CN101914037B - New process for producing high-purity iminodiacetonitrile - Google Patents
New process for producing high-purity iminodiacetonitrile Download PDFInfo
- Publication number
- CN101914037B CN101914037B CN2010102803834A CN201010280383A CN101914037B CN 101914037 B CN101914037 B CN 101914037B CN 2010102803834 A CN2010102803834 A CN 2010102803834A CN 201010280383 A CN201010280383 A CN 201010280383A CN 101914037 B CN101914037 B CN 101914037B
- Authority
- CN
- China
- Prior art keywords
- nsc
- purity
- iminodiacetonitrile
- sections
- reaction solution
- 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 relates to a new process for producing high-purity iminodiacetonitrile. The new process is characterized in that: high-purity reaction liquid is obtained by using a process for synthesizing iminodiacetonitrile at high conversion rate; and white or pale yellow high-purity iminodiacetonitrile with iminodiacetonitrile content of over 99 percent is produced by using a synthesis reaction liquid decolorizing process, an impurity removal process and three crystallization processes, wherein a part of thin waste liquid produced during the production is returned to a raw material preparation system, the rest part of waste liquid is conveyed to a biochemical device for processing, and the produced thick waste liquid is directly conveyed to an incinerator for processing, so that pollution-free production of the entire process is realized. The new process has the advantages of high product quality, white color, purity of over 99 percent high product yield, iminodiacetonitrile yield of about 90 percent during the entire production process and low three-waste treatment difficulty.
Description
Technical field
The present invention relates to a kind of technology of producing high-purity iminodiacetonitrile.
Background technology
NSC 263496 (IDAN) is the important source material of producing Glyphosate 62 IPA Salt, and the development in recent years impetus is powerful.
The production of NSC 263496 is divided into prussic acid method and hydroxyacetonitrile method with the raw material route branch.
USP discloses the technology that a large amount of prussic acid methods are produced NSC 263496, as: US2794044, US3167580, US3412137, US3886198, US3904668, US3988360, US4307037 etc.The shortcoming of above-mentioned technology is:
The first, feed hydrogen cyanic acid is difficult for preserving, and leaks easily in the production process and causes danger; The second, condition is harsh, and required time is long; The 3rd, the NSC 263496 yield is lower, and economy is relatively poor; The 4th, environmental protection pressure is big.
Produce the defective of NSC 263496 in order to overcome aforementioned prussic acid method, nearly all industrial NSC 263496 all is raw material production with the hydroxyacetonitrile.Wherein main technique comprises:
CN1830953A discloses a kind of high conversion, high-purity iminodiacetonitrile production technique, and characteristics are to add stopper, reaction solution in raw material preheating respectively, the building-up process to add inhibitor and stop polymerization, realize that the NSC 263496 yield reaches 90%.
CN101050191A discloses a kind of NSC 263496 production technique, and its control method is in hydroxyacetonitrile, to add certain vitriol in advance as buffering, and with the liquefied ammonia reaction, reaction solution adds stopper and prevents polymerization then.
Though produce NSC 263496 than high with prussic acid method yield with the hydroxyacetonitrile method, the reaction times is short, harmful toxic matter is more easy to control, and above-mentioned traditional technology still shows serious defective.Mainly show:
The first, traditional technology reaction control is relatively poor, and side reaction is many, and product purity is lower, and product appearance is second-rate.The reaction needs of hydroxyacetonitrile and ammoniacal liquor (liquefied ammonia) synthesizing iminodiacetic acid (salt) nitrile is strict carries out the change of microcosmic material proportion by material ratio hydroxyacetonitrile/ammonia (mol ratio) 2:1, all will cause the generation of a series of side reactions, thereby reduce quality product, reduces yield.In addition, the reaction pair residence time, temperature, reaction solution concentration etc. all have tangible influence to reaction.Traditional technology adopts common mixing, one section or two sections temperature controls, and the residence time is longer, thereby causes the synthesis phase polymkeric substance more, influences product yield and quality product.
The second, the reactionless liquor cleaning procedure of traditional technology.Research shows; Because there is the chemical reaction equilibrium restriction in the building-up reactions of NSC 263496; Therefore the hydroxyacetonitrile transformation efficiency generally can only reach about 95%, and that is to say still has 5% left and right sides hydroxyacetonitrile to exist in the reaction solution, and this part hydroxyacetonitrile is easy to generate polymerization under alkalescence or solutions of weak acidity; Generate the brown polymkeric substance, influence visual appearance and also influence downstream simultaneously attached to product surface and use.In addition, the by product that produces inevitably during reaction stays in the reaction solution for a long time, will bring out new polymerization and side reaction.Therefore, in order to reduce the generation of side reaction, must cut off reaction chain.And the reactionless liquor cleaning procedure of traditional technology can not cut off reaction solution generation polymeric reaction chain.Thus,, must cause the shortcoming of poor product quality though flow process has shortened, as: present industrial NSC 263496 product purity is generally about 92%, and color is a brown.
