CN105524107A - New process for clean production of pmida and cyclic utilization of byproducts - Google Patents
New process for clean production of pmida and cyclic utilization of byproducts Download PDFInfo
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Abstract
The invention relates to a new process for clean production of pmida and cyclic utilization of byproducts. According to the new process, iminodiacetonitrile serves as a main raw material, ammonia gas or/and a regenerated diacid monosodium salt are recovered by an alkaline hydrolysis or acid hydrolysis and alkaline hydrolysis coordinating process and an ammonium salt added and heating deamination double decomposition reaction, a qualified sodium chloride byproduct is precipitated and separated through the direct hydrolysis of pmida mother liquor and the common-ion effect of hydrogen chloride, acidic mother liquor can be cyclically applied mechanically, mother liquor, mother liquor, which cannot be applied mechanically, and washing water can be completely precipitated and separated through adding calcium hydroxide, raw materials and products can be regenerated from precipitates by an aqueous solution of acid or alkali, the precipitates are applied mechanically or are used for independently synthesizing the pmida, and regenerated calcium hydroxide can be repeatedly applied mechanically. According to the new process, the clean production of the pmida and the cyclic and high-added-value utilization of the byproducts can be realized.
Description
Technical field
The present invention relates to the process for cleanly preparing of glyphosate intermediate pmida98, belong to agricultural chemicals and technical field of fine.
Background technology
Pmida98 is the intermediate of the maximum herbicide glyphosate of preparation a kind of wide spectrum, global consumption; glyphosate chemical name is N-(phosphonomethyl) glycine; because it has good Uptake and translocation; very effective to the control of multiple dark root malignant weed; sales volume progressively increases in recent years; come out top in the most salable 50 pesticide species in the world, market scale surpasses 10,000,000,000 dollars, and in the whole world, more than 130 country's registrations use with a large amount of.
The industrial production of pmida98 is with iminodiethanoic acid, phosphorous acid and formaldehyde under hydrochloric acid catalysis, and reflux condensation, crystallisation by cooling are separated and obtain.Pmida98 has following several synthetic routes:
1, chloroactic acid method Mono Chloro Acetic Acid and ammoniacal liquor or sodium hydroxide react and produce sodium chloroacetate, react with hydrazine hydrate again and generate hydrazine and embrace oxalic acid, then under Sodium Nitrite effect again with hcl acidifying, generate iminodiacetic acid hydrochlorid, quiescent crystallization, suction filtration, pickling, be dissolved in hot water, add sodium hydroxide solution to neutralize, namely iminodiethanoic acid is generated, then through crystallization, separation, dry product, resynthesis pmida98.This method yield is low, and wastewater flow rate is large, and complex steps, material cost is high, is eliminated.
2, diethanolamine method diethanolamine method is the synthesis technique of the exploitation nineties in the world, take diethanolamine as main raw material, under the existence of Cu-Ni alloy catalyst and sodium hydroxide, by high temperature (170 DEG C), (0.8Mpa) with pressure deamination, generate iminodiacetic acid sodium, and then use phosphorus trichloride acidication, then add formaldehyde reaction synthesis pmida98.The investment of this method is large, and catalyzer easily catches fire, and by-product hydrogen explosive, exists potential safety hazard.Raw material diethanolamine affects very large by crude oil price simultaneously, and the pmida98 brine waste of high density is difficult to economy, technology, the environmental problems such as process, and this technique is replaced by prussic acid method substantially.
3, this method of prussic acid method is current main flow production method both domestic and external.US Patent No. 5,187,301 report and prepare iminodiacetonitrile with hydroxyacetonitrile, and Chinese patent CN1609112A reports and synthesizes pmida98 with iminodiacetic acid disodium salt.The iminodiacetonitrile intermediate of prussic acid synthesis, with sodium hydroxide hydrolysis, acidifying, crystallization, is separated and obtains iminodiethanoic acid, be condensed into pmida98 with formaldehyde, phosphorous acid.This method solid-liquid separation number of times is too many, and diacid yield only has about 80%, and the diacid waste water of a large amount of saliferous takes concentrated desalination, and the method for evaporation condensate biochemical treatment again, energy consumption is high, the poor quality of salt, is difficult to utilize.
What current most enterprises adopted is concentrated N-(phosphonomethyl) iminodiacetic acid wastewater desalination, the method for evaporation condensate biochemical treatment again, but causes biochemical difficulty due to the existence of formaldehyde, there is energy consumption high, the poor quality of abraum salt simultaneously, is difficult to the problems such as utilization.The waste water produced in dintrile technique and the process of mother liquor there is no good method, although also there is membrane technique to carry out wastewater treatment and desalination process, there is initial investment large, blocking and the damage of film are frequent, work-ing life is short, the problem that running cost is high, solves not yet very well at present.
It is raw material by iminodiacetonitrile that Chinese patent CN101891765A discloses a kind of, a kind of pmida98 getting the steps such as salt through alkaline hydrolysis, acidifying decolouring, condensation, crystallization, product washing, drying and wash water is production method, condensed mother liquor is applied mechanically the retraction conjunction stage by the method, wash water, by thickening and washing, obtains byproduct sodium chloride.But the method fails effectively to isolate organism wherein and by product enrichment problem, causes product purity to reduce, separating difficulty strengthens.Sodium-chlor and pmida98 product precipitate simultaneously and also make dissolving wash difficulty to add senior general and increase leaching requirement, strengthen concentrated load, increase energy consumption.
It is raw material with iminodiacetonitrile that Chinese patent CN103012473A announces a kind of, through nitration mixture hydrolysis, then iminodiacetonitrile hydrolyzed solution is carried out in presence of hydrochloric acid the method that pmida98 is prepared in condensation reaction with phosphorous acid and formaldehyde.The method adopts high temperature, ordinary-pressure hydrolysis iminodiacetonitrile, obtain the hydrochlorate of iminodiethanoic acid and the inorganic ammonium salt of qdx, direct polycondensation adds phosphorous acid and formaldehyde condensation, inorganic ammonium salt and formaldehyde generate hexamethylenetetramine, cause supplies consumption large, by-product is many, and productivity effect is poor, and therefore this technique has no and is used.
Wastewater treatment scheme adopted in the industry comprises at present: calcium hydroxide precipitation organism, Waste water concentrating and burning, pyrohydrolysis oxidation precipitation organics removal, reclaim the schemes such as phosphorus, these schemes or because calcium ion concn is inadequate, cannot precipitate the pmida98 in waste water, phosphorous acid and iminodiethanoic acid (publication number CN102674589A etc.) completely; Or it is large to there is investment, processing cost is high, the drawback (CN102874983A etc.) of the raw material high by added value and the low calcium phosphate salt of products production added value, although can reach the standard of industry discharge and the technical requirements of cleaner production, is not the wastewater treatment scheme of economical rationality.
