydrogen cyanide method production iminodiacetonitrile
The method of nitrilotriacetic acid.It specifically includes: 1) adding alkali to be hydrolyzed at 30~100 DEG C the raffinate of iminodiacetonitrile, in water
Monoxone is added in solution liquid, at 10~100 DEG C, with after the reaction of adjusting PH with base=9~14 0.5~10 hour, then in reaction solution plus
Acid acidification, is precipitated nitrilotriacetic acid crude product.2) nitrilotriacetic acid crude product is suspended in water, stirring is lower plus alkali neutralization dissolves, active carbon
Decoloration removes active carbon, is acidified, and filters, dry, obtains nitrilotriacetic acid finished product.The disadvantages of the method are as follows mother liquor cannot be efficiently used
In remaining great amount of hydroxy group acetonitrile, consume a large amount of alkali and acid, generate a large amount of inorganic salts, energy consumption is high, and wastewater flow rate can increase
Add.
Applicant has generated about 2000 tons of various waste materials since iminodiacetonitrile is gone into operation, and stores existing trend of environmental protection for a long time
Danger, and quality is caused to decline, it is difficult to it recycles.Iminodiacetonitrile feed liquid uses falling film evaporation, takes raffinate use after crystalline substance useless
Liquid incinerator burn that one side Product recycling utilization rate is low, energy consumption is high, on the other hand causes environmentally friendly risk, in incineration tail gas
Contain nitrogen, oxysulfide.
So applicant overstocks Resolving probiems and environmental issue by exploitation the device of the invention iminodiacetonitrile waste material,
And iminodiacetonitrile production feed liquid is effectively treated the iminodiacetic acid for being made and having economic value.
Summary of the invention
In view of this, preparing iminodiacetic acid using iminodiacetonitrile feed liquid the purpose of the present invention is to provide a kind of
Device and method, which, which can not only produce feed liquid to iminodiacetonitrile and be effectively treated to be made, the Asia of economic value
Aminodiacetic acid, and process flow is short, waste water is few, reduces environmentally friendly risk.
To achieve the above object, the technical solution of the present invention is as follows:
The device of iminodiacetic acid is prepared using iminodiacetonitrile feed liquid, which is characterized in that including sequentially connected
Complex acid device (1), ammonium hydroxide preparing device (2), reaction system (3), decoloration system (4), solid-liquid separation system I (5), evaporation and crystallization system
(6), (7) solid-liquid separation system II；The liquid outlet of the solid-liquid separation system Π (7) is connected with decoloration system (4)；The reaction
The feed inlet of system (3) connects complex acid device (1)；The solid-liquid separation system I (5) connects ammonium hydroxide preparing device (2).This covering device is adopted
It is produced with whole process intermittent mode.
As a preference, the material of consersion unit is enamel or modified glass steel material.Iminodiacetonitrile feed liquid
Sulfuric acid concentration when direct sour water solution is higher, and temperature is higher than 100 DEG C, and traditional glass steel can not be selected as the material of reaction kettle
Matter.
Further, the resulting condensate water circulatory of evaporation and crystallization system is prepared sulfuric acid solution into complex acid device and/or is recycled to
It is used in ammonium hydroxide preparing device with ammonium hydroxide.
The condensed water of evaporation and crystallization system of the present invention makes full use of, and reduces the generation of waste water, reduces production cost.
Further, the concentrated mother liquor that solid-liquid separation system II is obtained enters recycled in decoloration system, realizes imido
Base diacetonitrile mother liquor recycles.
Further, iminodiacetonitrile feed liquid is that (1) uses hydrogen cyanide, hexamethylenetetramine and formaldehyde for raw material reaction；
(2) aminoacetonitriles heats disproportionated reaction；(3) hydroxyacetonitrile is reacted with aminoacetonitriles；(4) hydroxyacetonitrile and ammonia are raw material reaction
Obtained by one or more of modes.
Further, iminodiacetonitrile feed liquid can also be reacted from this covering device reaction solution, crystalline mother solution,
One or more of concentrated mother liquor.