The 3rd, traditional technology generally adopts two sections to concentrate, and two sections crystalline modes reclaim product.Because the problem of reaction controlling unit, and reactionless liquor cleaning procedure, the product purity after twice crystallization of NSC 263496 is very low, and foreign matter content is also very high, can't carry out three sections and concentrate three sections crystallizations.Therefore, total yield of products generally only can reach 78 ~ 80%, and a large amount of NSC 263496s can't reclaim, and get into dense waste liquid and burn.Cause great waste.
The 4th, the NSC 263496 that traditional technology is produced all needed through feedstock purification before producing Glyphosate 62 IPA Salt, gave the downstream industry deleterious impact.The main application of NSC 263496 is the raw material as emerging agricultural chemicals Glyphosate 62 IPA Salt.The factor that influences glyphosate products quality and yield most critical is the quality of NSC 263496.But mostly about 92%, reaction solution is through neutralization for present industrial imido grpup diacetonitrile content, and solid-liquid separation goes out iminodiethanoic acid (IDA) back gained one hypo acid (IDA) product content can only guarantee 97%, and color is relatively poor, need handle through decolouring.And the mother liquor foreign matter content is high, can't apply mechanically (applying mechanically the back quality product sharply descends), can only be respectively with quadratic acid, and three hypo acid staging treating; Obtain quadratic acid (IDA, content 90%), three hypo acid (IDA; Content 70%), acid (IDA, content is below 50%) more than four times; And the above acid of secondary (shared IDA ratio 20%) all must be through refining, reaches could get into pmida98 97% or more and synthesize, and technological process is very loaded down with trivial details; Repeatedly refining, impurity is constantly accumulated in the mother liquor, exists mother liquor finally to withdraw from, and contains iminodiethanoic acid (about 20%) in the on the one hand final mother liquor, causes yield losses after withdrawing from, and increases three wastes processing costs on the other hand.
Summary of the invention
In view of above-mentioned weak point, the object of the present invention is to provide a kind of is the technology of raw material production high-purity iminodiacetonitrile with the hydroxyacetonitrile.This NSC 263496 new process of production is characterised in that: adopt high conversion NSC 263496 synthesis technique to obtain high-purity reaction solution; Adopt synthesis reaction solution decolouring, impurity removal process and three crystallization processes, produce NSC 263496 content more than 99%, color is white or lurid high-purity iminodiacetonitrile; Production process produces a rare waste liquid part and returns the preparation of raw material system, remainder dispensing biochemical treatment apparatus, and the dense waste liquid of generation directly send incinerator to handle, thereby realizes the cleaner production of whole technology.
Another object of the present invention is to provide a kind of high conversion NSC 263496 new synthetic process, and the hydroxyacetonitrile transformation efficiency is reached more than 95%, and the NSC 263496 yield reaches more than 90%.The reaction solution lighter color, side reaction is less, is easy to handle.
Another object of the present invention is to provide a kind of high conversion NSC 263496 synthesis reaction solution purification, purification technology.Particularly adopt the nanofiltration means that the impurity in the synthesis reaction solution is removed, form purified NSC 263496 mother liquor, again through crystallisation by cooling, become colours white, purity reaches the NSC 263496 product more than 99%.
Another object of the present invention also is to provide a kind of three crystallization processes of NSC 263496 product; Thereby guarantee to greatest extent NSC 263496 to be proposed from mother liquor; Make the yield of its NSC 263496 in whole production technology reach 86 ~ 92%, reduce three wastes intractability.
Another object of the present invention also is to provide a kind of color pure white, and purity reaches the NSC 263496 product more than 99%.This product is fit to directly be used for the production of iminodiethanoic acid.
To achieve these goals, embodiment of the present invention comprise that synthetic, reaction solution purifies and aspects such as product recovery, three wastes processing.The practical implementation step is following:
Synthesizing of NSC 263496
The reaction mechanism that with the hydroxyacetonitrile is the raw material production NSC 263496 is following:
Main reaction: 2HOCH
2CN+NH
3→ NH (CH
2CN)
2+ 2H
2O IDAN 1.
Side reaction: HOCH
2CN+NH
3→ NH
2CH
2CN+H
2The O aminoacetonitriles 2.
3HOCH
2CN+NH
3→ N (CH
2CN)
3+ 3H
2O nitrogen three acetonitriles 3.
Various not principal reactions 4.
Various polyreactions 5.
Through research, the contriver has grasped the various factors that influences above-mentioned reaction.