We are in patent CN100558699C, the reaction mixture with hydroxyacetonitrile synthesizing iminodiacetic acid (salt) nitrile or iminodiacetonitrile directly acidolysis in excessive hydrochloric acid are invented, separate out the technique of iminodiacetic acid hydrochlorid and ammonium chloride mixt crystal, achieve two acid crudes and being effectively separated containing mother liquor compositions such as excessive hydrochloric acid, by-product glycine, oxyacetic acids, can use by time containing acid mother liquor.Iminodiacetic acid hydrochlorid can be neutralized by ammonia with the crude mixture of ammonium chloride, be separated, mother liquor concentrations, crystallization are applied mechanically etc., and flow process is refined as iminodiethanoic acid fine work, co-production ammonium chloride, iminodiethanoic acid and formaldehyde and phosphorous acid high yield under hydrochloric acid catalysis synthesize pmida98, without the need to neutralization, mother liquor can be applied mechanically repeatedly.This technique saves the consumption of alkali and hydrochloric acid, but adds the consumption of ammonia, and add crude product refining, process is longer, invests bigger than normal.
Summary of the invention
For meeting the more strict demand of industry to the yield of pmida98, technique, desalination rate, phosphorus utilization and clearer production technology, overcome the deficiency of existing technique.Contriver is through further research and exploration, invented take iminodiacetonitrile as raw material comprehensive utilization alkaline hydrolysis and acidolysis process advantage, more easily accepted by existing manufacturing enterprise, available ammonium chloride or iminodiacetic acid hydrochlorid and the acidifying of ammonium chloride mixt crude product, significantly can reduce the consumption of hydrochloric acid, water, alkali, increase the output of diacid list sodium salt, reclaim the improving technique of more ammonolysis products.
Innovate direct phosphorus trichloride and pmida98 mother liquor reacts, equilibrium water and simultaneously desalination simultaneously, or directly passed into hydrogenchloride, utilize the energy-conserving and environment-protective novel method of the common-ion effcet desalination of chlorion.
Invent pmida98, phosphorous acid and the iminodiethanoic acid in the almost quantitative deposition recovery pmida98 mother liquor and wash water using calcium hydroxide formation calcium salt, and holomorphosis can go out sodium salt or the vitriol of product and raw material further by the hot solution of diluted acid or diluted alkaline, purification mother liquor, regeneration calcium hydroxide, and regeneration raw material and product can apply mechanically separately or completely.Achieve the cleaner production of pmida98 and the recycle of maximum by product and raw material, develop the pmida98 new process of production having more recycling economy advantage.
Concretely, the present invention relates to a kind of is raw material with iminodiacetonitrile, the disodium salt solution obtained by alkaline hydrolysis, the replacement(metathesis)reaction neutralization of hydrochloric acid by heating deamination is replaced as solid acid part with iminodiacetic acid hydrochlorid, iminodiethanoic acid mono-ammonium or ammonium chloride, the material obtaining single sodium salt, again through decolouring, acidifying, desalination mother liquor, utilizes the common-ion effcet of hydrogenchloride to carry out pmida98 cleaner production and the by product recycled novel process of desalination to pmida98 mother liquor simultaneously.
First, the invention provides a kind of method of producing pmida98, comprise the steps:
(1) by complete for iminodiacetonitrile aqueous sodium hydroxide solution alkaline hydrolysis part deamination, the reaction residual liquor of iminodiacetic acid disodium salt is obtained;
(2) by one or more of iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride by not completing in liquid higher than generating the alkaline hydrolysis that iminodiethanoic acid list sodium salt acidifying requirement joins in step (1), continue heating deamination, qualified to material free ammonia, obtain the aqueous solution of iminodiethanoic acid list sodium salt;
(3) iminodiethanoic acid list sodium salt solution qualified for step (2) deamination added hydrochloric acid or apply mechanically desalination condensed mother liquor and continue to be acidified to pH and be not more than 4.5, with rear decoloring;
(4) condensed mother liquor after adding phosphorous acid and logical hydrogenchloride desalination by the required proportioning of reaction in the decolorization material of step (3) gained or add phosphorous acid that phosphorus trichloride hydrolysis generates except salts solution, then add formaldehyde by proportioning, condensation reaction is carried out in heating;
(5) material of step (4) condensation reaction gained is obtained pmida98 product through aftertreatment.
Wherein, in step (2), described iminodiacetic acid hydrochlorid crude product is by iminodiacetonitrile acidolysis gained; Described iminodiethanoic acid mono-ammonium crude product is mixed by iminodiacetic acid hydrochlorid crude product and excess of ammonia water, heating deamination prepares, and wherein folding hundred consumption of ammoniacal liquor is to be no less than completely and iminodiacetic acid hydrochlorid is advisable for iminodiethanoic acid mono-ammonium.The add-on of iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride is the 0.70-1.00 of iminodiacetic acid disodium salt mol ratio, preferably 0.95; Iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride are neutralized to material pH between 7.5-10.5 with part alkaline hydrolysis being completed liquid, preferred 8.5-9.5.
Deamination pressure is normal pressure or decompression, temperature 100-105 DEG C; Can be used as the judging criterion of deamination terminal with steam condensate weakly acidic pH, the free ammonia content of material is qualified lower than 0.1%; The ammonia reclaimed or ammonia absorption liquid can be used as soda ash or other industrial chemicals.
In step (3), iminodiethanoic acid list sodium salt solution qualified for step (2) deamination is added hydrochloric acid or applies mechanically desalination condensed mother liquor and continues to be acidified to pH value 3.5-4.5, add activated carbon decolorizing, soaking time 0.5-1h, with millipore filter isolating active charcoal.
In step (4), described aftertreatment for described material is directly lowered the temperature, crystallization, separation, obtain pmida98 after solids wash drying, filtrate waits until further process.Preferably, add the phosphorous acid solution after phosphorous acid or condensed mother liquor hydrolyzing phosphorus trichloride to step (3) gained material, be warming up to more than 110 DEG C, in 1-4h, add formaldehyde, insulation reaction 1-3h, steam 20%-subsequently
50the water yield of %, obtains pmida98 synthesis liquid, crystallisation by cooling, need not neutralize, direct or benefit wash water filters, washs to obtain pmida98 product, and a wash water of pmida98 is for washing the salt of mother liquor concentrations and acid out, and secondary wash water is used for the once washing of the pmida98 product of next batch.
In the process, the mol ratio of iminodiacetonitrile and phosphorus trichloride or phosphorous acid is 1:0.8-1.6, is preferably 1:1.0-1.3; The mol ratio of iminodiacetonitrile and formaldehyde is 1:0.8-1.6, is preferably 1:1.0-1.3.
