CN101591255B - Clean production process of iminodiacetic acid - Google Patents
Clean production process of iminodiacetic acid Download PDFInfo
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- CN101591255B CN101591255B CN 200810113113 CN200810113113A CN101591255B CN 101591255 B CN101591255 B CN 101591255B CN 200810113113 CN200810113113 CN 200810113113 CN 200810113113 A CN200810113113 A CN 200810113113A CN 101591255 B CN101591255 B CN 101591255B
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Abstract
The invention provides a clean production process of iminodiacetic acid, comprising the following steps: using iminodiacetonitrile as a raw material to prepare iminodiacetic acid by alkaline hydrolysis, centrifugalizing the solution to obtain mother liquor, and recycling the mother liquor after separating salt by alkaline separation and acidic separation. The method can satisfy the clean production requirement of fully recycling atoms with little industrial waste, thus being a novel process with less investment, quick return, low production cost, remarkable economic effect and strong market competitiveness.
Description
Technical field
The present invention relates to a kind of is the process for cleanly preparing of feedstock production iminodiethanoic acid with the iminodiacetonitrile.
Background technology
Iminodiethanoic acid, CAS 142-73-4, the another name diglycinee, N-(carboxymethyl) glycine, the ammonia oxalic acid is called for short IDA, and white monoclinic crystal is slightly soluble in hot water, is dissolved in acetone, methyl alcohol, tetracol phenixin, heptane, ether and benzene hardly.Fusing point: 243 ℃, decompose when being heated to 247.5 ℃, generate salt with bronsted lowry acids and bases bronsted lowry, also form the huge legendary turtle compound with multiple metal.LD50 (medium lethal dose) is 250mg/kg, and pungency is arranged.Iminodiethanoic acid is mainly as the intermediate of agricultural chemicals such as synthesizing glyphosate, also can be used for doing aspects such as the raw material of ion exchange resin and rubber, plating, foodstuff additive simultaneously.
Surging the making with the bioenergy of oil price is the substitute energy rise of representative in recent years, and demand is advanced by leaps and bounds, and on December 13rd, 2007, passing through of U.S.'s new forms of energy bill indicates that the U.S. and even the whole world are clearer and more definite for the solid demand of bioenergy.Glyphosate has a good interior suction conductivity as a kind of, to the very effective Pesticidal products of the control of multiple dark root malignant weed, market demand constantly increases, to the end of the year 2006,500,000 tons of present global production capacities estimate that global glyphosate demand in 2010 is 1,000,000 tons.Therefore, as glyphosate synthetic intermediate, the iminodiethanoic acid production technology of developing clean and effective has great economic benefit.
The synthetic of present global iminodiethanoic acid can be divided into following several routes:
1, chloracetate is produced in the reaction of chloroactic acid method Mono Chloro Acetic Acid and ammoniacal liquor or sodium hydroxide, generate hydrazine with the hydrazine hydrate reaction again and embrace oxalic acid, then under the Sodium Nitrite effect again with hcl acidifying, generate the Iminodiacetate hydrochlorate, static crystallization, is dissolved in it in hot water suction filtration, pickling, adds sodium hydroxide solution and neutralizes, promptly generate iminodiethanoic acid, again through crystallization, separation, the dry product that gets.This method yield is low, and wastewater flow rate is big, complex steps, material cost height.
2, the diethanolamine method diethanolamine method is the new technology of the external exploitation nineties, this method is main raw material with the diethanolamine, in the presence of Cu-Ni alloy catalyst and sodium hydroxide, under the condition by high temperature (170 ℃), high pressure (0.8Mp), generate iminodiacetic acid sodium, with the hcl acidifying adjust pH, remember the iminodiacetic acid (salt) acid product through crystallization, separation, drying again.This method requires high to equipment, catalyzer, it is very big that the raw material diethanolamine is influenced by crude oil price, has the easy inactivation of catalyzer simultaneously, and the three wastes need economy, technology, environmental problems such as effectively processing, and this technology progressively is substituted.
