CN101914037A - New process for producing high-purity iminodiacetonitrile - Google Patents
New process for producing high-purity iminodiacetonitrile Download PDFInfo
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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 novel process of producing high-purity iminodiacetonitrile.
Background technology
Iminodiacetonitrile (IDAN) is the important source material of producing glyphosate, and the development in recent years impetus is powerful.
The production of iminodiacetonitrile is divided into prussic acid method and hydroxyacetonitrile method with the raw material route branch.
U.S. Patent Publication the technology of a large amount of prussic acid method production iminodiacetonitrile, 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, the condition harshness, required time is long; The 3rd, the iminodiacetonitrile yield is lower, and economy is relatively poor; The 4th, environmental protection pressure is big.
In order to overcome the defective of aforementioned prussic acid method production iminodiacetonitrile, nearly all industrial iminodiacetonitrile 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 antioxidant and stop polymerization, realize that the iminodiacetonitrile yield reaches 90%.
CN101050191A discloses a kind of iminodiacetonitrile production technique, and its control method is to add certain vitriol in advance as buffering in hydroxyacetonitrile, and with the liquefied ammonia reaction, reaction solution adds stopper and prevents polymerization then.
Though with prussic acid method yield height, the reaction times is short with hydroxyacetonitrile method production iminodiacetonitrile ratio, harmful toxic matter is more easy to control, and above-mentioned traditional technology still shows serious defective.Mainly show:
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 of hydroxyacetonitrile and ammoniacal liquor (liquefied ammonia) synthesizing iminodiacetic acid (salt) nitrile needs strictness to carry 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 reactionless liquor cleaning procedure of traditional technology.Studies show that, because there is the chemical reaction equilibrium restriction in the building-up reactions of iminodiacetonitrile, therefore the hydroxyacetonitrile transformation efficiency generally can only reach about 95%, that is to say still has 5% left and right sides hydroxyacetonitrile to exist in the reaction solution, 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 the 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 iminodiacetonitrile product purity is generally about 92%, and color is a brown.
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 iminodiacetonitrile 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 iminodiacetonitrile can't reclaim, and enter dense waste liquid and burn.Cause great waste.
The iminodiacetonitrile that traditional technology is produced all needed to bring disadvantageous effect through feedstock purification to downstream industry before producing glyphosate.The main application of iminodiacetonitrile is the raw material as emerging agricultural chemicals glyphosate.The factor that influences glyphosate products quality and yield most critical is the quality of iminodiacetonitrile.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 mother liquor foreign matter content height, can't apply mechanically (applying mechanically the back quality product sharply descends), can only be respectively with quadratic acid, 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, reach that just to enter pmida98 more than 97% synthetic, 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 novel process of raw material production high-purity iminodiacetonitrile with the hydroxyacetonitrile.This iminodiacetonitrile new process of production is characterised in that: adopt high conversion iminodiacetonitrile synthesis technique to obtain high-purity reaction solution; Adopt synthesis reaction solution decolouring, impurity removal process and three crystallization processes, production iminodiacetonitrile content is more than 99%, and 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 iminodiacetonitrile new synthetic process, and the hydroxyacetonitrile transformation efficiency is reached more than 95%, and the iminodiacetonitrile yield reaches more than 90%.The reaction solution color is more shallow, and side reaction is less, is easy to handle.
Another object of the present invention is to provide a kind of high conversion iminodiacetonitrile synthesis reaction solution purification, purification technology.Particularly adopt the nanofiltration means that the impurity in the synthesis reaction solution is removed, form purified iminodiacetonitrile mother liquor, again through crystallisation by cooling, become colours white, purity reaches the iminodiacetonitrile product more than 99%.
Another object of the present invention also is to provide a kind of three crystallization processes of iminodiacetonitrile product, thereby guarantee to greatest extent iminodiacetonitrile to be proposed from mother liquor, make the yield of its iminodiacetonitrile 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 iminodiacetonitrile product more than 99%.This product is fit to be directly used in 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.Concrete implementation step is as follows:
Synthesizing of iminodiacetonitrile
The reaction mechanism that with the hydroxyacetonitrile is the raw material production iminodiacetonitrile is as follows:
Main reaction: 2HOCH2CN+NH3 → NH (CH2CN) 2+2H2O IDAN 1.