When temperature of reaction at 80～170 ℃, material proportion hydroxyacetonitrile/ammonia (mol than) is 1.8～2.1, the residence time was at 30 seconds～4 minutes; The solution total concn is more than 40%; Under the uniform condition of mixing of materials, 1. main the generation react, and promptly mainly generates title product NSC 263496 (IDAN).
When synthesis condition changes, the following variation will take place in reaction:
A) when raw material hydroxyacetonitrile foreign matter content is higher, cause side reaction 4. to increase;
B) when material proportion is higher than 2.1,, cause side reaction 2. to increase because ammonia is not enough;
C) when material proportion is lower than 1.8,, will cause side reaction 3. to increase because ammonia is excessive;
D) when the residence time is longer, will cause side reaction 5. to increase;
E) when raw material hydroxyacetonitrile concentration is low, will cause side reaction 2. to increase;
F) when raw material hydroxyacetonitrile acidity is too low, will cause side reaction 4. to increase, and be prone to cause material rotten, quality product is descended significantly;
G) when mixing is inhomogeneous, will causes side reaction 2. to reach side reaction and 5. increase.
H) when synthesis temperature is too low, speed of response is too slow, causes side reaction 5. to increase; When synthesis temperature was too high, the polymerization between the raw material increased, and 3. side reaction increases.
Therefore, in DESIGN OF REACTOR and operating process, the present invention provides following measure to realize the synthetic of high rate of rotation NSC 263496:
A) aqueous ammonia to replace liquefied ammonia is adopted in the ammonia source, to increase the stability of reinforced process metering.
B) keep material proportion (hydroxyacetonitrile: be about 2.0 ammonia), adopt control charging system batching automatically at any time in order to keep.
C) in order to shorten the residence time as far as possible, reduce back-mixing, adopt tubular reactor.The residence time that the present invention suits is 0.5 ~ 4min, and the preferred residence time should be in 0.5 ~ 2min time range.
D) in order to guarantee hydroxyacetonitrile concentration, select the high density hydroxyacetonitrile, preferred hydroxyacetonitrile concentration is 48 ~ 50%.
E) in order to guarantee hydroxyacetonitrile acidity, in hydroxyacetonitrile, add buffered soln in advance, like ammonium phosphate buffer solution, ammonium sulfate buffered soln, making hydroxyacetonitrile raw material PH is 2.0 ~ 3.0.
F) in order to guarantee that mixing of materials is even, sets up material mixer.
G) in order to control side reaction as far as possible, synthesis temperature control condition is 80 ~ 170 ℃.Preferred control condition is 150 ~ 160 ℃ of reactor drum front end temperature controls, 145 ~ 155 ℃ of stage casing controlled temperature, 140 ~ 145 ℃ of back segment controlled temperature.
Detailed process is following:
The synthetic following steps that include of said NSC 263496: quality percentage composition behind the buffered soln is 48 ~ 50% with adding, pH value is that 2.0 ~ 3.0 hydroxyacetonitrile is preheated to 90 ~ 120 ℃, pressure 0.8MPa through hydroxyacetonitrile volume pump metering back entering hydroxyacetonitrile preheater; Simultaneously liquefied ammonia is become ammoniacal liquor through the ammoniacal liquor Preparation tank, after will disposing again ammoniacal liquor get into the ammoniacal liquor preheater through ammoniacal liquor volume pump metering back, be preheated to 90 ~ 120 ℃, pressure is 0.8MPa; With mol ratio after the preheating is that hydroxyacetonitrile and the ammoniacal liquor of 2:1 gets compound through the material mixer thorough mixing; Again compound is sent into the tubular reactor reaction; The control residence time is 0.5 ~ 4min in tubular reactor; Synthesis temperature control condition is 80 ~ 170 ℃, obtains the NSC 263496 synthesis reaction solution;
Through the control of above-mentioned condition, synthesis reactor outlet hydroxyacetonitrile transformation efficiency reaches more than 95%, and the NSC 263496 yield reaches more than 90%; The reaction solution color presents wine red; Impurity is mainly 5% left and right sides hydroxyacetonitrile, and 1% following molecular weight is 200 ~ 400 polymkeric substance, 3% left and right sides aminoacetonitriles.
The purification of NSC 263496 synthesis reaction solution and three crystallization processes
Product purifies: the NSC 263496 synthesis reaction solution is a weakly alkaline under the normal condition, and is very unstable under hot conditions, and various polyreactions, oxidizing reaction and other side reaction take place easily.The reason of traditional technology poor product quality that Here it is.The present invention has increased the reaction solution cleaning section newly on high conversion IDAN synthetic technology basis, through the purification of reaction solution, removed wherein by product, thereby improves product purity, improves product colour.
Through research, the contriver finds to adopt suitable nf membrane, sorbent material, flocculation agent, ion exchange resin etc. can the impurity in the IDAN solution be removed, and the IDAN loss amount seldom.