In preferred embodiments, the production method of described pmida98 comprises the steps:
(1) by sodium hydroxide and water mixing, holding temperature, at 50-80 DEG C, adds iminodiacetonitrile solid or mother liquor material wherein, and reinforced this temperature 0.5-1h of complete maintenance, reacts to obtain iminodiacetic acid disodium salt solution;
(2) iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride is added by not dropping into higher than being neutralized into single sodium salt requirement to the iminodiacetic acid disodium salt solution of gained in step (1), proceed ammonia removal and reclaimer operation, operation terminal is complete with steam pH=7-7.5 deamination, and the free ammonia content of material is qualified lower than 0.1%; Otherwise, deamination temperature should be improved and increase the deamination time, if the still defective input amount that should reduce ammonium salt, using hydrogen peroxide, gac decolours between 80-100 DEG C;
(3) add hydrochloric acid or condensed mother liquor continuation acidifying to step (1) gained material, control material pH value 3.5-4.5, add activated carbon decolorizing soaking time 0.5-1h, with millipore filter isolating active charcoal;
(4) add the phosphorous acid solution after phosphorous acid or condensed mother liquor hydrolyzing phosphorus trichloride to step (3) gained material, be warming up to more than 110 DEG C, in 1-4h, at the uniform velocity add formaldehyde, insulation reaction 1-3h, preferred 2h, can steam 20%-50% moisture after reaction 2h, obtains pmida98 synthesis liquid;
(5) gained pmida98 synthesis liquid in step (4), crystallisation by cooling filters, secondary washing obtains pmida98 product, and a wash water of pmida98 is for washing the salt of mother liquor concentrations and acid out, and secondary wash water is used for the once washing of the pmida98 product of next batch.
Secondly, the invention provides a kind of phosphorus trichloride and pmida98 mother liquor directly used and react, equilibrium water and simultaneously desalination, or directly pass into hydrogenchloride, utilize the energy-conserving and environment-protective novel method of the common-ion effcet desalination of chlorion, described method comprises the steps:
In pmida98 condensed mother liquor, add phosphorus trichloride prepare phosphorous acid and hydrochloric acid mixed solution or directly pass into hydrogenchloride, and utilize common-ion effcet to be settled out a large amount of sodium-chlor, hydrolysis completes, solution carries out solid-liquid separation, washing, obtain the sodium-chlor meeting soda ash or other industrial salt requirement, gained filtrate can be applied mechanically in the synthesis of pmida98.Preferably, the step (4) of described filtrate being applied mechanically to above-mentioned pmida98 production method carries out condensation.
Preferably, condensed mother liquor control temperature drip between 40-70 DEG C phosphorus trichloride carry out phosphorus trichloride hydrolysis utilize simultaneously common-ion effcet continue removing condensed mother liquor in sodium-chlor.Phosphorus trichloride dropwises insulation 0.5-1h, is separated afterwards, can be used for the raw material of soda ash or other chemical industry after the wash water washing of solid sodium chloride pmida98; Condensed mother liquor merges concentrated and acid out desalination, and filtrate is the reaction that step (3) that phosphorous acid and hydrochloric acid mixed solution join above-mentioned production pmida98 method carries out step (4).
Again, for mother liquor, wash water mother liquor, the mother liquor that can not apply mechanically, the single batch of mother liquor more than needed that occur in pmida98 production process, the invention provides a kind of calcium hydroxide or milk of lime precipitation, liquid caustic soda or acid recovery, apply mechanically the novel method that pmida98 is produced, the method comprises the steps:
(1) with calcium hydroxide or lime slurry neutralization pmida98 mother liquor to pH within the scope of 10-11, keep calcium ion concn to be not less than 4%, realize precipitating completely, filter, filter cake washing;
(2) in step (1) gained filter cake, excessive liquid caustic soda is added, stripping sodium phosphite, Iminodiacetic acid sodium salt, pmida98 sodium salt, filter, filtrate is continued cover as raw material and is used in the Basic fluxing raction of iminodiacetonitrile or the condensation reaction of synthesis pmida98, isolated calcium hydroxide precipitation cover be used for next batch pmida98 mother liquor as in and raw material, complete recycle;
Or in step (1) gained filter cake, add the mixing solutions of sulphuric acid soln or sulfuric acid and hydrochloric acid, holomorphosis can go out phosphorous acid, iminodiethanoic acid and pmida98, separately or can overlap and be used for pmida98 condensation reaction.
Wherein, step (1) is preferably at room temperature carried out.
After step (2) adds liquid caustic soda, be warming up to 80-85 DEG C, stir 1-2h; In the amount of substance of sodium hydroxide and filter cake, the amount of substance of calcium ion is than being 1-5:1, preferred 2-4:1.Filter gained and be precipitated as calcium hydroxide, isolated precipitation calcium hydroxide cover is used in next batch pmida98 mother liquor, realize recycle, filtrate is the alkaline solution containing phosphorous acid, pmida98, iminodiethanoic acid, this solution can be used for iminodiacetonitrile alkaline hydrolysis and prepares iminodiacetic acid sodium, overlaps for pmida98 condensation reaction after consuming excess base again.
In the amount of substance of sulfuric acid and filter cake, the amount of substance ratio of calcium ion controls at 1-1.2:1, preferred 1-1.05:1, and the consumption of hydrochloric acid controls iminodiethanoic acid, pmida98 can be made to dissolve completely or excessive salify dissolves.Particularly, in step (2), gained filter cake in step (1) is added water, stirs, add the mixing solutions of sulphuric acid soln or sulfuric acid and hydrochloric acid, be warming up to 90-95 DEG C, and stir 1-2h at this temperature, filter, washing, merging filtrate.Gained filtrate can be used for the preparation of acidifying iminodiacetic acid sodium or pmida98.
Preferably, described method comprises the steps:
(1) under room temperature, in pmida98 mother liquor, drop into calcium hydroxide, control pH value of solution within the scope of 10-11, under calcium ion concn is not less than the condition of 4%, continue to stir, make it precipitate completely, filtering reacting solution, filter cake washing is for subsequent use;
(2) gained filter cake in step (1) is added excessive liquid caustic soda, stir, be warming up to 80-85 DEG C, and stir 1-2h at this temperature, filter, washing, merging filtrate; In the amount of substance of sodium hydroxide and filter cake, the amount of substance ratio of calcium ion controls at 1-5:1, preferred 2-4:1; In step (2), gained filter cake is the calcium hydroxide of demutation, can be used for replacing calcium hydroxide in step (1), filtrate is the alkaline solution of imido-oxalic acid, phosphorous acid, pmida98, this solution can be used for iminodiacetonitrile alkaline hydrolysis and prepares iminodiacetic acid sodium, is used further to the condensation of pmida98 after consuming excess base;
Or, gained filter cake in step (1) is added suitable quantity of water, stirs, add sulfuric acid, be warming up to 90-95 DEG C, and stir 1-2h at this temperature, filter, washing, merging filtrate.