Side reaction: HOCH2CN+NH3 → NH2CH2CN+the H2O aminoacetonitriles 2.
3HOCH2CN+NH3 → N (CH2CN) 3+3H2O nitrogen three acetonitriles 3.
Various not principal reactions 4.
By 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 target product iminodiacetonitrile (IDAN).
When synthesis condition changes, following variation will take place in reaction:
When raw material hydroxyacetonitrile foreign matter content is higher, cause side reaction 4. to increase;
When material proportion is higher than 2.1, because the ammonia deficiency causes side reaction 2. to increase;
When material proportion is lower than 1.8,, will cause side reaction 3. to increase because ammonia is excessive;
When the residence time is longer, will cause side reaction 5. to increase;
When raw material hydroxyacetonitrile concentration is low, will cause side reaction 2. to increase;
When raw material hydroxyacetonitrile acidity is too low, will cause side reaction 4. to increase, and easily cause material rotten, quality product is descended significantly;
When mixing is inhomogeneous, will causes side reaction 2. to reach side reaction and 5. increase.
When synthesis temperature was too low, speed of response was too slow, caused 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 invention provides following measure and realize the synthetic of high rate of rotation iminodiacetonitrile:
Aqueous ammonia to replace liquefied ammonia is adopted in the ammonia source, to increase the stability of reinforced process metering.
In order to keep keeping material proportion (hydroxyacetonitrile: be about 2.0 ammonia), adopt control charging system batching automatically at any time.
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.
In order to guarantee hydroxyacetonitrile concentration, select the high density hydroxyacetonitrile, preferred hydroxyacetonitrile concentration is 48 ~ 50%.
In order to guarantee hydroxyacetonitrile acidity, in hydroxyacetonitrile, add buffered soln in advance, as ammonium phosphate buffer solution, ammonium sulfate buffered soln, making hydroxyacetonitrile raw material PH is 2.0 ~ 3.0.
In order to guarantee that mixing of materials is even, sets up material mixer.
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 front end temperature controls, 145 ~ 155 ℃ of stage casing controlled temperature, 140 ~ 145 ℃ of back segment controlled temperature.
Detailed process is as follows:
The synthetic following steps that include of described iminodiacetonitrile: quality percentage composition behind the buffered soln is 48 ~ 50% with adding, pH value is that 2.0 ~ 3.0 hydroxyacetonitrile enters the hydroxyacetonitrile preheater after by the metering of hydroxyacetonitrile volume pump and is preheated to 90 ~ 120 ℃, pressure 0.8Mpa; Simultaneously liquefied ammonia is become ammoniacal liquor by the ammoniacal liquor Preparation tank, after will preparing again ammoniacal liquor enter the ammoniacal liquor preheater by after the ammoniacal liquor volume pump metering, 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 by 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 iminodiacetonitrile synthesis reaction solution;
By the control of above-mentioned condition, synthesis reactor outlet hydroxyacetonitrile transformation efficiency reaches more than 95%, and the iminodiacetonitrile yield reaches more than 90%, the reaction solution color presents burgundy, 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 iminodiacetonitrile synthesis reaction solution and three crystallization processes
Product purifies: the iminodiacetonitrile 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, by the purification of reaction solution, removed wherein by product, thereby improves product purity, improves product colour.
By research, the contriver finds to adopt suitable nanofiltration membrane, sorbent material, flocculation agent, ion exchange resin etc. the impurity in the IDAN solution can be removed, and the IDAN loss amount seldom.
Wherein, suitable nanofiltration membrane should satisfy 80 ℃ of use temperatures, pressure 0.4MPa, the material of anti-system corrosion, the minimum molecular weight cut-off 150MWCO of nanofiltration 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 substantially.The preferred sorbent material of the present invention is the gac of specific surface area greater than 300m2/g, atlapulgite, diatomite 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%.