Wherein, suitable nf membrane should satisfy 80 ℃ of use temperatures, pressure 0.4MPa, the material of anti-system corrosion, the minimum molecular weight cut-off 150MWCO of nf membrane.
It is big that suitable sorbent material should satisfy specific surface area, and the band colored foreign is had very strong adsorptivity and IDAN is not had adsorptive power basically.The preferred sorbent material of the present invention is that specific surface area is greater than 300m
2The gac of/g, atlapulgite, zeyssatite etc.
Suitable flocculation agent, ion exchange resin should satisfy can effective elimination synthesis reaction solution color, and the IDAN rate of loss is lower than 2%.
Said three crystallization processes are: adopt three sections to concentrate, and three sections crystallization processes, concrete steps are:
NSC 263496 synthesis reaction solution after the purification is at one section cooling crystallizer crystallisation by cooling, 15 ℃ of Tcs, and crystal filters through a centrifugal filter; Get one section crystalline mother solution and filter cake; Filter cake is delivered to vacuum drying oven, and in 45 ℃ of oven dry down, getting purity is the pure white NSC 263496 product of color more than 99%; In one section crystallization, about 85% NSC 263496 in the NSC 263496 synthesis reaction solution behind the reclaiming clean; One section crystalline mother solution is neutralized to pH=3 with 60% sulfuric acid again, sends into first vaporizer and concentrates 55 ℃ of thickening temperatures; With NSC 263496 concentration in one section crystalline mother solution is 7.6% to be concentrated into approximately 25%, delivers to two sections cooling crystallizers then, 15 ℃ of crystallization control temperature; Filter through the secondary centrifuging filter; Get two sections crystalline mother solutions and filter cake, filter cake is delivered to vacuum drying oven, in 45 ℃ of oven dry down; Purity be the pure white NSC 263496 product more than 99%, about 13% NSC 263496 in the NSC 263496 synthesis reaction solution behind two sections crystallization reclaiming cleans; Approximately contain 5% NSC 263496 in two sections crystalline mother solutions; 10% left and right sides hydroxyacetonitrile verivate; 3 ~ 5% aminoacetonitriles verivates, again two sections crystalline mother solutions being delivered to second vaporizer, to be concentrated in two sections crystalline mother solutions NSC 263496 content about about 25%, gets into three sections cooling crystallizers; 15 ℃ of Tcs; The NSC 263496 of separating out filters through three centrifugal filters, and filter cake is in 45 ~ 50 ℃ of oven dry down, purity is about 99% white NSC 263496 product; About 1.5% NSC 263496 in three sections crystallizations NSC 263496 synthesis reaction solution after can reclaiming clean, these three crystallization processes can totally reclaim the NSC 263496 in the NSC 263496 synthesis reaction solution after purifying more than 99%;
The three wastes are handled
Contain little ammonia in the flashing tower exit gas, water vapour, nitrogen.After condensation, ammoniacal liquor is returned material mixer inlet dilution liquefied ammonia.Nitrogen is blow-off valve emptying through the top.
Contain the band look polymeric impurities of molecular weight 200 ~ 400 in the waste liquid that the nanofiltration strainer produces, other contains 32% left and right sides NSC 263496, small amount of hydroxyl groups acetonitrile, a small amount of aminoacetonitriles vitriol.This dense waste liquid directly send liquid waste incinerator to burn the back discharging.The NSC 263496 that loses from here accounts for 2 ~ 3%.
The liquid that first vaporizer-condenser and second vaporizer-condenser come out is the water of COD content about 500, and a part is returned the ammoniacal liquor preparation process, and residue send biochemical treatment tank to handle.
The mother liquor that after three sections cooling crystallizer crystallizations, filters out from three centrifugal filters contains a small amount of unreacted hydroxyacetonitrile, a small amount of NSC 263496; A small amount of aminoacetonitriles vitriol, small amount of ammonium sulfate is because complicated component; Recovery value is not high, directly send liquid waste incinerator to burn the back discharging.
Advantage of the present invention:
The hydroxyacetonitrile transformation efficiency is high, and the NSC 263496 yield is high.Owing to adopted automatic control system reinforced, set up static mixer, guaranteed to react and undertaken by metering, the hydroxyacetonitrile transformation efficiency is reached more than 95%.In addition,, improved product yield, the NSC 263496 yield is reached about 90% owing to adopt three crystallization processes.
Good product quality.The present invention makes product purity bring up to more than 99% owing to adopted the reaction solution purification system, and product colour is a white.
The three wastes are handled simple.Rare component of effluent is simple, can directly carry out routine biochemistry and handle; Dense waste liquid amount is less, send the incinerator burning disposal.