The second object of the present invention be to provide it is a kind of using above-mentioned device using iminodiacetonitrile feed liquid as raw material system
The method of standby iminodiacetic acid, comprising the following steps:
1) feed inlet that the sulfuric acid solution that the mass concentration prepared by complex acid device is 65%~75% is passed through into reaction system
It is sent into reaction system, then iminodiacetonitrile production feed liquid is continuously added to hydrolyze in reaction system, reaction is transferred to after carrying out
Decoloration system carries out decolorization, obtains destainer；
2) ammonium hydroxide that ammonium hydroxide preparing device is prepared is added to solid-liquid separation system I by ammonium hydroxide feed inlet, and decoloration system is obtained
To destainer be transferred to solid-liquid separation system I participate in reaction, adjust feed liquid pH value be 1.5~3, adjust pH value during,
PH value then continues logical ammonia less than 1~3, and pH value is greater than 1~3, then sulfuric acid is added.Decrease temperature crystalline after reaction, through solid-liquid separation system
I separates to obtain iminodiacetic acid and crystalline mother solution；
3) crystalline mother solution that step 2) obtains is transferred to evaporation and crystallization system, while being passed through ammonia, and the pH value of solution is adjusted to
7-7.5 is evaporated crystallization, then separates to obtain ammonium sulfate and concentrated mother liquor through solid-liquid separation system Π.
Reaction process are as follows:
(2)NH4HSO4+NH3→(NH4)2SO4
4) step 3) enters decoloration system progress recycled from the concentrated mother liquor that solid-liquid separation system Π is obtained, and continues to join
With reacting for next round.The problem of realizing iminodiacetonitrile mother liquid recycling.
Further, the temperature reacted in step 1) is 100~120 DEG C, and the temperature of decoloration is 70~90 DEG C.
Further, active carbon and/or hydrogen peroxide are also added into the decoloration system in step 1)；The dosage of active carbon is Asia
The 1%~10% of aminodiacetic acid weight；Dioxygen water consumption is 1%.As a preference, activated carbon dosage is iminodiacetic acid (salt)
The 6% of sour weight.
Further, the water that the temperature reacted in step 1) steams under 100~120 DEG C of micro-boiling states recycles after condensing
To decoloration system.
Configured sulfuric acid is transferred in reaction system, is added under the conditions of tiny structure, then by iminodiacetonitrile feed liquid
In reaction system, reaction temperature under micro-boiling state is kept to steam water in stream plus iminodiacetonitrile feed liquid at 100~120 DEG C.
Purified crystals are directly gone through the condensed water that steams.4h is kept the temperature at 105~120 DEG C after feeding intake.
Further, in step 1) conversion ratio of iminodiacetonitrile feed liquid be transferred to after 90%~97% decoloration system into
Row processing.
As a preference, the conversion ratio of iminodiacetonitrile production feed liquid is 95%~97% in middle control step 1).
As a preference, being cooled to 80 ± 5 DEG C after middle control is qualified, being gone again after addition active carbon progress decolorization pure
Change crystallization.
Further, obtained iminodiacetic acid is separated by solid-liquid separation in step 2) to be washed again, it is dry to get iminodiacetic acid (salt)
Acid product, wash water recycled.
Further, it is 1.5~3 that ammonification, which adjusts pH, in step 2)；The temperature of reaction is 60~80 DEG C.
Further, the temperature of decrease temperature crystalline is 10~40 DEG C in step 2), and crystallization time is 0.5~4h.
The present invention also provides a kind of methods for preparing ammonium sulfate mixture using mentioned-above device, and this method is with imido
Base diacetonitrile feed liquid is raw material, and water and sulfuric acid is added to occur hydrolysis, hydrolysate again with ammonia successive reaction, by evaporative crystallization
Ammonium sulfate mixture is obtained, contains ammonium sulfate and a small amount of iminodiacetic acid in the mixture.
The beneficial effects of the present invention are:
1) of the invention to prepare the device of iminodiacetic acid using iminodiacetonitrile feed liquid with iminodiacetonitrile material
Liquid is raw material, and production process is more simplified, and it is heavy to eliminate former iminodiacetonitrile technique crystallization, concentration, secondary crystallization, mother liquor
Multiple processes such as drop, liquid waste incineration avoid generating ropy iminodiacetonitrile product, and substantially increase IDA total recovery,
With preferable economic benefit.
2) present invention is effectively treated the obtained iminodiacetic acid (salt) for having economic value using by iminodiacetonitrile feed liquid
Acid, and the process flow is short, waste water is few, environment-friendly advantage is obvious, avoids being reduced production cost using sodium hydroxide, being reduced energy
Consumption, can be carried out large-scale production.
Detailed description of the invention
Fig. 1 is the schematic diagram for the device that the present invention prepares iminodiacetic acid using iminodiacetonitrile feed liquid.
Specific embodiment
Hereinafter reference will be made to the drawings, and the preferred embodiment of the present invention is described in detail.Tool is not specified in preferred embodiment
The experimental method of concrete conditions in the establishment of a specific crime, usually according to normal condition, illustrated embodiment are to preferably say to the contents of the present invention
It is bright, but be not that the contents of the present invention are only limitted to illustrated embodiment.So those skilled in the art are according to foregoing invention
Content carries out nonessential modifications and adaptations to embodiment, still falls within protection scope of the present invention.
Embodiment 1
The device of iminodiacetic acid is prepared using iminodiacetonitrile production feed liquid
The device of iminodiacetic acid is prepared using iminodiacetonitrile feed liquid, which is characterized in that including sequentially connected
Complex acid device (1), ammonium hydroxide preparing device (2), reaction system (3), decoloration system (4), solid-liquid separation system I (5), evaporation and crystallization system
(6), (7) solid-liquid separation system II；The liquid outlet of the solid-liquid separation system Π (7) is connected with decoloration system (4)；The reaction
The feed inlet of system (3) connects complex acid device (1)；The solid-liquid separation system I (5) connects ammonium hydroxide preparing device (2).Evaporative crystallization system
Resulting condensate water circulatory of uniting prepares sulfuric acid solution into complex acid device；The resulting condensate water circulatory of evaporation and crystallization system is to ammonium hydroxide system
Ammonium hydroxide is prepared in standby device；The concentrated mother liquor that solid-liquid separation system II is obtained enters recycled in decoloration kettle.
Embodiment 2
The method that iminodiacetic acid is prepared as raw material using iminodiacetonitrile production feed liquid using the device
The method that iminodiacetic acid is prepared as raw material using iminodiacetonitrile production feed liquid using the device, including
Following steps:
1) sulfuric acid solution prepared by complex acid device is transferred to consersion unit by the feed inlet of reaction system, then by imino group
Diacetonitrile feed liquid is continuously added to hydrolyze in reaction system, reacts at a temperature of 105~120 DEG C, the conversion of iminodiacetonitrile feed liquid
Rate, which is transferred in decoloration system after 90%~97%, is added active carbon progress decolorization, and the temperature of decoloration is 70~90 DEG C,
Obtain destainer.
2) ammonium hydroxide that ammonium hydroxide preparing device is prepared is added to solid-liquid separation system I by ammonium hydroxide feed inlet, the decoloration that will be obtained
Liquid, which is also transferred to, wherein to react, adjust feed liquid pH value be 1.5~3,60~80 DEG C reaction after 25~35 DEG C of decrease temperature crystallines 0.5~
4h separates to obtain iminodiacetic acid and crystalline mother solution through solid-liquid separation system I；Iminodiacetic acid is washed again, it is dry to get
Iminodiacetic acid (salt) acid product, wash water recycled；
3) crystalline mother solution that step 2) obtains is transferred to evaporation and crystallization system, while being passed through gas ammonia, by the pH value tune of solution
It is evaporated crystallization to 7 or more, then separates to obtain ammonium sulfate through solid-liquid separation system Π；The concentration that solid-liquid separation system Π is obtained is female
Liquid enters decoloration system and carries out recycled；The condensate water circulatory of evaporation and crystallization system is prepared sulfuric acid solution into complex acid device and is followed
Ring is used into ammonium hydroxide preparing device with ammonium hydroxide.
Embodiment 3
Prepare ammonium sulfate
Single batch of experiment
1) water and sulfuric acid are added into consersion unit, is made into 75% sulfuric acid solution.
2) 110 DEG C are warming up to, slowly continuous that iminodiacetonitrile feed liquid is added dropwise, reaction temperature controls at 110 ± 5 DEG C, adds
After material, in 110 DEG C of heat preservation 2h.
3) end of reaction adds water 100ml, ammonium hydroxide 100ml, active carbon, is filtered after heat preservation 1h (80~90 DEG C of temperature control).
4) with ammonium hydroxide tune pH to 2.0 (temperature control is no more than 70 DEG C), crystallisation by cooling after filtering.
5) it filters and obtains IDA product, residual filtrate, which is stayed, to be done mother liquor concentrations and continue to apply.
Concentration
1) obtained mother liquor tune pH to 7.0, heating concentration are filtered.
2) the 1/3 of total volume is concentrated for the first time, takes out ammonium sulfate crystallization body while hot.
3) second of mother liquor concentrations takes out ammonium sulfate crystallization body to total volume 1/3 while hot.
Single batch of experimental data
Embodiment 4
Iminodiacetic acid is produced using iminodiacetonitrile reaction solution or crystal solution as raw material
1, single batch of scheme
1) water and sulfuric acid are added into consersion unit, is made into 75% sulfuric acid solution.
2) 105 DEG C are warming up to, iminodiacetonitrile reaction solution is slowly added to, reaction temperature controls the charging at 110 DEG C or so
After carry out tiny structure steam water 3h or more.
3) iminodiacetonitrile reaction solution is continuously added, reaction temperature is controlled at 115 DEG C or so, added after charging
Sulfuric acid.
4) after sulfuric acid is added, iminodiacetonitrile reaction solution is added, reaction temperature controls the charging at 115 DEG C or so
After carry out tiny structure steam water 3h or more.
5) iminodiacetonitrile reaction solution is continuously added, reaction temperature is controlled at 115 DEG C or so, added after charging
Sulfuric acid.
6) after sulfuric acid is added, iminodiacetonitrile reaction solution is added, reaction temperature controls the charging at 115 DEG C or so
After carry out tiny structure steam water 3h or more.It is kept the temperature after steaming water.
7) heat preservation finishes, and is cooled to 80 DEG C or so, is slowly added to hydrogen peroxide, then in 80-90 DEG C of heat preservation 0.5h.
8) after keeping the temperature, water is added to reaction system, leading to ammonia to adjust pH is 2.
9) pH value is cooled to 20 DEG C after reaching requirement, is further continued for stirring 3h.
10) it after decrease temperature crystalline, is filtered, takes out partial mother liquid and used as lower batch reaction.IDA crude product water logging
It is filtered after bubble 30min.
2, scheme is applied
1) batch remaining mother liquor is added into reaction kettle, adjusts pH value to carry out primary concentration desalination after 7.0-7.5, according to reality
After border situation steams suitable quantity of water, carry out once going out salt.Salt 1 is slowly washed with 50 water.Concentrated mother liquor and wash water return to reaction
Secondary concentration desalination is carried out in equipment, after steaming suitable quantity of water according to the actual situation, is carried out secondary salt, salt 2 out and is slowly washed with water.
2) batch mother liquor and sulfuric acid are added into reaction system, is made into 75% sulfuric acid solution.
3) 105 DEG C are warming up to, iminodiacetonitrile reaction solution is slowly added to, reaction temperature controls the charging at 110 DEG C or so
After, it carries out tiny structure and steams water.
4) iminodiacetonitrile reaction solution is continuously added, reaction temperature is controlled at 115 DEG C or so, added after charging
Sulfuric acid.
5) after sulfuric acid is added, iminodiacetonitrile reaction solution is added, reaction temperature controls the charging at 115 DEG C or so
After carry out tiny structure steam water 3h or more.
6) iminodiacetonitrile reaction solution is continuously added, reaction temperature is controlled at 115 DEG C or so, added after charging
Sulfuric acid.
7) after sulfuric acid is added, iminodiacetonitrile reaction solution is added, reaction temperature controls the charging at 115 DEG C or so
After carry out tiny structure steam water 3h or more.
8) it is kept the temperature after steaming water.
9) heat preservation finishes, and is cooled to 80 DEG C or so, is slowly added to hydrogen peroxide, then in 80-90 DEG C of heat preservation 0.5h.
10) after keeping the temperature, water (above criticizing wash water and clear water) and upper batch concentrated mother liquor is added to reaction system, leads to ammonia adjusting
PH is 2.
11) pH value is cooled to 20 DEG C after reaching requirement, is further continued for stirring 3h.
12) it after decrease temperature crystalline, is filtered, takes out partial mother liquid and used as lower batch reaction.IDA crude product water logging
It is filtered after bubble 30min.
Using iminodiacetonitrile reaction solution as raw material sulphuric acid results of hydrolysis
In terms of effect, iminodiacetonitrile yield reaches average content after 94.7%, IDA product drying in reaction solution IDA
Reaching 98.10%, the direct yield of rear three batches of products reaches 83.8% or more, if considering IDA amount in mother liquor and product wash water,
IDA yield reaches 92% or more.
The present invention using iminodiacetonitrile reaction solution as raw material, by sulphuric acid hydrolysis, decoloration, ammonia or ammonium hydroxide neutralize,
Crystallization, washing and etc., obtain qualified iminodiacetic acid (salt) acid product, feasible process, production process safety and stability.And the technique
Process is short, waste water is few, environment-friendly advantage is obvious, avoids reducing production cost using sodium hydroxide.
Using iminodiacetonitrile reaction solution as raw material, production process is more simplified, eliminates former iminodiacetonitrile technique
Multiple processes such as crystallization, concentration, secondary crystallization, mother liquor sedimentation, liquid waste incineration avoid generating ropy iminodiacetonitrile production
Product, and IDA total recovery is substantially increased, there is preferable economic benefit.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the scope of the claims of invention.
Claims (14)
1. preparing the device of iminodiacetic acid using iminodiacetonitrile feed liquid, which is characterized in that match including sequentially connected
Sour device (1), ammonium hydroxide preparing device (2), reaction system (3), decoloration system (4), solid-liquid separation system I (5), evaporation and crystallization system
(6), (7) solid-liquid separation system II；The liquid outlet of the solid-liquid separation system Π (7) is connected with decoloration system (4)；The reaction
The feed inlet of system (3) connects complex acid device (1)；The solid-liquid separation system I (5) connects ammonium hydroxide preparing device (2).
2. the apparatus according to claim 1, which is characterized in that the resulting condensate water circulatory of evaporation and crystallization system is to matching
Sulfuric acid solution is prepared in sour device and/or is recycled in ammonium hydroxide preparing device uses with ammonium hydroxide.
3. the apparatus according to claim 1, which is characterized in that the concentrated mother liquor that the solid-liquid separation system II is obtained enters
Recycled in decoloration system.
4. the apparatus according to claim 1, which is characterized in that the iminodiacetonitrile feed liquid is using hydrogen cyanide, six
Methine tetramine and formaldehyde are raw material reaction, and aminoacetonitriles heats disproportionated reaction, and hydroxyacetonitrile is reacted with aminoacetonitriles, hydroxyl second
Nitrile and ammonia are obtained by one or more of modes of raw material reaction.
5. device according to claim 4, which is characterized in that the iminodiacetonitrile feed liquid can also derive from this set
One or more of reaction solution that device reaction obtains, crystalline mother solution, concentrated mother liquor.
6. preparing iminodiacetic acid using iminodiacetonitrile feed liquid as raw material using the described in any item devices of claim 1-5
Method, which comprises the following steps:
It 1) is that reaction system is added in 65%~75% sulfuric acid solution, then iminodiacetonitrile feed liquid is added and is reacted by mass concentration
It is hydrolyzed in system, carries out decolorization after the reaction was completed and obtain destainer；
2) solid-liquid separation system I is added in ammonium hydroxide, obtained destainer is transferred to solid-liquid separation system I, adjusts the pH value of feed liquid
It is 1.5~3, decrease temperature crystalline after reaction separates to obtain iminodiacetic acid and crystalline mother solution through solid-liquid separation system I；
3) crystalline mother solution that step 2) obtains is transferred to evaporation and crystallization system, while being passed through ammonia, and the pH value of solution is adjusted to 7-7.5
It is evaporated crystallization, then separates to obtain ammonium sulfate and concentrated mother liquor through solid-liquid separation system Π.
4) step 3) enters decoloration system progress recycled from the concentrated mother liquor that solid-liquid separation system Π is obtained, and participates in next round
Reaction.
7. according to the method described in claim 6, it is characterized in that, step 1) in react temperature be 100~120 DEG C, decoloration
Temperature be 70~90 DEG C.
8. method according to claim 6 or 7, which is characterized in that be also added into activity in the decoloration system in step 1)
Charcoal and/or hydrogen peroxide；The dosage of the active carbon is the 1%-10% of iminodiacetic acid weight.
9. according to the method described in claim 6, it is characterized in that, the temperature reacted in step 1) is in 100~120 DEG C of micro-boilings
The water steamed under state is recycled to decoloration system after condensing.
10. according to the method described in claim 6, it is characterized in that, the conversion ratio of iminodiacetonitrile feed liquid exists in step 1)
It is transferred to decoloration system after 90%~97% and carries out decolorization.
11. according to the method described in claim 6, it is characterized in that, the imino-diacetic that solid-liquid separation system I is obtained in step 2)
Acetic acid is washed again, dry to get iminodiacetic acid (salt) acid product, wash water recycled.
12. according to the method described in claim 6, it is characterized in that, it is 1.5~3 that ammonification, which adjusts pH, in step 2)；The temperature of reaction
Degree is 60~80 DEG C.
13. according to the method described in claim 6, it is characterized in that in step 2) decrease temperature crystalline temperature be 10~40 DEG C, knot
The brilliant time is 0.5~4h.
14. a kind of method for preparing ammonium sulfate mixture using the described in any item devices of claim 1-4, which is characterized in that
The method adds water and sulfuric acid that hydrolysis occurs, hydrolysate is continuously anti-with ammonia again using iminodiacetonitrile feed liquid as raw material
It answers, obtains ammonium sulfate mixture by evaporative crystallization, contain ammonium sulfate and a small amount of iminodiacetic acid in the mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811634558.XA CN109369429B (en) | 2018-12-29 | 2018-12-29 | Device and method for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid |
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| CN201811634558.XA CN109369429B (en) | 2018-12-29 | 2018-12-29 | Device and method for preparing iminodiacetic acid by utilizing iminodiacetonitrile feed liquid |
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| US5849950A (en) * | 1995-05-29 | 1998-12-15 | Basf Aktiengesellschaft | Preparation of glycine-N,N-diacetic acid derivatives |
| CN102241601A (en) * | 2011-05-07 | 2011-11-16 | 安徽国星生物化学有限公司 | Preparation technology for iminodiacetic acid |
| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN104557580A (en) * | 2015-01-29 | 2015-04-29 | 重庆紫光化工股份有限公司 | Method for preparing iminodiacetic acid |
| KR20180056162A (en) * | 2016-11-18 | 2018-05-28 | 동우 화인켐 주식회사 | A method of iminodiacetic acid |
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| US5849950A (en) * | 1995-05-29 | 1998-12-15 | Basf Aktiengesellschaft | Preparation of glycine-N,N-diacetic acid derivatives |
| CN102241601A (en) * | 2011-05-07 | 2011-11-16 | 安徽国星生物化学有限公司 | Preparation technology for iminodiacetic acid |
| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN104557580A (en) * | 2015-01-29 | 2015-04-29 | 重庆紫光化工股份有限公司 | Method for preparing iminodiacetic acid |
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