Described three crystallization processes are: adopt three sections to concentrate, and three sections crystallization processes, concrete steps are:
Iminodiacetonitrile synthesis reaction solution after the purification is at one section cooling crystallizer crystallisation by cooling, 15 ℃ of Tcs, crystal filters through a centrifugal filter, get one section crystalline mother solution and filter cake, filter cake is delivered to vacuum drying oven, in 45 ℃ of down oven dry, purity is the pure white iminodiacetonitrile product of color more than 99%, in one section crystallization, about 85% iminodiacetonitrile in the iminodiacetonitrile synthesis reaction solution behind the reclaiming clean; One section crystalline mother solution is neutralized to PH=3 with 60% sulfuric acid again, sending into first vaporizer concentrates, 55 ℃ of thickening temperatures, with iminodiacetonitrile concentration in one section crystalline mother solution is 7.6% to be concentrated into about 25%, deliver 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 down oven dry, purity is pure white iminodiacetonitrile product more than 99%, about 13% iminodiacetonitrile in the iminodiacetonitrile synthesis reaction solution behind two sections crystallization reclaiming cleans; Approximately contain 5% iminodiacetonitrile in two sections crystalline mother solutions, 10% left and right sides hydroxyacetonitrile derivative, 3 ~ 5% aminoacetonitriles derivatives, again two sections crystalline mother solutions are delivered to second vaporizer and be concentrated into iminodiacetonitrile content about about 25% in two sections crystalline mother solutions, enter three sections cooling crystallizers, 15 ℃ of Tcs, the iminodiacetonitrile of separating out is filtered through three centrifugal filters, filter cake is in 45 ~ 50 ℃ of oven dry down, purity is about 99% white iminodiacetonitrile product, about 1.5% iminodiacetonitrile in three sections crystallizations iminodiacetonitrile synthesis reaction solution after can reclaiming clean, these three crystallization processes can totally reclaim the iminodiacetonitrile in the iminodiacetonitrile 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 the material mixer inlet and dilute liquefied ammonia.Nitrogen is through top blow-off valve emptying.
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 iminodiacetonitrile, 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 iminodiacetonitrile 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 filters out from three centrifugal filters after three sections cooling crystallizer crystallizations contains a small amount of unreacted hydroxyacetonitrile, a small amount of iminodiacetonitrile, 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:
Hydroxyacetonitrile transformation efficiency height, iminodiacetonitrile yield height.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 iminodiacetonitrile 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 novel process process flow diagram of production of high purity iminodiacetonitrile 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
Certain 20,000 tons of/year iminodiacetonitrile full scale plant.According to scheme operation provided by the invention, its operating parameter and control indexes are as follows:
Two materials enter material mixer 6 thorough mixing immediately, mix 140 ℃ of back temperature of charge, pressure 0.75MPa.Enter tubular reactor 7 and carry out the reaction of synthesizing iminodiacetic acid (salt) nitrile.150 ℃ of reactor front-end temperature controls, 145 ℃ of stage casing controlled temperature, 140 ℃ of back segment controlled temperature.Material total residence time in reactor is 2 minutes.
Tubular reactor outlet reaction solution is a weak yellow liquid, and its IDAN concentration is 29.5%, to flashing tower 8, removes wherein unreacted little ammonia and portion water steam by self pressure current.For ammonia removal is abundant, the flashing tower bottom feeds 10000Nm3/h nitrogen stripping.The flashing tower liquid phase of working off one's feeling vent one's spleen after condenser 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 substantially 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 iminodiacetonitrile product 2378kg/h of color.
One section crystalline mother solution is neutralized to PH=3 with 60% sulfuric acid, sending into first vaporizer 12 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, two sections crystalline mother solutions and the oven dry of filter cake filter cake, purity is pure white iminodiacetonitrile product 372kg/h more than 99%.