3, this method of prussic acid method is generally good both at home and abroad method, and U.S. Pat 5187301 has reported with hydroxyacetonitrile and prepared iminodiacetonitrile that Chinese patent CN1609112 has reported with the synthetic pmida98 of Iminodiacetic acid sodium salt salt.Iminodiacetonitrile sodium hydroxide alkaline hydrolysis, acidifying, crystallization separates, and can prepare iminodiethanoic acid.This processing method is extensively adopted by each producer at present, but the yield of the diacid that this method is produced has only about 80%, contain the iminodiethanoic acid and the by product of a large amount of sodium-chlor and a great deal of in the mother liquor, the mother liquor waste water of generation does not also have the ideal treatment process.Existing technology exists that production cost height, wastewater flow rate are big, saltiness and ammonia nitrogen value are high-leveled and difficult big with biochemical treatment, long reaction time, product loss, is difficult to meet the requirement of cleaner production.The treatment process that generally adopts at present for this class high-salt wastewater is a simmer down to solid waste, and power consumption is big, does not meet the requirement of energy-saving and cost-reducing and cleaner production.Therefore directly isolating iminodiethanoic acid from reaction mass, to carry out the enterprise of pmida98 condensation more few.As a kind of replacement scheme, mainly adopt at present in the iminodiacetic acid sodium solution behind the alkaline hydrolysis deamination and directly add formaldehyde again behind the adding phosphorus trichloride acidication, add thermal condensation and generate the very little pmida98 production process route of solubleness, though the recovery utilization rate of diacid increases, but owing to added excessive phosphorus trichloride and raw materials such as formaldehyde, hydrochloric acid, isolating pmida98 is carried a large amount of salt secretly to be needed to contain a large amount of salt, hydrochloric acid, formaldehyde, phosphorous acid, diacid, pmida98 etc. in washing repeatedly, mother liquor and the water lotion, more handles.Also need to consume in a large number alkali as concentrating desalination, investment is big, energy consumption is high, and the abraum salt of generation is difficult to utilize because of forming complexity.The reaction of phosphorus trichloride and diacid is violent in addition, causes the reactor damage serious, changes frequent.
At above-mentioned defective, the contriver is through studying for a long period of time and exploration discovery: the alkaline hydrolysis of iminodiacetonitrile exists reaction efficiency low, with the reaction that is decomposed into oxyacetic acid and glycine, therefore need long-time at a lower temperature reaction could obtain higher yields and improve selectivity.But since dintrile dissolve temperature higher (about 70 ℃), and alkaline hydrolysis temperature of reaction (about 40 ℃), reaction yield is undesirable, this is because due to heterogeneousization of solid-liquid reaction; We have developed alkaline hydrolysis reaction homogeneous phaseization by deep research and exploration repeatedly, and simultaneously by decompression deamination fast cooling, have realized that the high yield of quick alkaline hydrolysis prepares the target of iminodiacetic acid sodium; We have also utilized common-ion effcet cleverly, and the sodium-chlor in the mother liquor is separated out, and mother liquor is recovered system again, has not only avoided concentrated power consumption, can make two acid recoverys in the solution again; By the hydrogenchloride common-ion effcet of utilizing the synthetic required phosphorus trichloride hydrolysis of synthetic required sodium hydroxide of diacid and pmida98 to produce, realized that not only acid out and alkali analyses cold desalination, can also accomplish water balance substantially, got rid of the link of concentrated desalination, new process fundamentally overcomes the deficiency of other technologies, has improved product yield and has reached target energy-saving and cost-reducing, cleaner production.