Description of drawings
The make a living technology process schematic flow sheet of production of high purity NSC 263496 of Fig. 1.
Among the figure, 1. ammoniacal liquor Preparation tank; 2. ammoniacal liquor volume pump; 3. ammoniacal liquor preheater; 4. hydroxyacetonitrile volume pump; 5. hydroxyacetonitrile preheater; 6. material mixer; 7. tubular reactor; 8. flashing tower; 9. cleaner; 10. one section cooling crystallizer; 11. centrifugal filter; 12. first vaporizer; 13. two sections cooling crystallizers; 14. secondary centrifuging filter; 15. second vaporizer; 16. three sections cooling crystallizers; 17. three centrifugal filters; 18. flash condenser; 19. first vaporizer-condenser; 20. second vaporizer-condenser; 21. vacuum drying oven.
Embodiment
Embodiment 1
Certain 20,000 tons of/year NSC 263496 full scale plant.According to scheme operation provided by the invention, its operating parameter and control indexes are following:
Flash condenser 18; The water of condensation that first evaporator-condenser, 19, the second evaporator-condensers 20 produce amounts to 5660kg/h, and wherein the 1639kg/h water of condensation is with being pumped to ammoniacal liquor Preparation tank 1; With 555kg/h purity is that 99.5% liquefied ammonia mixes; Generate the 2194kg/h weak ammonia, through detecting, this ammonia concn is 25.3%.After 3 meterings of ammoniacal liquor volume pump, get into ammoniacal liquor preheater 4, be preheated to 90 ~ 120 ℃, pressure 0.8MPa.The pH that regulates through ammonium phosphate buffer solution or ammonium sulfate buffered soln is that 2.0 ~ 3.0 50% raw material hydroxyacetonitrile 7407kg/h press hydroxyacetonitrile via the hydroxyacetonitrile volume pump 4 of automatic feeding system control: the amount adding hydroxyacetonitrile preheater 5 of ammonia=2:1 (mol than); Heater outlet temperature is 90 ~ 120 ℃, pressure 0.8MPa.
Two materials get into material mixer 6 thorough mixing immediately, mix 140 ℃ of back temperature of charge, pressure 0.75MPa.Get into tubular reactor 7 and carry out the reaction of synthesizing iminodiacetic acid (salt) nitrile.150 ℃ of reactor drum front-end temperature controls, 145 ℃ of stage casing controlled temperature, 140 ℃ of back segment controlled temperature.Material total residence time in reactor drum is 2 minutes.
Tubular reactor outlet reaction solution is a weak yellow liquid, and its IDAN concentration is 29.5%, leans on self pressure current to flashing tower 8, removes wherein unreacted little ammonia and portion water steam.For ammonia removal is abundant, the flashing tower bottom feeds 10000Nm
3/ h nitrogen stripping.The flashing tower liquid phase of working off one's feeling vent one's spleen after condensing surface 18 condensations is returned ammoniacal liquor Preparation tank 1, and gas phase is directly discharged.
Material IDAN concentration 34% after the flash distillation, 50 ℃ of temperature, flow is 8337kg/h, is pumped to the nanofiltration strainer through nanofiltration, control nanofiltration strainer sewage discharge rate 2%, the operational condition of soiling solution/clear liquid throughput ratio 20 obtains the colourless basically nanofiltration liquid of 8170kg/h.Nanofiltration liquid is at one section cooling crystallizer 10 crystallisation by cooling, 15 ℃ of Tcs, and crystal filters through a centrifugal filter 11; Get one section crystalline mother solution and filter cake; Filter cake is delivered to vacuum drying oven 21, in 45 ℃ of down oven dry, purity is 99.3% the pure white NSC 263496 product 2378kg/h of color.
One section crystalline mother solution is neutralized to PH=3 with 60% sulfuric acid, sends into first vaporizer 12 and concentrates 55 ℃ of thickening temperatures; Solution is concentrated into about 25% from IDAN concentration 7.6%; Deliver to two sections cooling crystallizers 13 then, 15 ℃ of crystallization control temperature are filtered through secondary centrifuging filter 14; Get the oven dry of two sections crystalline mother solutions and filter cake, getting purity is the pure white NSC 263496 product 372kg/h more than 99%.
Approximately contain 5%IDAN in two sections crystalline mother solutions, 10% left and right sides hydroxyacetonitrile verivate, 3 ~ 5% aminoacetonitriles verivates.Deliver to second vaporizer 15 and be concentrated into IDAN content about about 25%.Get into three sections crystallisation by cooling molds 16,15 ℃ of Tcs.The NSC 263496 of separating out filters through three centrifugal filters 17, and filter cake is in 45 ~ 50 ℃ of oven dry down, purity is about 99% white NSC 263496 product 48kg/h.