Approximately contain 5%IDAN in two sections crystalline mother solutions, 10% left and right sides hydroxyacetonitrile derivative, 3 ~ 5% aminoacetonitriles derivatives.Deliver to second vaporizer 15 and be concentrated into IDAN content about about 25%.Enter three sections crystallisation by cooling crystallizers 16,15 ℃ of Tcs.The iminodiacetonitrile of separating out is filtered through three centrifugal filters 17, and filter cake is in 45 ~ 50 ℃ of oven dry down, purity is about 99% white iminodiacetonitrile product 48kg/h.
By calculating, three crystalline products amount to and reclaim purity is 99% white iminodiacetonitrile 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.
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 iminodiacetonitrile 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 600m2/g gac 100kg/h.
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 iminodiacetonitrile 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 (7)
1. novel process of producing high-purity iminodiacetonitrile, it is characterized in that: this novel process comprises: synthetic, the purification of iminodiacetonitrile synthesis reaction solution of iminodiacetonitrile, three crystallizations and three wastes treatment process;
The synthetic following steps that include of described iminodiacetonitrile: quality percentage composition behind the buffered soln is 48 ~ 50% with adding, pH value is to enter hydroxyacetonitrile preheater (5) after 2.0 ~ 3.0 hydroxyacetonitrile measures by hydroxyacetonitrile volume pump (4) to be preheated to 90 ~ 120 ℃, pressure 0.8Mpa; Simultaneously liquefied ammonia is become ammoniacal liquor by ammoniacal liquor Preparation tank (1), after will dispose again ammoniacal liquor enter ammoniacal liquor preheater (3) after measuring by ammoniacal liquor volume pump (2), 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 by 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 iminodiacetonitrile synthesis reaction solution;
The purification of described iminodiacetonitrile synthesis reaction solution comprises can remove iminodiacetonitrile synthesis reaction solution color and removal impurity, and iminodiacetonitrile loss amount nanofiltration, absorption, flocculation, ion exchange process seldom;
Described three crystallization processes are: adopt three sections to concentrate, and three sections crystallization processes, its concrete steps are:
Iminodiacetonitrile synthesis reaction solution after the purification is at one section cooling crystallizer (10) crystallisation by cooling, 15 ℃ of Tcs, 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 the pure white iminodiacetonitrile product of color more than 99%, in one section crystallization, about 85% iminodiacetonitrile in the iminodiacetonitrile synthesis reaction solution behind the reclaiming clean; One section crystalline mother solution is neutralized to PH=3 with 60% sulfuric acid again, sending into first vaporizer (12) concentrates, 55 ℃ of thickening temperatures, with iminodiacetonitrile concentration in one section crystalline mother solution is 7.6% to be concentrated into about 25%, deliver 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 down oven dry, purity is pure white iminodiacetonitrile product more than 99%, about 13% iminodiacetonitrile in the iminodiacetonitrile synthesis reaction solution behind two sections crystallization reclaiming cleans; Approximately contain 5% iminodiacetonitrile in two sections crystalline mother solutions, 10% left and right sides hydroxyacetonitrile derivative, 3 ~ 5% aminoacetonitriles derivatives, again two sections crystalline mother solutions are delivered to second vaporizer (15) and be concentrated into iminodiacetonitrile content about about 25% in two sections crystalline mother solutions, enter three sections cooling crystallizers (16), 15 ℃ of Tcs, the iminodiacetonitrile of separating out is filtered through three centrifugal filters (17), filter cake is in 45 ~ 50 ℃ of oven dry down, purity is about 99% white iminodiacetonitrile product, about 1.5% iminodiacetonitrile in three sections crystallizations iminodiacetonitrile synthesis reaction solution after can reclaiming clean, these three crystallization processes can totally reclaim the iminodiacetonitrile in the iminodiacetonitrile synthesis reaction solution after purifying more than 99%;
Described three wastes treatment process comprises:
1. contain little ammonia in the flashing tower 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% left and right sides iminodiacetonitrile, 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 about 500 mg/litre of chemical oxygen demand COD content, 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 iminodiacetonitrile, 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 novel process of production high-purity iminodiacetonitrile according to claim 1 is characterized in that: described damping fluid is selected from ammonium phosphate buffer solution or ammonium sulfate buffered soln.