Summary of the invention
The purpose of this invention is to provide a kind of is the clean preparation method of feedstock production iminodiethanoic acid with the iminodiacetonitrile.The characteristics of this method are that alkaline hydrolysis speed is fast, production capacity is big, the mother liquor that process acid out, alkali are analysed after the processing centrifugation can be used as the raw material recycled, by-product salt (sodium-chlor) can by with replacement(metathesis)reactions such as ammonia gas as byproduct and carbonated boiler exhaust gas, generate bigger ammonium chloride solution and the littler sodium bicarbonate solid of solubleness of solubleness, leach sodium bicarbonate, mother liquor adds byproduct sodium chloride saltouts except that ammonium chloride, is re-used as the raw material cover and uses in the building-up reactions of next batch sodium bicarbonate.The ammonium chloride that generates is as fertilizer sources or industrial raw material sale directly, also can be used as ammonia source and Lewis acid.The sodium bicarbonate that produces also is an important chemical material, can sell, and also can use the synthetic liquid caustic soda of new patent processing method of our company's invention.During acid out desalination (sodium-chlor), the phosphorous acid that is produced can be used for the direct production pmida98 or takes out as important chemical material.The fully recycle of the material of the inventive method does not have generation of waste materials on the technology, can solve the problem of the best comprehensive utilization of by-product ammonia and sodium-chlor well.The required main raw material of circulation technology of the present invention is seen as iminodiacetonitrile, sodium hydroxide, phosphorus trichloride, three's molecular ratio near 1: 2: 1 from proportioning, bimolecular ammonia of by-product and bimolecular salt (sodium-chlor), required hydrochloric acid and sodium hydroxide can be analysed desalination from acid out desalination and alkali and be obtained and the confession that circulates.Therefore technology of the present invention can reach atom and can recycle entirely, and the cleaner production requirement of the no three wastes is that a less investment instant effect production cost is low, and remarkable in economical benefits has the new cleanproduction process of the very strong market competitiveness.
The principal reaction equation:
NH(CH
2CN)
2+2NaOH+2H
2O＝＝＝NH(CH
2COONa)
2+2NH
3
NH(CH
2COONa)
2+2HCl＝＝＝NH(CH
2COOH)
2+NaCl
NaCl+CO
2+NH
3＝＝＝NaHCO
3+NH
4Cl
Concretely, the invention provides a kind of is the novel method of raw material direct production iminodiethanoic acid with the iminodiacetonitrile, and this method comprises the steps:
1) with iminodiacetonitrile at water or/and in the mother liquor after the heat of solution, obtain the heat of solution liquid of iminodiacetonitrile.
2) iminodiacetonitrile heat of solution liquid that step 1) is obtained and hot dissolution of sodium hydroxide liquid (or alkali is analysed the desalination mother liquor) short mix enter reactor and carry out the alkaline hydrolysis reaction, remove part ammonia and water simultaneously, remove reaction heat and control reaction temperature.
3) with step 2) alkali solution liquid that obtains enters deammoniation tower and carries out deamination, behind the ammonia to be purified (free ammonia content≤0.1%), obtains deamination liquid.
4) the deamination liquid that obtains of step 3), dripping hydrochloric acid (or acid out desalination mother liquor) is regulated pH to 2, and stirring and crystallizing is separated, and obtains iminodiethanoic acid solid and iminodiacetic acid (salt) acid mother liquor, contains sodium-chlor about 24% and about 5% iminodiethanoic acid in the mother liquor.
5) the iminodiacetic acid (salt) acid mother liquor that obtains of step 4), can partly be used for the acid out desalination, promptly be used to absorb the phosphorus trichloride hydrolysis and produce hydrogen chloride gas, sodium-chlor in the iminodiacetic acid (salt) acid mother liquor is under the common-ion effcet effect of chlorion, form with solid sodium chloride is separated out, after the centrifugation solid sodium chloride, obtain acid out desalination mother liquor, can replace hydrochloric acid to be used for the raw material of acidifying deamination liquid; Another part is used for alkali and analyses desalination, the liquid caustic soda that promptly is used for solution tablet alkali or diluting high-concentration, sodium-chlor in the iminodiacetic acid (salt) acid mother liquor is under the common-ion effcet effect of sodium ion, separate out with the solid sodium chloride form, two wherein iminodiethanoic acids then form the disodium salt of the bigger iminodiethanoic acid of solubleness and stay in the solution, after the centrifugation solid sodium chloride while hot, obtain alkali and analyse the desalination mother liquor, replace liquid caustic soda to be used for the raw material of iminodiacetonitrile alkaline hydrolysis.As with the liquid caustic soda desalination then part two acid mother liquors can be used for dissolving dintrile with equilibrium water amount.