In this step, gained filtrate can add and applies mechanically mother liquor, for the synthesis of iminodiacetic acid hydrochlorid or pmida98.
Preferably, the method for described process pmida98 mother liquor is applied to the method for above-mentioned production pmida98 and the method for pmida98 mother liquor desalination.
Finally, the present invention also provides a kind of clean preparation method of pmida98, comprises the steps:
(1) by complete for iminodiacetonitrile aqueous sodium hydroxide solution alkaline hydrolysis part deamination, the reaction residual liquor of iminodiacetic acid disodium salt is obtained;
(2) iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride are completed in liquid by the alkaline hydrolysis do not joined in step (1) higher than the single sodium salt acidifying requirement of generation, continue heated and stirred deamination, qualified to material free ammonia, obtain the aqueous solution of iminodiethanoic acid list sodium salt;
(3) single sodium salt solution qualified for step (2) deamination added hydrochloric acid or apply mechanically desalination condensed mother liquor and continue to be acidified to pH and be not more than 4.5, with rear decoloring;
(4) condensed mother liquor after adding phosphorous acid and logical hydrogenchloride desalination by the required proportioning of reaction in the decolorization material of step (3) gained or add phosphorous acid that phosphorus trichloride hydrolysis generates except salts solution, formaldehyde is added again by proportioning, be heated to more than 110 DEG C and carry out condensation reaction, the moisture of 30%-50% after reaction 2h, can be steamed;
(5) material of step (4) condensation reaction gained is not neutralized direct cooling, crystallization, separation, obtain qualified pmida98 product after solids wash drying, filtrate waits until further process;
(6) step (5) gained condensed mother liquor adds phosphorus trichloride and prepares phosphorous acid and hydrochloric acid mixed solution or add hydrogenchloride, and utilize common-ion effcet precipitable go out a large amount of sodium-chlor, hydrolysis completes, solution carries out solid-liquid separation, washing, can obtain the sodium-chlor meeting soda ash or other industrial salt requirement, filtrate can be applied mechanically to step (5) and be carried out condensation;
(7) mother liquor can not applied mechanically again or washings more than needed can with calcium hydroxide or lime slurry neutralizations, at pH within the scope of 10-11, under calcium ion concn is not less than the condition of 4%, precipitable go out the calcium salt of raw material and product;
(8) step (7) gained calcium salt adds that excess base makes to regenerate sodium phosphite, Iminodiacetic acid sodium salt, pmida98 sodium salt dissolve in the solution, continuing cover as raw material is used in alkaline hydrolysis or condensation reaction, isolated precipitation calcium hydroxide cover is used for next batch pmida98 mother liquor and carries out neutralization precipitation, complete recycle;
Or step (7) gained calcium salt is added the hot solution of diluted acid, holomorphosis can go out product and raw material, separately or can overlap and be used for pmida98 condensation operation.
Method tool of the present invention has the following advantages:
(1) the iminodiacetic acid (salt) disodium salt produced with alkaline hydrolysis is as alkali, the iminodiacetic acid hydrochlorid utilizing acidolysis process to produce, iminodiethanoic acid mono-ammonium or ammonium chloride are as solid acid, the hydrochloric acid substituting nearly half carries out acidifying to material, by Hybrid Heating deamination, promote that the replacement(metathesis)reaction generating single sodium salt is carried through to the end, make the iminodiacetic acid hydrochlorid of acidification technique and ammonia chloride be neutralized into iminodiethanoic acid list sodium salt simultaneously, and discharge ammonia, decrease acid and alkali consumption.Get through the ammonium chloride of iminodiacetonitrile alkali solution liquid low cost or acid technological process and obtain iminodiacetic acid hydrochlorid and ammonium chloride salt mixture crude product directly as the novel process of solid acid manufacture order sodium salt.Novel process can save the acid about half, the higher ammonia of half left and right added value or iminodiethanoic acid list sodium salt can be produced by ammonium salt metathesis, simplify the former loaded down with trivial details purification operations flow process of iminodiethanoic acid fine work, decrease mother liquid evaporation amount, better can advance the direct application of acid technological process, play its energy-saving and cost-reducing and cleaner production advantage further.
Iminodiacetic acid sodium mixture is after ammonium salt metathesis acidifying, free ammonia can be reduced to less than 0.1%, and through decolouring, condensation, crystallization, product washing, dry and mother liquor concentrations and acid out desalination, condensed mother liquor concentrate cleaner production and the whole recycle of by product that acid out desalination and precipitation decon and recovery etc. can realize pmida98.Novel process atom utilization is high, does not substantially produce the three wastes, can save the operation of concentrated waste water; Novel process makes full use of acidolysis process, at utmost can achieve the recycle of water, ammonia, sodium-chlor, phosphorous acid, formaldehyde, hydrochloric acid, energy-saving and cost-reducing remarkable benefit.
For iminodiacetic acid hydrochlorid crude product, reaction equation is:
(2) innovate direct phosphorus trichloride and pmida98 mother liquor reacts, equilibrium water and simultaneously desalination, or directly passed into hydrogenchloride, utilize the energy-conserving and environment-protective novel method of the common-ion effcet desalination of chlorion.Reaction equation is:
HCl
(g)?HCl
(aq)?H
+ (aq)+Cl
- (aq)
(3) invent calcium ion content in control solution and be not less than 4%, pH is within the scope of 10-11, pmida98, phosphorous acid and the iminodiethanoic acid in pmida98 mother liquor and wash water is reclaimed by the almost quantitative deposition using calcium hydroxide to form calcium salt, and holomorphosis can go out sodium salt or the vitriol of product and raw material further by the hot solution of diluted acid or diluted alkaline, purification mother liquor, regeneration calcium hydroxide, and regeneration raw material and product can apply mechanically separately or completely.Reaction equation is:
The invention provides pmida98 new cleanproduction process, simple to operate, reaction conditions is gentle, ingenious make use of each technique advantage and raw material complementary, achieve by product at utmost recycle.Novel process is according to practical situation, above steps also can break, in ammonium chloride or iminodiacetic acid hydrochlorid crude product and iminodiacetic acid disodium salt reclaim ammonia and diacid salt, condensed mother liquor recycled and acid out desalination, reclaim raw material and pmida98 etc., it is central inventive point that calcium hydroxide or milk of lime precipitation-soda acid reclaim raw material and pmida98-apply mechanically synthesis pmida98, can break or combinationally use, all belong to flesh and blood and the right of this patent.
Embodiment
the acidolysis of embodiment 1 iminodiacetonitrile is applied mechanically and is prepared iminodiacetic acid hydrochlorid crude product embodiment
32% hydrochloric acid 300g and 50g water are joined in 500mL four-hole boiling flask, and be preheated to 60-80 DEG C, by 95% iminodiacetonitrile solid 50g or solution, constant-speed material-adding in 30min is added in the hydrochloric acid of preheating, add and completely between 95-120 DEG C, be incubated 30min, decrease temperature crystalline is also separated, obtain 101g Iminodiacetate hydrochloride, crude, 295g acidolysis mother liquor; 60-80 DEG C is preheated to after passing into HCl gas 55g after acidolysis mother liquor is added 50g water, by the iminodiacetonitrile solid 50g of 95% or solution, constant-speed material-adding in 30min is added in the acidolysis mother liquor of logical HCl gas of preheating, add and completely between 95-120 DEG C, be incubated 30min, decrease temperature crystalline is also separated, obtain 151g Iminodiacetate hydrochloride, crude, 296g acidolysis mother liquor; Acidolysis mother liquor so repeats 5 times, and the Iminodiacetate hydrochloride, crude obtained is collected for subsequent use.Concrete data and yield as follows:
embodiment 2 iminodiacetonitrile alkaline hydrolysis and interpolation Iminodiacetate hydrochloride, crude condensation embodiment
96% sodium hydroxide 44g and 150g water are mixed to join in 500mL four-hole boiling flask, stir and holding temperature at 50-80 DEG C, 95% iminodiacetonitrile solid 50g or solution are at the uniform velocity joined in sodium hydroxide solution, feed time 0.5-1h, reinforced complete maintenance 50-80 DEG C insulation 30min, is progressively warming up to 100-110 DEG C and carries out deamination about 1h by alkali solution liquid.Add 38g(IDA%=40.36%, acidity is in HCl 50%) mixing iminodiacetic acid hydrochlorid crude product in embodiment 1, partial acidification alkali solution liquid also continues heating deamination, and sampling tracking and measuring free ammonia after between deamination to steam pH=7-7.5, dissociate NH
3-N%=0.03%, the complete hydrochloric acid 60g(content that adds of deamination is 37%) continue to be acidified between system pH=3.5-4.5, add hydrogen peroxide and gac, and between 80-100 DEG C, be incubated 30min decolour, material after decolouring adds the phosphorous acid solution 115g of 45%, at the uniform velocity drips the formaldehyde solution 55g of 35% after being heated to 110 DEG C within 3h, dropwises insulation 2h, decrease temperature crystalline is separated, and product washs.Obtain the pmida98 product that 125g content is 98.5%.
embodiment 3 iminodiacetonitrile disodium salt adds Iminodiacetate hydrochloride, crude condensation embodiment
Disodium salt feed liquid 200g after an iminodiacetonitrile alkaline hydrolysis of picking up the car completes, wherein iminodiacetic acid content is 25.09%; Get two acid crude 17.30g, wherein IDA content is 48.38%, and the two is mixed to join in 500mL four-hole boiling flask, is progressively warming up to 100-110 DEG C and carries out deamination, sampling tracking and measuring free ammonia after between deamination to steam pH=7-7.5, free NH
3-N%=0.01%, after deamination, moisturizing to iminodiacetic acid concentration is 27.5%, add hydrogen peroxide and gac, and between 80-100 DEG C, be incubated 30min decolour, the feed liquid after decolouring is incubated the phosphorus trichloride solution 72.30g slowly dripping 98.26% between 60-70 DEG C, dropwises rear insulation 30min, within 3h, the formaldehyde solution 40.51g of 36.75% is at the uniform velocity dripped after being heated to 110 DEG C, dropwise insulation 2h, decrease temperature crystalline is separated, and product washs.Obtain the pmida98 product that 93.60g content is 98.1%.
embodiment 4 iminodiacetonitrile alkaline hydrolysis and interpolation ammonium chloride condensation embodiment
96% sodium hydroxide 45g and 150g water are mixed to join in 500mL four-hole boiling flask, stir and holding temperature at 50-80 DEG C, 95% iminodiacetonitrile solid 50g or solution are at the uniform velocity joined in sodium hydroxide solution, feed time 0.5-1h, reinforced complete maintenance 50-80 DEG C insulation 30min, is progressively warming up to 100-110 DEG C and carries out deamination about 1h by alkali solution liquid.Add 25g ammonium chloride, partial acidification alkali solution liquid also continues heating deamination, sampling tracking and measuring free ammonia after between deamination to steam pH=7-7.5, free NH
3-N%=0.042%, deamination is complete adds hydrochloric acid 48g(content 37%) continue to be acidified between system pH=3.5-4.5, add hydrogen peroxide and gac, and between 80-100 DEG C, be incubated 30min decolour, material after decolouring adds the phosphorous acid solution 93g of 45%, at the uniform velocity drips the formaldehyde solution 45g of 35% after being heated to 110 DEG C within 3h, dropwises insulation 2h, decrease temperature crystalline is separated, and product washs.Obtain 103g, content is the pmida98 product of 98.6%, and pmida98 yield in kind is 89.48% relative to iminodiacetonitrile.
embodiment 5 iminodiacetonitrile disodium salt adds ammonium chloride condensation embodiment
Disodium salt feed liquid 200g after an iminodiacetonitrile alkaline hydrolysis of picking up the car completes, wherein iminodiacetic acid content is 25.09%; Get the ammonium chloride 18.67g that content is 97%, the two is mixed to join in 500mL four-hole boiling flask, is progressively warming up to 100-110 DEG C and carries out deamination, sampling tracking and measuring free ammonia after between deamination to steam pH=7-7.5, free NH
3-N%=0.09%, after deamination, moisturizing to iminodiacetic acid concentration is 27.5%, add hydrogen peroxide and gac, and between 80-100 DEG C, be incubated 30min decolour, the feed liquid after decolouring is incubated the phosphorus trichloride solution 61.15g slowly dripping 98.26% between 60-70 DEG C, dropwises rear insulation 30min, within 3h, the formaldehyde solution 34.30g of 36.75% is at the uniform velocity dripped after being heated to 110 DEG C, dropwise insulation 2h, decrease temperature crystalline is separated, and product washs.Obtain the pmida98 product that 77.02g content is 98.3%, pmida98 yield in kind is 93.7% relative to iminodiacetonitrile disodium salt.
the preparation of embodiment 6 iminodiethanoic acid mono-ammonium
After taking the acidolysis of 70g iminodiacetonitrile mother liquor, crude product (imido-oxalic acid: 33.9g) is in 150mL beaker, adds 20g water, stirs, and passes into ammonia to reaction solution gross weight when no longer increasing under room temperature, stops logical ammonia.Solid suction filtration, collects mother liquor.Obtain iminodiethanoic acid mono-ammonium crude product solution 58g, imido-oxalic acid mono-ammonium: 27.5g, ammonium chloride 10.3g.
embodiment 7 iminodiacetic acid disodium salt adds iminodiethanoic acid mono-ammonium condensation embodiment
Disodium salt feed liquid 200g after an iminodiacetonitrile alkaline hydrolysis of picking up the car completes, imido-oxalic acid 52.3g; Get iminodiethanoic acid mono-ammonium crude product solution 58g(imido-oxalic acid mono-ammonium: 27.5g, ammonium chloride 10.3g), the two is mixed to join in 200mL four-hole boiling flask, progressively be warming up to 100-110 DEG C and carry out deamination, sampling tracking and measuring free ammonia after between deamination to steam pH=7-7.5, free NH
3-N%=0.09%, after deamination, moisturizing to iminodiacetic acid concentration is 27.5%, add hydrogen peroxide and gac, and between 80-100 DEG C, be incubated 30min decolour, the feed liquid after decolouring is incubated the phosphorus trichloride solution 90g slowly dripping 98.26% between 60-70 DEG C, dropwises rear insulation 30min, within 3h, the formaldehyde solution 50.5g of 36.75% is at the uniform velocity dripped after being heated to 110 DEG C, dropwise insulation 2h, decrease temperature crystalline is separated, and product washs.Obtain the pmida98 product that 113g content is 98.5%, pmida98 yield in kind is 93.5% relative to iminodiacetonitrile.
embodiment 8 iminodiacetonitrile alkaline hydrolysis and add dintrile mother liquor acid hydrolysis products iminodiacetic acid hydrochlorid crude product condensation carry out mother liquid recycle embodiment
The process of applying mechanically is the repeatability that inspection crude product adds, and directly a large amount of iminodiacetic acid disodium salt solution of preparation carries out repeating to apply mechanically.Take iminodiacetonitrile alkaline hydrolysis deamination liquid and be about 100g(IDA=28.75%, NH
3-N%=0.01%) in the four-hole boiling flask of 250mL, add crude product 13g(IDA%=22.28% after the acidolysis of iminodiacetonitrile mother liquor, acidity is in HCl about 60%), deamination is continued at 100-110 DEG C, reclaim ammonia, the free ammonium of the complete sampling and measuring system of deamination, NH simultaneously
3-N%=0.02%.Deamination is complete add 32% hydrochloric acid 70g and 45g phosphorous acid solution (H
3pO
3%=64.30%, HCl%=10.21%), continue heating under stirring, at 110-130 DEG C, at the uniform velocity drip 35% formaldehyde solution 24g, dropwise insulation 2h; Insulation terminates cooling, and the sodium hydroxide solution 75g simultaneously adding 15% regulates between pH=0-1.Continue decrease temperature crystalline, Tc controls between 20-25 DEG C.Suction filtration is separated, and be separated to obtain condensed mother liquor (L1) 250g, condensed mother liquor passes into the condensation that next batch applied mechanically back by HCl desalination after concentrating the moisture of 35-40%; Suction filtration is separated the pmida98 product weight in wet base 60g obtained through 2 washings, gross weight 53.2g after dry, yield 96.60% in kind.So repeat to apply mechanically 4 times according to aforesaid operations, experimental result is as follows:
embodiment 9 calcium hydroxide precipitation the time pmida98 in gained pmida98 mother liquor and raw material
To the pmida98 mother liquor that 40g time is crossed, imido-oxalic acid: 0.24g, phosphorous acid: 0.64g, pmida98: in 2.84g, substep drops into 98% calcium hydroxide 8.8g, substep charging capacity is to keep solution temperature not higher than 45 DEG C, pH value of solution is within the scope of 10-11, and feed intake stirring at room temperature 2h after terminating.Filtering-depositing, washing, merging filtrate.
React to obtain phosphorous precipitation 4.32g, imido-oxalic acid: 0.23g, phosphorous acid: 0.70g, pmida98: 2.62g, filtrate merges washing lotion 51g, does not detect iminodiethanoic acid, phosphorous acid and pmida98.Prove that calcium hydroxide under these processing condition can iminodiethanoic acid, phosphorous acid and pmida98 completely in mother liquor of precipitation of ammonium.
pmida98 in embodiment 10 calcium hydroxide precipitation list batch reaction gained pmida98 mother liquor and raw material
To single batch reaction gained 300g pmida98 mother liquor (imido-oxalic acid: 0.46g, phosphorous acid: 2.31g, pmida98: 0.76g) middle substep input 98% calcium hydroxide 11g, substep charging capacity is to keep solution temperature not higher than 45 DEG C, pH value of solution is within the scope of 10-11, feed intake stirring at room temperature 2h after terminating, and filters.
React to obtain phosphorous precipitation 45g, imido-oxalic acid: 0.42g, phosphorous acid: 2.28g, pmida98: 0.70g, filtrate 344g, calcium ions: 14g, iminodiethanoic acid, phosphorous acid, pmida98 does not detect.Calcium hydroxide can make all pmida98s, most phosphorous acid, the iminodiethanoic acid of part precipitates from mother liquor.
the phosphorous precipitation of embodiment 11 sulfuric acid acidation
Filter cake 10g in Example 10, imido-oxalic acid: 0.06g, phosphorous acid: 0.167g, pmida98: 0.276g, the 10g that adds water dilutes, and adds 98% sulfuric acid 2.82g.90-95 DEG C is stirred 30 minutes, filters, washing, merging filtrate.
React to obtain semi-hydrated gypsum 3.9g, filtrate merges washing lotion 13g, imido-oxalic acid: 0.06g, phosphorous acid: 0.153g, pmida98: 0.265g.Prove that sulfuric acid holomorphosis can go out raw material and product.
the phosphorous precipitation of embodiment 12 sulfuric acid acidation
Filter cake 15g(imido-oxalic acid in Example 10: 0.14g, phosphorous acid: 0.76g, pmida98: 0.23g), the 15g that adds water dilutes, and adds 95% sulfuric acid 2.63g.90-95 DEG C is stirred 30 minutes, filters, washing, merging filtrate.
React to obtain semi-hydrated gypsum 3.6g, filtrate merges washing lotion 23g, imido-oxalic acid: 0.12g, phosphorous acid: 0.73g, pmida98: 0.23g.Prove that sulfuric acid holomorphosis can go out raw material and product.
embodiment 13 sulfuric acid acidation liquid synthesis pmida98
Take iminodiacetonitrile alkaline hydrolysis deamination liquid 10g(imido-oxalic acid: 2.88g) in the four-hole boiling flask of 50mL, add crude product 1.3g(imido-oxalic acid: 0.29g after the acidolysis of iminodiacetonitrile mother liquor), at 100-110 DEG C, continue deamination.The complete filtrate 11g(imido-oxalic acid added in embodiment 11 of deamination: 0.06g, phosphorous acid: 0.35g), the water of concentrated about about 10g, add 32% hydrochloric acid 7g and 4g phosphorous acid solution again (containing phosphorous acid: 2.57g, hydrogenchloride: 0.4g), continue heating under stirring, at 110-130 DEG C, at the uniform velocity drip 35% formaldehyde solution 2.4g, dropwise insulation 2h; Insulation terminates cooling.Continue decrease temperature crystalline, Tc controls between 20-25 DEG C.Suction filtration, dry, obtain pmida98 solid 5.3g, yield 96.60%.
embodiment 14 sulfuric acid acidation liquid synthesis pmida98
Take iminodiacetonitrile alkaline hydrolysis deamination liquid 10g(imido-oxalic acid: 2.88g) in the four-hole boiling flask of 50mL, add crude product 1.3g(imido-oxalic acid: 0.29g after the acidolysis of iminodiacetonitrile mother liquor), at 100-110 DEG C, continue deamination, reclaim ammonia simultaneously.The complete filtrate 11g(imido-oxalic acid added in embodiment 11 of deamination: 0.06g, phosphorous acid: 0.35g) add the pmida98 mother liquor 30g(imido-oxalic acid of gained in embodiment 9: 0.06g, phosphorous acid: 0.31g, pmida98: 0.07g), the water of concentrated about 20g, add again 32% hydrochloric acid 7g and 4.0g phosphorous acid solution (containing phosphorous acid: 2.57g, hydrogenchloride: 0.4g), heating is continued under stirring, at 110-130 DEG C, at the uniform velocity drip 35% formaldehyde solution 2.4g, dropwise insulation 2h; Insulation terminates cooling.Continue decrease temperature crystalline, Tc controls between 20-25 DEG C.Suction filtration, dry, obtain pmida98 solid 5.3g, yield 96.60% in kind.
the phosphorous precipitation of embodiment 15 liquid caustic soda process, reclaims pmida98, phosphorous acid and iminodiethanoic acid
Filter cake 10g(imido-oxalic acid in Example 9: 0.06g, phosphorous acid: 0.16g, pmida98: 0.27g), add 30% liquid caustic soda 16g.90-95 DEG C is stirred 1h, filters, washing, merging filtrate.
React filtrate 19.4g(contains sodium hydroxide: 4.5g, iminodiethanoic acid: 0.06g, phosphorous acid: 0.17g, pmida98: 0.26g), filter cake 9.2g.Filter cake is the calcium hydroxide of regeneration.
embodiment 16 regenerated hydrogen calcium oxide recovering effect is tested
Pmida98 mother liquor 20g(imido-oxalic acid to time: 0.12g, phosphorous acid: 0.32g, pmida98: 1.42g) the middle calcium hydroxide 9.2g dropping into demutation in embodiment 14 step by step, substep charging capacity is to keep solution temperature not higher than 45 DEG C, pH value of solution is not more than 10, and feed intake stirring at room temperature 2h after terminating.Filter, washing, merge liquid phase.
React to obtain phosphorous precipitation 5.5g, imido-oxalic acid: 0.11g, phosphorous acid: 0.35g, pmida98: 1.3g, filtrate merges washing lotion 21g, does not detect iminodiethanoic acid, phosphorous acid and pmida98.Prove that the calcium hydroxide of regeneration can make iminodiethanoic acid equally, phosphorous acid and pmida98 can precipitate completely from mother liquor.
embodiment 17 alkali regenerative raw materials and product apply mechanically the experiment of synthesis pmida98
By the filtrate 19.4g(of gained in embodiment 15 containing sodium hydroxide: 4.5g, iminodiethanoic acid: 0.06g, phosphorous acid: 0.17g, pmida98: 0.26g) join in 50mL four-hole boiling flask, stir also holding temperature, at 50-80 DEG C, 95% iminodiacetonitrile solid 5g at the uniform velocity to be joined in sodium hydroxide solution, feed time 0.5-1h, reinforced complete maintenance 50-80 DEG C insulation 30min, is progressively warming up to 100-110 DEG C and carries out deamination about 1h by alkali solution liquid.Add 3.8g(imido-oxalic acid: 1.53g) mixing iminodiacetic acid hydrochlorid crude product in embodiment 1, partial acidification alkali solution liquid also continues heating deamination, the complete hydrochloric acid that adds of deamination continues to be acidified between system pH=3.5-4.5, add hydrogen peroxide and gac, and between 80-100 DEG C, be incubated 30min decolour, material after decolouring adds 45% phosphorous acid solution 11.5g, within 3h, 35% formaldehyde solution 5.5g is at the uniform velocity dripped after being heated to 110 DEG C, dropwise insulation 2h, decrease temperature crystalline is separated, and product washs.Obtain pmida98 product 12.8g, purity 98.5%.
More than experiment demonstrates, and what the raw material after the regeneration of pmida98 calcium hydroxide precipitation thing alkali or product can realize circulating completely twoly applies mechanically.
Claims (10)
1. produce a method for pmida98, comprise the steps:
(1) by complete for iminodiacetonitrile aqueous sodium hydroxide solution alkaline hydrolysis part deamination, the reaction residual liquor of iminodiacetic acid disodium salt is obtained;
(2) one or more in iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride are completed in liquid by the alkaline hydrolysis do not joined in step (1) higher than generation iminodiethanoic acid list sodium salt acidifying requirement, heating deamination, qualified to material free ammonia, obtain the aqueous solution of iminodiethanoic acid list sodium salt;
(3) iminodiethanoic acid list sodium salt solution qualified for step (2) deamination added hydrochloric acid or apply mechanically desalination condensed mother liquor and continue to be acidified to pH and be not more than 4.5, with rear decoloring;
(4) condensed mother liquor after adding phosphorous acid or logical hydrogenchloride desalination in the decolorization material of step (3) gained or add phosphorous acid that phosphorus trichloride hydrolysis generates except salts solution, then add formaldehyde, condensation reaction is carried out in heating;
(5) material of step (4) condensation reaction gained is obtained pmida98 product through aftertreatment.
2. method according to claim 1, wherein iminodiacetic acid hydrochlorid crude product described in step (2) is by iminodiacetonitrile acidolysis gained; Described iminodiethanoic acid mono-ammonium crude product is mixed by iminodiacetic acid hydrochlorid crude product and excess of ammonia water, and heating deamination prepares; One or more add-on in iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride is the 0.70-1.00 of iminodiacetic acid disodium salt mol ratio, preferably 0.95;
The ammonia reclaimed or ammonia absorption liquid can be used as soda ash or other industrial chemicals; Deamination pressure is normal pressure or decompression, and temperature 100-105 DEG C can be used as the judging criterion of deamination terminal with steam condensate weakly acidic pH, and the free ammonia content of material is qualified lower than 0.1%;
Iminodiacetonitrile and iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride are neutralized to material pH between 7.5-10.5 with part alkaline hydrolysis being completed liquid, preferred 8.5-9.5.
3. according to the method for any one of claim 1-2, wherein, the mol ratio of iminodiacetonitrile and phosphorus trichloride or phosphorous acid is 1:0.8-1.6, is preferably 1:1.0-1.3; The mol ratio of iminodiacetonitrile and formaldehyde is 1:0.8-1.6, is preferably 1:1.0-1.3.
4. according to the method for any one of claim 1-3, wherein, in step (3), iminodiethanoic acid list sodium salt solution qualified for step (2) deamination is added hydrochloric acid or applies mechanically desalination condensed mother liquor and continues to be acidified to pH value 3.5-4.5, add activated carbon decolorizing soaking time 0.5-1h, subsequently isolating active charcoal.
5. according to the method for any one of claim 1-4, wherein, in step (4), the phosphorous acid solution after phosphorous acid or condensed mother liquor hydrolyzing phosphorus trichloride is added to step (3) gained material, be warming up to more than 110 DEG C, formaldehyde is added in 1-4h, insulation reaction 1-3h, steam the water yield of 20%-50% subsequently, obtain pmida98 synthesis liquid, crystallisation by cooling, need not neutralize, direct or benefit wash water filters, wash to obtain pmida98 product, a wash water of pmida98 is for washing the salt of mother liquor concentrations and acid out, secondary wash water is used for the once washing of the pmida98 product of next batch.
6. method according to claim 1, it comprises the steps:
(1) by sodium hydroxide and water mixing, holding temperature, at 50-80 DEG C, adds iminodiacetonitrile solid or mother liquor material wherein, and reinforced this temperature 0.5-1h of complete maintenance, reacts to obtain iminodiacetic acid disodium salt solution;
(2) iminodiacetic acid hydrochlorid crude product, iminodiethanoic acid mono-ammonium crude product or ammonium chloride is added by not dropping into higher than being neutralized into single sodium salt requirement to the iminodiacetic acid disodium salt solution of gained in step (1), proceed ammonia removal and reclaimer operation, operation terminal is complete with steam pH=7-7.5 deamination, and the free ammonia content of material is qualified lower than 0.1%;
(3) add hydrochloric acid or condensed mother liquor continuation acidifying to step (1) gained material, control material pH value 3.5-4.5, add activated carbon decolorizing soaking time 0.5-1h, subsequently isolating active charcoal;
(4) add the phosphorous acid solution after phosphorous acid or condensed mother liquor hydrolyzing phosphorus trichloride to step (3) gained material, be warming up to more than 110 DEG C, in 1-4h, at the uniform velocity add formaldehyde, insulation reaction 1-3h, preferred 2h, can steam the moisture of 20%-50% after reaction, obtain pmida98 synthesis liquid;
(5) gained pmida98 synthesis liquid in step (4), crystallisation by cooling filters, secondary washing obtains pmida98 product, and a wash water of pmida98 is for washing the salt of mother liquor concentrations and acid out, and secondary wash water is used for the once washing of the pmida98 product of next batch.
7. a method for pmida98 cleaner production, comprises the steps:
(6) step (1)-(5) of the production method of the pmida98 as described in claim 1-6 are implemented;
(7) step (5) gained condensed mother liquor is added phosphorus trichloride and prepare phosphorous acid and hydrochloric acid mixed solution, and utilize common-ion effcet to be settled out sodium-chlor, hydrolysis completes, solution carries out solid-liquid separation, washing, can obtain the sodium-chlor meeting soda ash or other industrial salt requirement, filtrate can be applied mechanically to step (5) and be carried out condensation.
8. method according to claim 7, it comprises the steps: further
(8) mother liquor can not applied mechanically again or washings calcium hydroxide more than needed or lime slurry neutralization, to keeping pH at 10-11, keep calcium ion concn to be not less than 4%, the calcium salt realizing raw material and product precipitates completely, filters, washing leaching cake;
(9) step (8) gained filter cake adds excessive liquid caustic soda and makes to regenerate sodium phosphite, Iminodiacetic acid sodium salt, pmida98 sodium salt, and dissolved in the solution, can continue cover as raw material is used in alkaline hydrolysis or condensation reaction, isolated precipitation calcium hydroxide cover be used for next batch pmida98 mother liquor as in and raw material, realize complete recycle;
Or step (8) gained filter cake is added the mixing solutions of sulfuric acid or sulfuric acid and hydrochloric acid, holomorphosis can go out product and raw material, separately or can overlap and be used for pmida98 condensation operation.
9. method according to claim 8, wherein, under room temperature, drops into calcium hydroxide or milk of lime in pmida98 mother liquor or the mother liquor that can not apply mechanically again or washings more than needed, controls pH value of solution within the scope of 10-11, keeps calcium ion concn to be not less than 4%; Feed intake complete after, continue stir, make it precipitate completely, filtering reacting solution, gained filtrate can be applied mechanically, wash or enter biochemistry pool.
10. the method for according to Claim 8 or 9, wherein, in step (9), adds water gained filter cake in step (8), stir, add the mixing solutions of sulfuric acid or sulfuric acid and hydrochloric acid, be warming up to 90-95 DEG C, and stir 1-2h at this temperature, filter, washing, merging filtrate; In the amount of substance of sulfuric acid and filter cake, the amount of substance ratio of calcium ion controls at 1-1.2:1, preferred 1-1.05:1, the consumption of hydrochloric acid controls iminodiethanoic acid, pmida98 can be made to dissolve completely or the dissolving of excessive salify, and gained filtrate can be used for the acidifying of iminodiacetic acid sodium or the synthesis of pmida98;
Or gained filter cake in step (8) is added excessive liquid caustic soda, stirs, be warming up to 80-85 DEG C, and stir 1-2h at this temperature, filter, washing, merging filtrate; In the amount of substance of sodium hydroxide and filter cake, the amount of substance ratio of calcium ion controls at 1-5:1, preferred 2-4:1, filter gained and be precipitated as calcium hydroxide, isolated calcium hydroxide precipitation also separately or can be applied mechanically and carry out neutralization precipitation with next batch pmida98 mother liquor, realize recycle, filtrate is the alkaline solution containing excessive sodium hydrate, iminodiacetic acid sodium, sodium phosphite, pmida98 sodium, and this solution can overlap preparation for iminodiacetic acid sodium or pmida98 condensation operation.
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