3. the novel process of production high-purity iminodiacetonitrile according to claim 1, it is characterized in that: described 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 novel process of described production high-purity iminodiacetonitrile according to claim 1, it is characterized in that: adopt in the described nanofiltration technique nanofiltration membrane should satisfy 80 ℃ of use temperatures, pressure 0.4MPa, the material of anti-system corrosion, the minimum molecular weight cut-off 150MWCO of nanofiltration membrane.
5. the novel process of described production high-purity iminodiacetonitrile according to claim 1, it is characterized in that: it is big that the sorbent material that described absorbing process adopts should satisfy specific surface area, and the band colored foreign is had very strong adsorptivity and iminodiacetonitrile is not had adsorptive power substantially.
6. the novel process of described production high-purity iminodiacetonitrile according to claim 1, it is characterized in that: described flocculation process and ion exchange process should satisfy can effective elimination iminodiacetonitrile synthesis reaction solution color, and the iminodiacetonitrile rate of loss is lower than 2%.
7. the novel process of described production high-purity iminodiacetonitrile according to claim 5 is characterized in that: described sorbent material is selected from specific surface area greater than in the gac of 300m2/g, atlapulgite, the diatomite one or more.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787919A (en) * | 2012-12-27 | 2014-05-14 | 三达膜科技（厦门）有限公司 | Decolorizing method of iminodiacetonitrile |
| CN103910651A (en) * | 2014-03-10 | 2014-07-09 | 河北诺达化工设备有限公司 | Iminodiacetonitrile continuous crystallization method |
| CN104892454A (en) * | 2015-05-11 | 2015-09-09 | 重庆紫光化工股份有限公司 | Novel crystalline form of iminodiacetonitrile and preparation method therefor |
| CN105272881A (en) * | 2015-06-09 | 2016-01-27 | 重庆紫光化工股份有限公司 | Cleaning production method for iminodiacetonitrile |
| CN105315175A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Iminodiacetonitrile cleaner production method |
| CN105315173A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Iminodiacetonitrile decoloration method |
| CN105315174A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Application of sulphurous acid as formaldehyde blocking agent and decolorizing agent |
| CN113292453A (en) * | 2021-06-04 | 2021-08-24 | 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 (1)
| Title |
|---|
| 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》, vol. 34, no. 1, 31 January 2009 (2009-01-31) * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103787919A (en) * | 2012-12-27 | 2014-05-14 | 三达膜科技（厦门）有限公司 | Decolorizing method of iminodiacetonitrile |
| 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 |
| CN103910651A (en) * | 2014-03-10 | 2014-07-09 | 河北诺达化工设备有限公司 | Iminodiacetonitrile continuous crystallization method |
| CN103910651B (en) * | 2014-03-10 | 2016-01-20 | 河北诺达化工设备有限公司 | Iminodiacetonitrile continuous crystallisation technique |
| CN104892454A (en) * | 2015-05-11 | 2015-09-09 | 重庆紫光化工股份有限公司 | Novel crystalline form of iminodiacetonitrile and preparation method therefor |
| CN105272881A (en) * | 2015-06-09 | 2016-01-27 | 重庆紫光化工股份有限公司 | Cleaning production method for iminodiacetonitrile |
| CN105315175A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Iminodiacetonitrile cleaner production method |
| CN105315173A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Iminodiacetonitrile decoloration method |
| CN105315174A (en) * | 2015-06-09 | 2016-02-10 | 重庆紫光化工股份有限公司 | Application of sulphurous acid as formaldehyde blocking agent and decolorizing agent |
| 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 |
| CN113292453A (en) * | 2021-06-04 | 2021-08-24 | 四川能投建工集团设计研究院有限公司 | Continuous crystallization process of iminodiacetonitrile |
| 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 |
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