Through calculating, three crystalline products amount to and reclaim purity is 99% white NSC 263496 product 2798kg/h, calculates with hydroxyacetonitrile, and total recovery is 89.8%.
During normal the operation, rare waste liquid 1264kg/h that flash condenser 18 produces, rare waste liquid 4098kg/h that first vaporizer-condenser 19 produces, second vaporizer-condenser 20 produces rare waste liquid 1057kg/h.Wherein, rare waste liquid 375kg/h that rare waste liquid that flash distillation produces returns the generation of ammoniacal liquor Preparation tank 1, the first vaporizer-condenser fully returns ammoniacal liquor Preparation tank 1, remains rare waste liquid and amounts to 4780kg/h.This waste water COD content about 500 send biochemical treatment apparatus.
The dense waste liquid amount that nanofiltration produces is 167kg/h, complicated component, and recovery difficult is big, directly send the incinerator burning disposal.
The dense waste liquid amount of three centrifugal filter generations is 76kg/h, complicated component, and recovery difficult is big, directly send the incinerator burning disposal.
Embodiment 2
Same set of device changes reaction solution purification and decoloration technology into the charcoal absorption decolouring, and all the other technologies are constant.Examine 1 hourly output to get:
Purity is 99% white NSC 263496 product 2718kg/h, calculates with hydroxyacetonitrile, and total recovery is 87.2%.
Send rare waste liquid 4880kg/h of biochemical treatment.
The dense waste liquid that send incinerator to handle is total to 175kg/h.
Consumption rate surface-area 600m
2/ g gac 100kg/h.
Embodiment 3
Same set of device changes reaction solution purification and decoloration technology into ion-exchange resin decolorization, and all the other technologies are constant.Examine 1 hourly output to get:
Purity is 99% white NSC 263496 product 2685kg/h, calculates with hydroxyacetonitrile, and total recovery is 86.0%.
Send rare waste liquid 4980kg/h of biochemical treatment.
The dense waste liquid that send incinerator to handle is total to 165kg/h.
Consume wastewater treatment resin 500kg/h.
Claims (6)
1. technology of producing high-purity iminodiacetonitrile, it is characterized in that: this technology comprises: synthetic, the purification of NSC 263496 synthesis reaction solution of NSC 263496, three crystallizations and three wastes treatment process;
The synthetic following steps that include of said NSC 263496: quality percentage composition behind the buffered soln is 48 ~ 50% with adding, pH value be 2.0 ~ 3.0 hydroxyacetonitrile through hydroxyacetonitrile volume pump (4) metering afterwards entering hydroxyacetonitrile preheater (5) be preheated to 90 ~ 120 ℃, pressure 0.8MPa; Simultaneously liquefied ammonia is become ammoniacal liquor through ammoniacal liquor Preparation tank (1), the ammoniacal liquor after will disposing again gets into ammoniacal liquor preheater (3) through ammoniacal liquor volume pump (2) metering back, is preheated to 90 ~ 120 ℃, and pressure is 0.8MPa; With mol ratio after the preheating is that hydroxyacetonitrile and the ammoniacal liquor of 2:1 gets compound through material mixer (6) thorough mixing; Again compound is sent into tubular reactor (7) reaction; The control residence time is 0.5 ~ 4min in tubular reactor (7); Synthesis temperature control condition is 80 ~ 170 ℃, obtains the NSC 263496 synthesis reaction solution;
The purification of said NSC 263496 synthesis reaction solution comprises can remove NSC 263496 synthesis reaction solution color and removal impurity, and few nanofiltration, absorption, flocculation, the ion exchange process of NSC 263496 loss amount;
Said three crystallization processes are: adopt three sections to concentrate, and three sections crystallization processes, its concrete steps are:
NSC 263496 synthesis reaction solution after the purification is at one section cooling crystallizer (10) crystallisation by cooling, 15 ℃ of Tcs, and crystal filters through a centrifugal filter (11); Get one section crystalline mother solution and filter cake; Filter cake is delivered to vacuum drying oven (21), and in 45 ℃ of oven dry down, getting purity is the pure white NSC 263496 product of color more than 99%; In one section crystallization, 85% NSC 263496 in the NSC 263496 synthesis reaction solution behind the reclaiming clean; One section crystalline mother solution is neutralized to pH=3 with 60% sulfuric acid again, sends into first vaporizer (12) and concentrates 55 ℃ of thickening temperatures; With NSC 263496 concentration in one section crystalline mother solution is 7.6% to be concentrated into 25%, delivers to two sections cooling crystallizers (13) then, 15 ℃ of crystallization control temperature; Filter through secondary centrifuging filter (14); Get two sections crystalline mother solutions and filter cake, filter cake is delivered to vacuum drying oven (21), in 45 ℃ of oven dry down; Purity be the pure white NSC 263496 product more than 99%, 13% NSC 263496 in the NSC 263496 synthesis reaction solution behind two sections crystallization reclaiming cleans; Contain 5% NSC 263496 in two sections crystalline mother solutions; 10% hydroxyacetonitrile verivate; 3 ~ 5% aminoacetonitriles verivates are delivered to second vaporizer (15) with two sections crystalline mother solutions again and are concentrated into NSC 263496 content 25% in two sections crystalline mother solutions, get into three sections cooling crystallizers (16); 15 ℃ of Tcs; The NSC 263496 of separating out filters through three centrifugal filters (17), and filter cake is in 45 ~ 50 ℃ of oven dry down, purity is 99% white NSC 263496 product; 1.5% NSC 263496 in three sections crystallizations NSC 263496 synthesis reaction solution after can reclaiming clean, these three crystallization processes can totally reclaim the NSC 263496 in the NSC 263496 synthesis reaction solution after purifying more than 99%;
Said three wastes treatment process comprises:
1. contain little ammonia in flashing tower (8) exit gas, water vapour, nitrogen returns ammoniacal liquor to ammoniacal liquor Preparation tank (1) inlet dilution liquefied ammonia after flash condenser (18) condensation, and nitrogen is through flash condenser (18) top blow-off valve emptying;
2. contain the band look polymeric impurities of molecular weight 200 ~ 400 in the waste liquid that cleaner (9) produces, other contains 32% NSC 263496, small amount of hydroxyl groups acetonitrile, a small amount of aminoacetonitriles vitriol; This dense waste liquid directly send liquid waste incinerator to burn the back discharging; The liquid that first vaporizer-condenser (19) and second vaporizer-condenser (20) come out is the water of chemical oxygen demand COD content 500 mg/litre, and a part is returned the ammoniacal liquor preparation process, and residue send biochemical treatment tank to handle;
3. the mother liquor that after three sections cooling crystallizer crystallizations, filters out from three centrifugal filters (17); Contain a small amount of unreacted hydroxyacetonitrile, a small amount of NSC 263496, a small amount of aminoacetonitriles vitriol; Small amount of ammonium sulfate; Because complicated component, recovery value is not high, directly send liquid waste incinerator to burn the back discharging.
2. the technology of production high-purity iminodiacetonitrile according to claim 1 is characterized in that: said damping fluid is selected from ammonium phosphate buffer solution or ammonium sulfate buffered soln.
3. the technology of production high-purity iminodiacetonitrile according to claim 1; It is characterized in that: said synthesis temperature control condition is 150 ~ 160 ℃ of tubular reactor front end temperature controls; 145 ~ 155 ℃ of stage casing controlled temperature, 140 ~ 145 ℃ of back segment controlled temperature.
4. the technology of production high-purity iminodiacetonitrile according to claim 1; It is characterized in that: the nf membrane that adopts in the said nanofiltration technique should satisfy 80 ℃ of use temperatures; Pressure 0.4MPa, the material of anti-system corrosion, the minimum molecular weight cut-off 150MWCO of nf membrane.
5. the technology of production high-purity iminodiacetonitrile according to claim 1 is characterized in that: said sorbent material is selected from specific surface area greater than 300m
2In the gac of/g, atlapulgite, the zeyssatite one or more.
6. the technology of production high-purity iminodiacetonitrile according to claim 1; It is characterized in that: said flocculation process and ion exchange process should satisfy can effective elimination NSC 263496 synthesis reaction solution color, and the NSC 263496 rate of loss is lower than 2%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102803834A CN101914037B (en) | 2010-09-14 | 2010-09-14 | New process for producing high-purity iminodiacetonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102803834A CN101914037B (en) | 2010-09-14 | 2010-09-14 | New process for producing high-purity iminodiacetonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101914037A CN101914037A (en) | 2010-12-15 |
| CN101914037B true CN101914037B (en) | 2012-11-28 |
Family
ID=43321716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102803834A Active CN101914037B (en) | 2010-09-14 | 2010-09-14 | New process for producing high-purity iminodiacetonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101914037B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787919B (en) * | 2012-12-27 | 2016-06-29 | 三达膜科技（厦门）有限公司 | A kind of discoloration method of Iminodiacetonitrile 1,1'-Imidodiacetonitrile |