6) byproduct sodium chloride that obtains of step 5) can be used as raw material, part is made sodium chloride solution, be used for absorption step 3) ammonia that obtains, make the ammonia soln of sodium-chlor, make sodium bicarbonate behind the logical carbonic acid gas, after centrifugation obtained the sodium bicarbonate product, mother liquor added above-mentioned byproduct sodium chloride again and saltouts except that ammonium chloride, after centrifugation obtained ammonium chloride product, mother liquor was re-used as the raw material cover and uses in the building-up reactions of next batch sodium bicarbonate.
Side product sodium chloride and sodium bicarbonate all can be used as by-product sale, or further recycle.
Wherein, the mol ratio of iminodiacetonitrile and sodium hydroxide is 1: 2-3 is preferably 1: 2-2.5; The mol ratio of iminodiacetonitrile and hydrochloric acid is 1: 2-3 is preferably 1: 2-2.5.
In preferred embodiments, the inventive method comprises the steps:
1) hot water temperature is raise about 80 ℃, stir down the iminodiacetonitrile solid is dropped into dissolution kettle, open steam, keep solvent temperature about 70 ℃, obtain the iminodiacetonitrile lysate; Also can in mother liquor or cold water, add rising temperature for dissolving behind the dintrile.
2) under reduced pressure, squeeze in the mixing reactor fast liquid caustic soda (or alkali is analysed except that saline solution) and iminodiacetonitrile lysate by reaction ratio, carry out quick alkaline hydrolysis reaction, deamination and remove reaction heat, alkaline hydrolysis can be finished within a short period of time, Controllable Temperature further heats deamination again and can obtain deamination liquid built in below 60 ℃.
3) deamination liquid is cooled to about below 60 ℃, adds hydrochloric acid (or acid out desalination mother liquor) and regulate pH, be preferably 1.5-2.5 to 1-3, control adds the speed of hydrochloric acid, maintains the temperature at below 100 ℃, slowly stirs down, preceding 1/2 hydrochloric acid adds fast, and the salt slow acid of back 1/2 adds.After regulating that pH is reinforced and finishing, the about 1-5 of stirring and crystallizing hour, preferably be about 1.5-2.5 hour, treat that crystallization finishes after, centrifugation obtains iminodiethanoic acid solid and iminodiacetic acid (salt) acid mother liquor.
The hydrogen chloride gas that produces when 4) resulting iminodiacetic acid (salt) acid mother liquor desirable 1/2 is used to absorb the phosphorus trichloride hydrolysis carries out the acid out desalination.The hydrogen chloride gas that hydrolysis produced absorbs through the interchanger circulation in reactor with the iminodiacetic acid (salt) acid mother liquor, after mother liquor absorbs hydrogen chloride gas, be subjected to common-ion effcet and the precipitated sodium chloride solid, treat that mother liquor absorbs when wherein concentration of hydrochloric acid reaches 28% left and right sides, stop to absorb, separate and obtain solid sodium chloride and acid out desalination mother liquor, acid out desalination recycled.
5) resulting iminodiacetic acid (salt) acid mother liquor is got 1/2-1/4 and is used to add sheet alkali or liquid caustic soda and carries out alkali and analyse desalination.This process also is a physical and chemical process, and wherein, sheet alkali charging capacity is the reaction needed amount, continue to stir about 2 hours after having thrown sheet alkali or liquid caustic soda, centrifugation obtains sodium-chlor and alkali is analysed the desalination mother liquor, wherein, the centrifugation temperature is 50-90 ℃, and optimum condition is 60-80 ℃.
Post-processing step is with above described.
The iminodiethanoic acid product analysis content of the inventive method preparation can reach 98%, can reach more than 95% the iminodiacetonitrile yield.
Method provided by the invention, be a kind of employing iminodiacetonitrile under comparatively high temps with liquid caustic soda (or acid out remove saline solution) alkaline hydrolysis fast, add hydrochloric acid (perhaps acid out desalination mother liquor) behind the deamination again and regulate the pH post crystallization and separate, mother liquor is analysed the method for recycled behind the desalination through acid out, alkali, and speed of response is fast, the selectivity height, need not specific installation, Recycling Mother Solution is applied mechanically, and can reduce investment outlay widely, simplify the operation, reduce cost.According to practical situation, two cores of this Technology are the utilization that mother liquor acid out, alkali are analysed recycled and by-product ammonia and sodium-chlor behind the desalination, even partition or use separately also belongs to the flesh and blood and the claim scope of this patent.
Embodiment
Embodiment 1
In the flask of 500ml, add 200 gram water, stir down, in flask, add iminodiacetonitrile (95%) 200 gram (2 moles), heat and maintain the temperature at about 70 ℃, make material molten entirely.Simultaneously, sodium hydroxide 587 grams (4.4 moles) of adding 30% in the 1000ml flask, keep the liquid caustic soda temperature at 40 ℃, liquid caustic soda and iminodiacetonitrile hot solution under agitation are added drop-wise in the flask of 1000ml simultaneously, decompression is alkaline hydrolysis and deamination down, in the dropping process, maintain the temperature between 50-70 ℃, after dropwising, continue insulation 30 minutes down at 50-60 ℃, after insulation finishes, begin to heat up and under 60-100 ℃, carry out deamination (total obtains 25% ammoniacal liquor 135 grams), after 4 hours, deamination finish deamination liquid, deamination liquid is transferred in the flask of 2000ml, cool, when treating that temperature drops to 60 ℃, begin to drip 30% hydrochloric acid 502 grams, maintain the temperature in the dropping process between 50-80 ℃, after dropwising, reduce feed temperature to 20 ℃ after, continue to stir 2 hours, suction filtration, obtain 246.3 gram iminodiacetic acid (salt) acid crystals and 1107.6 gram mother liquors, through dividing analysis, iminodiethanoic acid content is 84.65% in the crystal, moisture content weightlessness is 13.23%, and wherein cl content is 1.29%; Mother liquor iminodiacetic acid (salt) acid content is 4.71%, cl content 13.79%.Wherein iminodiethanoic acid is to the folding hundred solid yields 78.38% of iminodiacetonitrile, and the transformation efficiency that iminodiacetonitrile is converted into iminodiethanoic acid is 97.90%.
Resulting 1100 gram mother liquors (wherein, sampling is done to divide and consumed about 7 grams) are divided into two parts, every part 550 gram.Portion is respectively applied for and absorbs the hydrogen chloride gas that the phosphorus trichloride hydrolysis produces, after absorbing hydrogen chloride gas, reaction solution gross weight 708 grams after suction filtration separates, obtain solid sodium chloride 123 grams, acid out desalination mother liquor 585 grams, through dividing analysis, content of hydrochloric acid is 26.69% in the acid out desalination mother liquor, and cl content 58.50% in the solid sodium chloride, acid out desalination sodium-chlor clearance is 92.28%, and this acid out desalination mother liquor gives over to down batch replacement hydrochloric acid recycled.Another part adds solid sodium hydroxide (96.5%) 180 gram, stir after 2 hours, suction filtration obtains solid sodium chloride 135 grams, alkali is analysed desalination mother liquor 595 grams, and through dividing analysis, cl content is 52.32% in the solid sodium chloride, alkali analyses that sodium hydrate content is 29.14% in the desalination mother liquor, wherein to analyse desalination sodium-chlor clearance be 90.42% to alkali, and this alkali is analysed the desalination mother liquor when giving over to down batch alkaline hydrolysis iminodiacetonitrile, replaces liquid caustic soda.
After resulting 258 gram mixing, join in the 135 gram ammoniacal liquor of recovery, add water 300 grams then, stir down and feed carbonic acid gas, generate the sodium bicarbonate suspension liquid, suction filtration obtains sodium bicarbonate 356 grams, absorption water when mother liquid recycle reclaims ammonia as next batch, after absorbing ammonia, add byproduct sodium chloride again and separate out ammonium chloride, mother liquor is applied mechanically after being used further to absorb a collection of ammoniacal liquor in back.
Embodiment 2
The hot water that adds 85 ℃ of 200 grams in the flask of 500ml stirs down, adds iminodiacetonitrile (95%) 200 gram (2 moles) in flask, maintains the temperature at 68 degree in the reinforced process.Simultaneously, in the 1000ml flask, add content and be 29.14% alkali and analyse desalination mother liquor 576 grams (4.2 moles), keep alkali to analyse desalination mother liquor temperature at 50 ℃, alkali is analysed the desalination mother liquor and the iminodiacetonitrile hot solution under agitation is added drop-wise in the flask of 1000ml simultaneously, decompression is alkaline hydrolysis and deamination down, in the dropping process, maintain the temperature between 65-75 ℃, after dropwising, continue insulation 30 minutes at 60-70 ℃, after insulation finishes, begin to heat up and carrying out deamination under 60-110 ℃ (with the 330 gram absorption ammonias of the mother liquor behind the preceding batch of removal sodium bicarbonate, add up to and obtain 18% ammoniacal liquor 398 grams), after 4 hours, deamination finish deamination liquid, deamination liquid is transferred in the flask of 2000ml, cool, when treating that temperature drops to 60 ℃, begin to drip 26.69% acid out desalination mother liquor 563.5 grams, maintain the temperature in the dropping process between 50-80 ℃, after dropwising, after reducing feed temperature to 18 ℃, continue to stir 1.5 hours, suction filtration obtains 302.8 gram iminodiacetic acid (salt) acid crystals and 1171.6 gram mother liquors, through dividing analysis, iminodiethanoic acid content is 82.03% in the crystal, and moisture content weightlessness is 10.23%, and wherein cl content is 2.85%; Mother liquor iminodiacetic acid (salt) acid content is 4.37%, cl content 14.36%.Wherein iminodiethanoic acid is 95.46% to the folding hundred solid yields of iminodiacetonitrile, and the transformation efficiency that iminodiacetonitrile is converted into iminodiethanoic acid is 96.90%.
Resulting 1160 gram mother liquors (wherein, sampling is done to divide and consumed about 10 grams) are divided into two parts, every part 580 gram.Portion is respectively applied for and absorbs the hydrogen chloride gas that the phosphorus trichloride hydrolysis produces, after absorbing hydrogen chloride gas, reaction solution gross weight 745 grams after suction filtration separates, obtain solid sodium chloride 137 grams, acid out desalination mother liquor 608 grams, through dividing analysis, content of hydrochloric acid is 27.13% in the acid out desalination mother liquor, and cl content 57.50% in the solid sodium chloride, acid out desalination sodium-chlor clearance is 91.07%, and this acid out desalination mother liquor gives over to down batch replacement hydrochloric acid recycled.Another part adds solid sodium hydroxide (96.5%) 193 gram, stir after 2 hours, suction filtration obtains solid sodium chloride 144 grams, alkali is analysed desalination mother liquor 629 grams, and through dividing analysis, cl content is 53.32% in the solid sodium chloride, alkali analyses that sodium hydrate content is 28.52% in the desalination mother liquor, wherein to analyse desalination sodium-chlor clearance be 92.42% to alkali, and this alkali is analysed the desalination mother liquor when giving over to down batch alkaline hydrolysis iminodiacetonitrile, replaces liquid caustic soda.
Before batch ammonium chloride mother liquor be used to absorb ammoniacal liquor behind totally 398 grams, separate out chloride solid, after suction filtration separates, obtain chloride solid 151 grams, mother liquor 247 grams, resulting byproduct sodium chloride is joined in the mother liquor, add water 300 grams then, stir down and feed carbonic acid gas, generate sodium bicarbonate suspension, suction filtration obtains sodium bicarbonate 386 grams, absorption water when mother liquid recycle reclaims ammonia as next batch, after absorbing ammonia, add byproduct sodium chloride again and separate out ammonium chloride, mother liquor is applied mechanically after being used further to absorb a collection of ammoniacal liquor in back.
Embodiment 3
Add process water 1200L to 3000L dintrile dissolution kettle, open steam elevated temperature to 85 ℃, stir the dintrile solid 1032kg (10kmol) that adds content 92% down, dissolved the back temperature in the kettle at 70 ℃, alkali is analysed except that saline solution (sodium hydrate content 29.80%, proportion 1.34) after 2150L is preheating to 50 ℃ through interchanger, through the material loading volume pump dintrile hot solution and thermokalite are analysed except that saline solution and to squeeze into static mixer simultaneously, feed liquid temperature in static mixer remains on 70-80 ℃, feed liquid is through behind the static mixer, squeeze into alkaline hydrolysis deammoniation tower still, tower still feed liquid is played circulation through recycle pump and is carried out deamination, during deamination, vacuum tightness is-0.06MPa that feed temperature raises 85 ℃ gradually from 70 ℃ in the tower still.The ammonia of deviating from carries out ammonia through one-level, secondary amine absorption tower and absorbs after separating through spinning liquid, and wherein, absorption liquid is the ammonium chloride solution of recycled in one-level, the secondary amine absorption tower.
Through behind 2 hours circulation deaminations, change the acidizing crystal still in the deamination liquid over to, the deamination liquid temp is reduced to 65 ℃, beginning adds acid out desalination mother liquor (content of hydrochloric acid 28%, proportion 1.15) in the acidizing crystal still, added 1200L altogether through 30min., regulate about pH to 7, continue to drip acid out and remove saline solution, slowly stir, dripped 1000L acid out desalination mother liquor in 2 hours altogether, regulate pH to 1.98, reduce temperature, after still temperature to be crystallized is reduced to 20 ℃, continue to stir 1.5 hours, the beginning blowing is centrifugal.Centrifugal 1328 kilograms of the iminodiethanoic acid solids that obtain, iminodiacetic acid (salt) acid mother liquor 4750L, through dividing analysis, iminodiethanoic acid content 89.40% in the iminodiethanoic acid solid, moisture content weightlessness is 5.78%, cl content 2.93%; Mother liquor iminodiacetic acid (salt) acid content is 5.03%, cl content 14.33%, and the iminodiacetic acid (salt) acid content is 4.14%, proportion 1.25.
Wherein, iminodiethanoic acid is 95.37% to the folding hundred solid yields of iminodiacetonitrile, and the transformation efficiency of iminodiethanoic acid is 96.85%.
Resulting 4750L mother liquor is divided into two parts, every part of 2370L, the phosphorus trichloride tail gas of the mother liquor of this 2370L being put into 3000L absorbs still, open the phosphorus trichloride hydrolysis system, the ON cycle pump is opened falling liquid film interchanger water coolant, carries out hydrogen chloride gas and absorbs, after absorbing hydrogen chloride gas, sampling analysis, behind the suction filtration, content of hydrochloric acid is 28.56% in the filtrate, stop to absorb hydrogen chloride gas, stop recycle pump, falling liquid film interchanger water coolant, temperature is reduced to about 20 ℃, centrifugation, obtain 693 kilograms of solid sodium chlorides, acid out desalination mother liquor 2600L.Through dividing analysis, wherein cl content is 56.5%, and the folding sodium chloride content is 93.11%, and weightlessness is 6.57%, and acid out desalination rate is 92.10%; In the acid out desalination mother liquor, content of hydrochloric acid is 28.52%, and proportion is 1.18.This acid out desalination mother liquor gives over to down when transferring pH after batch alkaline hydrolysis iminodiacetonitrile, replaces hydrochloric acid.
2370L iminodiacetic acid (salt) acid mother liquor is squeezed into 3000L alkali and is analysed except that salt oven in addition, to wherein adding 825 kilograms in sheet alkali (content 95.91%), added in 2 hours and to finish, after adding, continue to stir 1 hour, at this moment, in still, take a sample the suction filtration analysis, sodium hydrate content 27.83% in the liquid, blowing is centrifugal while hot, centrifugal 753 kilograms of the solid sodium chlorides that get, and alkali is analysed desalination mother liquor 2200L.Through dividing analysis, in the solid sodium chloride, cl content is 53.12%, folding sodium-chlor 87.53%, and weightlessness 7.73%, it is 93.34% that alkali is analysed the desalination rate; Alkali is analysed in the desalination mother liquor, and sodium hydrate content is 28.02%, and proportion is 1.34.This alkali is analysed the desalination mother liquor and is given over to down when criticizing the alkaline hydrolysis iminodiacetonitrile, replaces liquid caustic soda.
After preceding batch ammonium chloride mother liquor was used to absorb ammoniacal liquor, centrifugation got 380 kilograms of solid ammonium chlorides, mother liquor 1500L.This mother liquor is squeezed into the 5000L reactor, then under agitation with this resulting byproduct sodium chloride totally 1446 kilograms all add in the mother liquors, add water 1000L then, stir and feed carbonic acid gas down, generate sodium bicarbonate suspension, after cooling to 20 degree, continue to stir, centrifugal 1300 kilograms of the sodium bicarbonates that obtain, absorption water when mother liquor 2200L, this mother liquid recycle reclaim ammonia as next batch is behind the absorption ammonia, add byproduct sodium chloride again and separate out ammonium chloride, mother liquor is applied mechanically after being used further to absorb a collection of ammoniacal liquor in back.
Embodiment 4
Implementation method is imitated embodiment 3, different is replaces the water dissolution dintrile with 1200L iminodiacetic acid (salt) acid mother liquor (1/4 mother liquor), can salt out sodium-chlor 320kg with the liquid caustic soda 1890kg (replacement sheet alkali) of other a part of mother liquor (1200L iminodiacetic acid (salt) acid mother liquor) dilution 42%.Last iminodiethanoic acid is 96.0% to the folding hundred solid yields of iminodiacetonitrile, and the transformation efficiency of iminodiethanoic acid is 96.5%.
Claims (5)
1. produce the clean preparation method of iminodiethanoic acid with iminodiacetonitrile for one kind, this method comprises the steps:
1.1, iminodiacetonitrile and water and/or mother liquor mix, dissolving obtains the heat of solution liquid of iminodiacetonitrile under stirring heating, the mass ratio of iminodiacetonitrile and water is 1: 1～2.
1.2, heat of solution liquid that step 1.1 is obtained and liquid caustic soda or alkali analyses the desalination mother liquor under reduced pressure, carries out alkaline hydrolysis and deamination, obtains alkali solution liquid, the mol ratio of iminodiacetonitrile and sodium hydroxide is 1: 2～2.5.
1.3, the alkali solution liquid that obtains of step 1.2, through the decompression deamination, obtain deamination liquid.
1.4, the deamination liquid that obtains of step 1.3 adds hydrochloric acid or acid out desalination mother liquor is regulated the pH value, the decrease temperature crystalline centrifugation obtains iminodiethanoic acid solid and mother liquor.
1.5, the two acid mother liquors part that obtains of step 1.4 feeds hydrogen chloride gas and separates out and separate sodium-chlor and obtain acid out desalination mother liquor, be inserted in the step 1.4; A part two acid mother liquors add sheet alkali or liquid caustic soda separates out and separates sodium-chlor and obtain alkali and analyse the desalination mother liquor, is inserted in the step 1.2; A part two acid mother liquors are directly used in and dissolve dintrile in the step 1.1.
1.6, the ammonia of sodium-chlor that step 1.5 obtains and step 1.3 by-product is by method carbonate synthesis hydrogen sodium and the ammonium chloride known.
2. method according to claim 1, wherein in the step 1.1, used water is hot water or two acid mother liquors, solvent temperature is between 60-80 ℃.
3. method according to claim 1, wherein in the step 1.2, the temperature of alkaline hydrolysis is in 40-100 ℃ of scope.
4. method according to claim 1, wherein in the step 1.5, the acid out temperature is below 30 ℃.
5. method according to claim 1, wherein in the step 1.5, used hydrogenchloride derives from the phosphorus trichloride hydrolysis, perhaps derives from alternate manner.
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| CN 200810113113 CN101591255B (en) | 2008-05-28 | 2008-05-28 | Clean production process of iminodiacetic acid |
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| 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 |
| CN106631846A (en) * | 2016-12-18 | 2017-05-10 | 南通江山农药化工股份有限公司 | Preparation method of N-phosphonomethyl aminodiacetic acid intermediate |
| CN109851513A (en) * | 2018-12-24 | 2019-06-07 | 荆州鸿翔化工有限公司 | A kind of method of continuous production iminodiacetic acid disodium salt |
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| US3852344A (en) * | 1972-12-29 | 1974-12-03 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium chloride solutions |
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| US3852344A (en) * | 1972-12-29 | 1974-12-03 | Grace W R & Co | Process for recovering iminodiacetic acid from sodium chloride solutions |
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