| CN103910651B (en) * | 2014-03-10 | 2016-01-20 | 河北诺达化工设备有限公司 | Iminodiacetonitrile continuous crystallisation technique |
| CN104892454B (en) * | 2015-05-11 | 2017-08-25 | 重庆紫光化工股份有限公司 | A kind of iminodiacetonitrile crystal formation I and preparation method thereof |
| CN105272881B (en) * | 2015-06-09 | 2019-10-08 | 重庆紫光化工股份有限公司 | The clean preparation method of iminodiacetonitrile |
| CN105315175B (en) * | 2015-06-09 | 2018-01-16 | 重庆紫光化工股份有限公司 | The clean preparation method of iminodiacetonitrile |
| CN105315173B (en) * | 2015-06-09 | 2017-08-22 | 重庆紫光化工股份有限公司 | The discoloration method of iminodiacetonitrile |
| CN105315174B (en) * | 2015-06-09 | 2017-11-07 | 重庆紫光化工股份有限公司 | Sulfurous acid as formaldehyde blocking agent and decolorising agent application |
| CN113292453B (en) * | 2021-06-04 | 2023-05-02 | 四川能投建工集团设计研究院有限公司 | Continuous crystallization process of iminodiacetonitrile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187301A (en) * | 1989-10-26 | 1993-02-16 | W. R. Grace & Co.-Conn. | Preparation of iminodiacetonitrile from glycolonitrile |
| CN101148424A (en) * | 2006-09-18 | 2008-03-26 | 李斌 | Continuous and clean producing method for iminodiacetonitrile by using combined reactor |
| CN101544574A (en) * | 2008-03-28 | 2009-09-30 | 李斌 | Environment-friendly clean process method for continuously synthesizing iminodiacetic acid (salt) |
-
2010
- 2010-09-14 CN CN2010102803834A patent/CN101914037B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187301A (en) * | 1989-10-26 | 1993-02-16 | W. R. Grace & Co.-Conn. | Preparation of iminodiacetonitrile from glycolonitrile |
| CN101148424A (en) * | 2006-09-18 | 2008-03-26 | 李斌 | Continuous and clean producing method for iminodiacetonitrile by using combined reactor |
| CN101544574A (en) * | 2008-03-28 | 2009-09-30 | 李斌 | Environment-friendly clean process method for continuously synthesizing iminodiacetic acid (salt) |
Non-Patent Citations (2)
| Title |
|---|
| 以天然气为原料生产亚氨基二乙腈的污染物产生及治理措施;王红磊 等;《环境科学与管理》;20090131;第34卷(第1期);84-88，92 * |
| 王红磊 等.以天然气为原料生产亚氨基二乙腈的污染物产生及治理措施.《环境科学与管理》.2009,第34卷(第1期),84-88，92. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101914037A (en) | 2010-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101914037B (en) | New process for producing high-purity iminodiacetonitrile | |
| CN102295379B (en) | Method for treating desulfurization waste liquid of wet oxidation method | |
| CN103435211B (en) | A kind of method for purifying and recycling of F-T synthesis water | |
| JP2002511832A (en) | Method and plant for treating liquid organic waste | |
| FR2474901A1 (en) | PROCESS AND EQUIPMENT FOR THE TREATMENT OF ORGANIC MATTER CONTAINING NITROGEN COMPOUNDS | |
| CN105110587A (en) | Sludge pretreatment technology with desalting effect | |
| CN102491562A (en) | High-ammonia-nitrogen waste water resource recovery technology | |
| CN105254141A (en) | Treatment method and treatment system for high-concentration mixed salt organic wastewater | |
| CN101200336B (en) | Process for zero-discharge treatment of o-phenylenediamine sodium sulfide reduction wastewater | |
| CN1986390A (en) | Process of purifying and recovering waste sulfuric acid containing organic impurity | |
| CN110615456B (en) | Device and process for continuously producing aluminum sulfate octadecahydrate | |
| CN109912096A (en) | A kind of pretreated method of o-methyl formate benzene sulfonamide waste water sub-prime | |
| CN105859005A (en) | Method and system for treating stainless steel cold-rolling and pickling waste acid | |
| CN102336650B (en) | Stripping process and device for removing organic impurities in brufen sodium salt | |
| CN115010309A (en) | Iron phosphate wastewater zero-discharge treatment system and treatment process | |
| CN206858347U (en) | A kind of device of desulfurization wastewater sub-prime crystallization treatment | |
| CN101117314A (en) | Production method of sodium citrate | |
| CN101607891B (en) | Recrystallization production method for citric acid | |
| CN102153224A (en) | Treatment technology for industrial sewage from sodium carboxymethylcellulose | |
| CN109095691A (en) | A kind of recycling processing method of brine waste | |
| CN108569812A (en) | A kind of processing system and processing method of the waste water containing low-concentration sulfuric acid | |
| CN206188554U (en) | Zero discharge system of coal fired power plant desulfurization waste water | |
| CN102515384A (en) | Technology for turning wastewater of melamine resin production into resource | |
| CN102602890A (en) | Method and device for recycling useful substances from waste hydrochloric acid liquor | |
| CN114634271A (en) | Waste water zero-discharge treatment process for garbage transfer station |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |