CN101747369A - Environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid - Google Patents

Environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid Download PDF

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CN101747369A
CN101747369A CN201010011402A CN201010011402A CN101747369A CN 101747369 A CN101747369 A CN 101747369A CN 201010011402 A CN201010011402 A CN 201010011402A CN 201010011402 A CN201010011402 A CN 201010011402A CN 101747369 A CN101747369 A CN 101747369A
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acid
iminodiacetonitrile
reaction
preparing
iminodiethanoic
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CN101747369B (en
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高庆昌
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Yingkou Yingxin Chemical Technology Co ltd
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Zibo Wanchang Science & Technology Co Ltd
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Abstract

The invention relates to an environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid, belonging to the comprehensive utilization of acrylonitrile device byproduct hydrocyanic acid in industrial scale. The method includes that: step first, acrylonitrile byproduct hydrocyanic acid is used for preparing hydroxyl acetonitrile, and then iminodiacetonitrile is prepared; step two, the obtained iminodiacetonitrile is used for preparing iminodiacetic acid by acid hydrolysis method; and step three, the obtained iminodiacetic acid is used for preparing N-phosphonomethyl iminodiacetic acid. No report of preparing PMIDA by utilizing acrylonitrile byproduct hydrocyanic acid in industrial scale is seen, and the inventor uses local materials, utilizes the advantages of being adjacent to Qilu petrochemical and having resource of hydrocyanic acid (4000 ton/year) transmitted by pipeline and initially provides the method for preparing PMIDA by utilizing acrylonitrile byproduct hydrocyanic acid in industrial scale. The invention solves the problem of region restriction of product production caused by inconvenient transportation of hydrocyanic acid. A gas and liquor mixer is applied to iminodiacetonitrile reaction, and by virtue of DCS control system, quality and yield of iminodiacetonitrile are improved.

Description

A kind of environmental-friendly new method that utilizes vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid
Technical field
The invention belongs to plant-scale acrylonitrile installation coproduct hydrogen cyanic acid comprehensive utilization category, be specifically related to a kind of environmental-friendly new method that utilizes vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid.
This law divides work three steps:
The first step, vinyl cyanide coproduct hydrogen cyanic acid be preparation hydroxyacetonitrile (Glycolonitrile) earlier; Refabrication iminodiacetonitrile (Iminodiacetonitrile);
Second step, the iminodiacetonitrile of acquisition, the acid system hydrolysis prepares iminodiethanoic acid (Iminodiacetic Acid is called for short IDA);
The 3rd step, the iminodiethanoic acid of acquisition, preparation N-phosphonomethyl iminodiethanoic acid N-(Phosphonomethyl) Iminodiacetic Acid is called for short PMIDA.
Background technology
When petro-chemical corporation utilizes ammoxidation of propylene manufactured vinyl cyanide, produce a large amount of prussic acid.Applicant and Qilu Petrochemical are adjoined, the resources advantage that has the prussic acid (4000 tons/year) of pipe-line transportation, utilize vinyl cyanide coproduct hydrogen cyanic acid to do initial raw material, technical scale prepares a series of fine-chemical intermediates---ortho-formiate, 3,3-dimethyl-4-pentenoic acid methyl ester, anilinoacetic acid potassium, hydroxyacetonitrile, nitrilotriacetic acid sodium etc.; And a plurality of Chinese patent mandates (CN00111314.3, CN 200310112977.4, CN 200610048134.6, CN200610048135.0, CN200610048136.5, CN200610048195.2) have been obtained at this point.
The present invention is applicant extending again and development utilization on above-mentioned resources advantage and technical superiority basis, utilize vinyl cyanide coproduct hydrogen cyanic acid to do initial raw material equally, the preparation iminodiacetonitrile, and prepare iminodiethanoic acid, and then produce improving one's methods of pmida98 through thus obtained iminodiacetonitrile acidic hydrolysis.
About the preparation of iminodiacetonitrile, the US4307037 report, DEGUSSA company adopts prussic acid method production iminodiacetonitrile.But with prussic acid and formaldehyde, hexamethyl tetramine is raw material, catalysis synthesizing iminodiacetic acid (salt) nitrile under acidic conditions, and reaction formula is as follows:
(CH 2) 6N 4+6HCN+1/2H 2SO 4→3NH(CH 2CN) 2+1/2(NH 4) 2SO 4
(CH 2) 6N 4+8HCN+2HCHO→4NH(CH 2CN) 2+2H 2O
The iminodiacetonitrile yield that this method is produced is on the low side, and because of raw material hexamethyl tetramine cost is too high, and technology can not recycled, and waste water is too many.
Also having report, is to be material synthesis gas body prussic acid with the Sweet natural gas, directly leads to synthesis of hydroxy acetonitrile in the formaldehyde again, synthesizing iminodiacetic acid (salt) nitrile then, and this method synthesizing iminodiacetic acid (salt) nitrile wastewater flow rate is relatively large, and impurity is many.
For example: patent application CN200710049105.6, title: " preparation method of iminodiacetonitrile " applicant: Natural Gas in Sichuan chemical research institute, narrated a kind of method of utilizing the tubular reactor produced iminodiacetonitrile, feature is the compound stopper that adds ammonium salt and substituting group diphenol in hydroxyacetonitrile, the mol ratio of hydroxyacetonitrile and ammonia react is 0.8 ~ 1.3: 1, utilize ammonia and solid ammonium salt as raw material, operation is complicated, and industrial scale is easily limited.
Patent application CN200610054172.2, title: " preparation technology of iminodiacetonitrile ", applicant: Chongqing purple light chemical industry company limited, narrated a kind of method of utilizing the tubular reactor produced iminodiacetonitrile, feature is to add the poly-agent of aluminum oxide sun and oxidation inhibitor dihydroxy-benzene or naphthalenediol.Reaction times, yield was relatively poor more in short-term, and the bad or impurity of outward appearance increased when the time was long.
Patent application CN200610032261.7, title: " clean preparation method of combined reactor continuously synthesizing iminodiacetic acid (salt) nitrile ", applicant: Li Bin, what narrate is the combined reactor that utilizes a kind of tubular reactor and thermopnore formula reactor to form, and product impurity that obtains like this and polymkeric substance still are difficult to control.
For another example, 5187301 of US are called " Preparation of iminodiacetonitrile from glycolonitrile ", narrated a method of utilizing hydroxyacetonitrile and ammonia or ammonium salt intermittent type or serialization to prepare iminodiacetonitrile, the iminodiacetonitrile outward appearance that this method obtains is a brown, polymkeric substance is more, and content is only about 95%.
Above method is all failed when gas-liquid mixed to the in addition accurately control of the proportioning of hydroxyacetonitrile and ammonia.Hydroxyacetonitrile and ammonia is different proportionings when high temperature, the principal product difference.
Main reaction:
2CH 2OHCN+NH 3→HN(C2CN) 2+2H 2O
Side reaction:
CH 2OHCN+NH 3→NH 2CH 2CN+H 2O
3CH 2OHCN+NH 3→N(CH2CN) 3+3H 2O
4CH 2OHCN+HCHO+2NH 3→CH 2[N(CH 2CN) 2] 2+3H 2O
In addition, hydroxyacetonitrile and product nitrile are decomposed into prussic acid when at high temperature the time keeps longer easily, and the prussic acid polymerization causes product colour to deepen easily.
Produce in pmida98 or the glyphosate method iminodiacetonitrile hydrolysis at present in IDA (Iminodiacetic acid) method
The producer of technology adopts the alkaline hydrolysis method:
HN(CH 2CN) 2+2H 2O+2NaOH→HN(CH 2COONa) 2+2NH 3
2NH 3+H 2SO 4→(NH 4) 2SO 4
And in fact this important intermediate of iminodiethanoic acid does not all obtain; The product that in fact alkaline hydrolysis obtains is an iminodiacetic acid sodium; The ammonia sulfuric acid absorption of overflowing, perhaps water absorbs.Concentration is low, and amount is big.Ammonia excretion finishes the afterreaction product also to be needed to concentrate a large amount of water, and the concentration of iminodiacetic acid sodium is reached more than 32%, could guarantee to obtain the pmida98 of higher yields.Drip phosphorus trichloride then, this moment, jar internal volume was little, and the solid sodium chloride amount is big, and is big to equipment corrosion.
HN(CH 2COONa) 2+PCl 3+2H 2O+HCHO →(HO) 2P(O)CH 2N(CH 2COOH) 2+2NaCl+HCl
Reaction finishes, and does not separate out simultaneously with pmida98 in order to guarantee sodium-chlor, must add enough water and guarantee that sodium-chlor dissolves fully, could satisfy pmida98 content and reach more than 98%.Hydrogen chloride content also needs to continue further to neutralize with alkali than higher in addition.So the amount of sodium-chlor will be higher than the amount of the pmida98 that obtains in the filtrate that obtains behind the separation pmida98, the aftertreatment more complicated.
Patent No. ZL 00116540.2, " a kind of preparation N of applicant Shanghai Kaipu Fine Chemical Co., Ltd, the technology of N-oxalic acid amino methane phosphoric acid (pmida98) ", disclose and a kind ofly under vacuum, cold condition, reacted with phosphorus trichloride with the imido oxalic acid disodium salt, make phosphorus trichloride hydrolysis in system obtain phosphorous acid and hydrochloric acid simultaneously, preparation imido oxalic acid hydrochloride; Carry out the method for phosphine methylation prepared in reaction pmida98 again with formaldehyde.But because the phosphorus trichloride hydrolysis is thermopositive reaction, be difficult to control, easily produce the oxidized byproduct of by product, particularly phosphorous acid, therefore this method also exists very big defective.
Chinese patent application number 03131089.3, " the pmida98 new preparation process " of applicant Zhejiang Xinan Chemical Industry Group Co.Ltd discloses a kind ofly with the source of alkyl phosphite as phosphorous acid, originate as formaldehyde to contain formaldehyde carbon or acetal,
By-product chloroparaffin in the time of the preparation pmida98.This method complex process is unfavorable for production control.
" a kind of clean preparation method for preparing pmida98 with the hydroxyacetonitrile for the raw material one kettle way " of number of patent application 2000710090976.2 applicant Qinghuaziguang Yingli Chemical Technology Co. Ltd., Beijing, the method of narration remains the iminodiacetonitrile alkaline hydrolysis, in order to remedy above-mentioned deficiency, increased recovery sodium-chlor, reclaim hydrogenchloride, absorb ammoniacal liquor, preparation bicarbonate of ammonia, lime carbonate, sodium hydroxide, multistep technologies such as ammonium chloride, wherein containing multistep separates, mother liquor reclaims, feedstock production reuse etc., increase a large amount of utility appliance, increased the various wastewater generation.
In sum, all there are various deficiencies in the various methodologies of preparation pmida98 in the prior art, and raising haves much room for improvement.
Summary of the invention
Purpose of the present invention is to utilize vinyl cyanide coproduct hydrogen cyanic acid to do initial raw material, the preparation iminodiacetonitrile, and prepare iminodiethanoic acid through iminodiacetonitrile acidic hydrolysis thus, and then produce improving one's methods of pmida98.
Its reaction process is:
1.HCN+HCHO→HOCH 2CN
2COCH 2CN+NH 3→HN(CH 2CN) 2+H 2O
2.HN(CH 2CN) 2+4H 2O+H 2SO 4→HN(CH 2COOH) 2+(NH 4) 2SO 4
Perhaps
HN(CH 2CN) 2+4H 2O+2HCl→HN(CH 2COOH) 2+2NH 4Cl
3.HN(CH 2COOH) 2+H 3PO 3+HCHO(HO) 2P(O)CH 2N(CH 2COOH) 2+H 2O
The objective of the invention is to implement by following technical proposals:
Develop a kind of environmental-friendly new method that utilizes vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid, it is characterized in that reaction was divided into for three steps:
The first step, vinyl cyanide coproduct hydrogen cyanic acid be the preparation hydroxyacetonitrile earlier; The refabrication iminodiacetonitrile;
Second step, the iminodiacetonitrile of acquisition, the acid system hydrolysis prepares iminodiethanoic acid;
The 3rd step, the iminodiethanoic acid of acquisition, preparation N-phosphonomethyl iminodiethanoic acid;
(1) processing condition of the described the first step are:
1. prepare hydroxyacetonitrile
Batching mol ratio: prussic acid: formaldehyde: catalyzer=1: 1.0～1.1: 0.001～0.015;
Add catalyzer in the formaldehyde under stirring, 10～25 ℃ add vinyl cyanide coproduct hydrogen cyanic acid, and again in 10～40 ℃, addition reaction 1～6h is adjusted to solution PH≤6 with mineral acid, obtain hydroxyacetonitrile;
2. prepare iminodiacetonitrile
Batching mol ratio: hydroxyacetonitrile: ammonia=2: 1
Enter gas liquid mixer continuously with the ammonia after the vaporization, again by internal and external casing formula reactor reaction, the tubular reactor outlet material cools to 85～100 ℃ immediately behind the mixing;
Regulate material that 2. step obtains to PH 3～6 with mineral acid, stir and drop to room temperature, crystallization, fractional crystallization; Mother liquor concentrates through vaporizer under the vacuum of 0.04～0.099Mpa, and concentrated mother liquor drops to room temperature crystallization, fractional crystallization again; The iminodiacetonitrile of twice acquisition merges;
(2) processing condition in described second step are:
The preparation iminodiethanoic acid
Batching mol ratio: iminodiacetonitrile: sulfuric acid=1: 1.5～3.0;
Stir down, in 50～95 ℃ 20%～80% dilute sulphuric acid, slowly add the iminodiacetonitrile that the first step obtains, 100～125 ℃ of back flow reaction 1～6h; Reaction is finished, and batch recovery set with ammonia or ammoniacal liquor PH=1.9～2.7 that neutralize, is reduced to room temperature with the mother liquor that steams behind water and the recovery sulphur ammonium addings in, stirring and crystallizing 1～3h, and separation obtaining iminodiethanoic acid;
Mother liquor with ammonia PH=4.0～6.0 that neutralize, steams water to there being solid to separate out once more again, reduces to below 10 ℃, separates by-product sulphur ammonium, steams water and centrifuge mother liquor by batch applying mechanically;
(3) processing condition in described the 3rd step are:
Preparation N-phosphonomethyl iminodiethanoic acid
Batching mol ratio: iminodiethanoic acid: hydrochloric acid: phosphorous acid: formaldehyde=1: 1～1.5: 1～1.5: 1～2.0;
To the iminodiethanoic acid that mixes, drip formaldehyde in phosphorous acid and the hydrochloric acid, 108～115 ℃ of stirring reaction 2～8h, the phosphine methylation reaction is finished, and obtains N-phosphonomethyl iminodiethanoic acid; Mother liquor is applied mechanically by criticizing.
Above-mentioned method, when it is characterized in that preparing hydroxyacetonitrile, described catalyzer is a sodium bisulfite, S-WAT, ammonium sulphite or ammonium bisulfite; Or their mixture.
The method of the above, when it is characterized in that preparing iminodiacetonitrile, the stablizer that adds in the described hydroxyl acetonitrile aqueous solution is an acidic alumina, natural zeolite, acid type ZSM5 zeolite or their mixture.
The above-mentioned method of utilizing vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid, sulfuric acid process hydrolysis when it is characterized in that preparing iminodiacetonitrile, mol ratio is: iminodiacetonitrile: sulfuric acid=1: 1.5～3.0; 100～125 ℃ of temperature of reaction, reaction 1～6h; While producing ammonium sulfate byproduct salt.
The above-mentioned method of utilizing vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid, salt acid system hydrolysis when it is characterized in that preparing iminodiacetonitrile, mol ratio is: iminodiacetonitrile: hydrochloric acid=1: 2.5～5.0; 100～125 ℃ of temperature of reaction, reaction 1～6h; While side product sodium chloride salt.
Advantage of the present invention is:
1. not seeing so far has technical scale to utilize vinyl cyanide coproduct hydrogen cyanic acid to make the report of pmida98, the applicant gathers materials on the spot, utilize with Qilu Petrochemical and adjoin, the resources advantage that has the prussic acid (4000 tons/year) of pipe-line transportation has been started technical scale and has been utilized vinyl cyanide coproduct hydrogen cyanic acid to make the beginning of pmida98.Solve prussic acid transportation inconvenience, and influenced the region limitation of these products productions.
The present invention except utilize the applicant in first to file 200610048135.0 technology, obtain outside the hydroxyacetonitrile than low formaldehyde content, utilize the excellent properties of gas liquid mixer commodity to be applied in the iminodiacetonitrile reaction, through distributed control system (Distributed Control System, be called for short DCS control), guarantee hydroxyacetonitrile and two kinds of raw materials of ammonia, strict with 1.98 ~ 2.02: as enter reactor behind 1 the ratio uniform mixing, and pyroreaction to finish cooling immediately.Also investigate the stablizer that prevents product iminodiacetonitrile and polymerization of raw material hydroxyacetonitrile or decomposition in addition, effectively prevented the polymerization and the decomposition of nitrile product, made appearance color more shallow, improved iminodiacetonitrile quality and yield.
Hydroxyacetonitrile by first section internal and external casing formula interchanger after by outer reaction the heating of heat material or directly superheated water be heated to after 85 ~ 100 ℃ with vaporization after ammonia, enter into a gas liquid mixer continuously and mix earlier;
The reaction solution that mixes is about 2～3 minutes of the residence time (this moment, the temperature of reaction solution approximately was 160～170 ℃) in second section tubular reactor, enters into first section double-tube reactor skin then immediately and cools to 85～100 ℃ with the heat exchange of internal layer charging hydroxyacetonitrile;
The reaction mass of emitting from tubular reactor receives the tundish, regulates PH to 3～6 with corresponding acid, flows to continuously to stir in the crystallizer through siphon pipe to drop to room temperature, and best below 20 ℃, crystallization obtained iminodiacetonitrile more than 2 hours.
Mother liquor receives in the mother liquor tank, squeezes into falling-film evaporator with pump and concentrates under the vacuum of 0.4～0.99Mpa, concentrates the back mother liquor and is put into cooling crystallization in the crystallizer for the second time, and iminodiacetonitrile is wherein reclaimed in centrifugation.
3. acidolysis process of the present invention has been avoided the generation of sodium salt, and the ammonium salt that obtains can be according to different solubility, and effectively and product separation, the ammonium salt outward appearance that obtains is a white crystals, the sulphur ammonium nitrogen content reaches 20.8%, and the ammonium chloride nitrogen content reaches 25.7%, can be sold to fertilizer enterprise as raw material.
4. phosphine methylation conversion unit utilization ratio height of the present invention, output are big, and reaction mother liquor is applied mechanically fully, and wherein contained phosphorous acid and formaldehyde and catalyzer hydrochloric acid utilize fully once more, cut down the consumption of raw materials greatly.Avoid the generation of a large amount of three wastes.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is further set forth:
Shown among Fig. 1 that the present invention is a raw material with the prussic acid of Qilu Petrochemical company vinyl cyanide by-product, the whole process of preparation pmida98.(the first step, preparation hydroxyacetonitrile earlier; The refabrication iminodiacetonitrile; Second step, the iminodiacetonitrile of acquisition, the acid system hydrolysis prepares iminodiethanoic acid; The 3rd step, the iminodiethanoic acid of acquisition, preparation N-phosphonomethyl iminodiethanoic acid, i.e. " pmida98 ")
Embodiment 1: salt acid system hydrolysis iminodiacetonitrile: hydrochloric acid=1: 2.5～5.0; Finalize a text at last
(1) preparation hydroxyacetonitrile
Mol ratio dosage: prussic acid: formaldehyde=1: 1
Prussic acid is Shandong vinyl cyanide by-product; Formaldehyde is available from Qingzhou, Shandong; S-WAT, reagent.
Consumption: formaldehyde 25.0Kg (content 36%, pure 9.0Kg, 0.30kmol)
Prussic acid 8.14Kg (content 99.5%, pure 8.1Kg, 0.3kmol)
S-WAT 37.8g (0.3mol)
In the 50L glass reactor, add formaldehyde 24.25Kg, the 37.8g S-WAT is added the suitable quantity of water dissolving with 750g formaldehyde solution, splash in the reactor, after stirring evenly, open the cooling of refrigeration cycle pump interlayer and make reaction mass to 15 ℃, the liquid hydrogen cyanic acid of freezing preservation is added drop-wise in the reaction flask by constant pressure funnel, keep temperature of reaction at 10～15 ℃ in the dropping process,, finish, maintain the temperature at 10～15 ℃, it is 0.002% that stirring reaction 6 hours, sampling are surveyed free cyanogen content, formaldehyde content 0, surveying hydroxyacetonitrile content with hydrochloric acid adjusting PH at last to 4.0. is 50.38%, weight 33.89Kg, scale 17.07Kg, yield are 99.82%.
(2) preparation iminodiacetonitrile
The powder mixing that the hydroxyacetonitrile 33Kg that makes is added 10g aluminum oxide and 56gZSM5 zeolite, squeeze into internal and external casing formula reactor internal layer with ram pump, the outer circulation with superheated water earlier is heated to 85 ℃, then with the ammonia that measures by gas meter, mol ratio with 2: 1 regulates flow, enter the gas liquid mixer mixing simultaneously,, regulate the input speed of hydroxyacetonitrile and ammonia then by another section tubular reactor, the time that is reaction solution by second section reactor is about 2 minutes, discharging is by the skin of first section telescoping tubular reactor, and temperature is at 95 ℃ when cooling to outlet with internal layer charging hydroxyacetonitrile, and reaction solution is collected in the 501 glass reaction bottles, stirring down with the hydrochloric acid PH that neutralizes immediately is 5.5～6.0, with the cooling of refrigeration system via interlayer, reaction finishes, reaction solution PH=4.0 simultaneously, cool to 20 ℃ under continuing to stir, crystallization 2 hours, blowing suction filtration, the shallow white iminodiacetonitrile that obtains, room temperature is dried, heavy 12.1Kg, content 98.3%, scale 11.9Kg.Mother liquor concentrates between 48～55 ℃ in temperature under the 0.099Mpa vacuum, finishes back cooling crystallization, filter, after drying light brown iminodiacetonitrile 0.38Kg, content 97.4%, twice of scale 0.37Kg altogether iminodiacetonitrile scale 12.27Kg.Yield 88.59% (theoretical amount 13.85Kg)
(3) preparation iminodiethanoic acid
Method one
Mol ratio dosage: iminodiacetonitrile: hydrochloric acid=1: 5.0;
Iminodiacetonitrile, self-control; Technical hydrochloric acid, the commercial goods, Shandong;
Consumption: iminodiacetonitrile 48.3g (self-control, content 98.3%, pure 47.5g, 0.5mole);
Hydrochloric acid 294.4g (industry, the commercial goods, Shandong, content 31%, pure 91.25g, 2.5mole)
Hydrolysising condition is to stir 80～95 ℃ down, gradation adding iminodiacetonitrile in the hydrochloric acid, reaction 1～6h; Reaction is finished, the mother liquor after batch recovery steams water and reclaims the sulphur ammonium in the adding, ammonia or ammoniacal liquor neutralization, cooling, acquisition intermediate iminodiethanoic acid; Reaction mother liquor with the neutralization of ammonia or ammoniacal liquor, steams water once more again, and when having solid to separate out, cooling separates by-product sulphur ammonium, steams water and mother liquor by batch applying mechanically;
Add 294.4g technical hydrochloric acid 31% in 500ml four-hole reaction flask, stir down, temperature adds 98.3% iminodiacetonitrile 48.3 grams in the gradation of 80～95 ℃ of a small amount of.Add and slowly be warmed up to about 125 ℃, kept back flow reaction 6 hours, be inserted in (last crowd of mother liquor 256g that reclaims behind the ammonium chloride, wherein contain 12g iminodiacetic acid (salt) acid content 4.69%), at 70 ± 5 ℃ with the 25% ammoniacal liquor PH 1.9 that neutralizes, stir down and slowly cool to 10 ℃, be incubated one hour, filter.Obtain 98.0% iminodiethanoic acid 65.6g, pure 64.29g, 0.4834mole, productive rate 96.68%; Filtrate under agitation neutralizes under PH 4.0～4.5 normal pressures with 25% ammoniacal liquor and steams water, to will have solid to separate out the time till, reduce to 10 ℃,, analysed ammonium chloride 1 hour, filter and obtain ammonium chloride 84.7g, nitrogen content 25.7%, mother liquor 262g, the iminodiacetic acid (salt) acid content is that 4.60% cover is used down and criticized.
Method two
Mol ratio dosage: iminodiacetonitrile: hydrochloric acid=1: 4.0;
Iminodiacetonitrile, self-control; Technical hydrochloric acid, the commercial goods, Shandong;
Consumption: iminodiacetonitrile 48.3kg (self-control, content 98.3%, pure 47.5kg, 0.5kmole);
Hydrochloric acid 235.5kg (industry, the commercial goods, Shandong, content 31%, pure 73kg, 2.0kmole)
Hydrolysising condition is to stir 50～60 ℃ down, gradation adding iminodiacetonitrile in the hydrochloric acid, 100 ℃ of temperature of reaction. back flow reaction 1h; Reaction is finished, and batch reclaims the mother liquor after steaming water and reclaiming the sulphur ammonium addings in, 70 ± 5 ℃ with the ammonia PH 2.7 that neutralizes, slowly cool to 10 ℃ under stirring, be incubated one hour, filtration.Obtain 98.2% iminodiethanoic acid 66.2kg, pure 65.0kg, 0.4887kmole, productive rate 97.74%; Filtrate is under agitation with the ammonia PH 5.5～6.0 that neutralizes, and normal pressure steams water down, to will have solid to separate out the time till, reduce to 10 ℃,, analysed ammonium chloride 1 hour, filter and obtain ammonium chloride 86.2kg, nitrogen content 24.9%, mother liquor 262kg, the iminodiacetic acid (salt) acid content is that 4.60% cover is used down and criticized.
Method three
Mol ratio dosage: iminodiacetonitrile: hydrochloric acid=1: 2.5;
Iminodiacetonitrile, self-control; Technical hydrochloric acid, the commercial goods, Shandong;
Consumption: iminodiacetonitrile 48.3kg (self-control, content 98.3%, pure 47.5kg, 0.5kmole);
Hydrochloric acid 147.2kg (industry, the commercial goods, Shandong, content 31%, pure 45.63kg, 1.25kmole)
Hydrolysising condition is to stir 75～85 ℃ down, gradation adding iminodiacetonitrile in the hydrochloric acid, 110 ℃ of backflows of temperature of reaction. reaction 3h; Reaction is finished, and batch reclaims the mother liquor after steaming water and reclaiming the sulphur ammonium addings in, 70 ± 5 ℃ with the ammonia PH 2.5 that neutralizes, slowly cool to 10 ℃ under stirring, be incubated 1 hour, filtration.Obtain 98.5% iminodiethanoic acid 64.8kg, pure 63.83kg, 04799kmole, productive rate 95.98%; Filtrate under agitation neutralizes under PH 5.0～5.5 normal pressures with ammonia and steams water, to will have solid to separate out the time till, reduce to 10 ℃,, analysed ammonium chloride 1 hour, filter and obtain ammonium chloride 82.6kg, nitrogen content 25.9%, mother liquor 262kg, the iminodiacetic acid (salt) acid content is that 4.60% cover is used down and criticized.
(4) preparation N-phosphonomethyl iminodiethanoic acid
In the 500ml reaction flask, add 70% phosphorous acid 70.3g, 31% hydrochloric acid 76.5g opens stirring, add 98.0% iminodiethanoic acid 67.86g, stir down and slowly is warmed up to more than 110 ℃, begin to drip 37% formaldehyde 52g then, regulate the speed, in 3 hours, evenly add.Temperature remains on 108 ℃.After adding, continue to maintain the temperature at 108 ℃ of back flow reaction 4 hours.Drop to room temperature, filter, obtain pmida98, oven-dried weight 101.5g, content 98.50%, yield 88.09%.
Embodiment 2:
(1) preparation hydroxyacetonitrile
Mol ratio dosage: prussic acid: formaldehyde=1: 1.1
Prussic acid is Shandong vinyl cyanide by-product; Formaldehyde is available from Qingzhou, Shandong; S-WAT, sodium bisulfite, reagent.
Consumption: formaldehyde 22.92g (content 36%, pure 8.25Kg, 0.275kmol)
Prussic acid 6.78Kg (content 99.5%, pure 6.75Kg, 0.25kmol)
S-WAT 189g (1.5mol) sodium bisulfite 104g (1.0mol)
Schedule of operation is with embodiment 1.
Maintain the temperature at 20～25 ℃, stirring reaction 1 hour, it is 0 that free cyanogen content is surveyed in sampling, formaldehyde content 0001%, surveying hydroxyacetonitrile content with vitriol oil adjusting PH at last to 3.0. is 48.36%, weight 29.30Kg, scale 14.17Kg, yield are 99.44%.
(2) preparation iminodiacetonitrile
The hydroxyacetonitrile 29Kg that makes being added the powder mixing of 58gZSM5 zeolite, press embodiment 1 and prepare the iminodiacetonitrile program, is 3.0～3.5 with the vitriol oil PH that neutralizes immediately under agitation at last, with the cooling of refrigeration system via interlayer, reaction finishes, reaction solution PH=5.0 simultaneously, cool to 10 ℃ under continuing to stir, crystallization 2 hours, blowing suction filtration, the shallow white iminodiacetonitrile that obtains, room temperature is dried, heavy 9.71Kg, content 98.1%, scale 9.53Kg.Mother liquor concentrates between 75～85 ℃ in temperature under the 0.04Mpa vacuum, finishes back cooling crystallization, filter, after drying brown iminodiacetonitrile 0.31Kg, content 97.8%, twice of scale 0.30Kg altogether iminodiacetonitrile scale 9.83Kg.Yield 84.09% (theoretical amount 11.69Kg)
(3) preparation iminodiethanoic acid
In the 1000ml reaction flask, add 67.5 gram water, carefully splash into the 300 gram vitriol oils under the restir, with the iminodiacetonitrile of 96.84g98.1% 50～65 ℃ of gradation join add in the bottle after, be warmed up to 120～125 ℃, reacted 1 hour, add the 250ml recovery and steam water, be inserted in the mother liquor (346.7g, wherein the iminodiacetic acid (salt) acid content 4.58%) that reclaims behind the sulphur ammonium under 60～65 degree with the neutralization of 25% ammoniacal liquor, arrive PH 2.7.Drop to 20 ℃, stir 3 hours after-filtration of insulation crystallization down. get iminodiethanoic acid 132g, content 98.4%.Yield 97.66%.The logical ammonia of mother liquor transfers PH to steam water to 6.0. under normal pressure, when having solid to separate out till.Reduce to 15 ℃, filter out sulphur ammonium 346.7 grams, nitrogen content 20.8%.Mother liquor (350g, iminodiacetic acid (salt) acid content 4.57%) cover is used down and is criticized.
(4) preparation N-phosphonomethyl iminodiethanoic acid
In the 500ml reaction flask, add 70% phosphorous acid 87.9g, 31% hydrochloric acid 88.3g opens stirring, add 98.4% iminodiethanoic acid 67.6g, stir down and slowly is warmed up to 108 ℃, begin to drip 37% formaldehyde 81.1g then, regulate the speed, in 3 hours, evenly add.Temperature remains on 108 ℃.After adding, continue to maintain the temperature at 115 ℃ of back flow reaction 6 hours. drop to room temperature, filter, obtain pmida98, oven-dried weight 108.8g, content 98.6%, yield 94.52%.Mother liquid recycle adds the phosphorous acid that scale is 64.4g70% again to following batch, and scale is the iminodiethanoic acid of 66.5g, and 31% hydrochloric acid 57.6g is warmed up to and drips formaldehyde 56.76g more than 110 ℃ ... repeat above operation.Pmida98 weight is respectively that 106.0g, 106.6g, 107.1g content are respectively 98.46%, 98.32%98.28%, yield is respectively 91.95%, 92.34%, 92.7%
Embodiment 3
(1) preparation hydroxyacetonitrile
Mol ratio dosage: prussic acid: formaldehyde=1: 1.05
Prussic acid is Shandong vinyl cyanide by-product; Formaldehyde is available from Qingzhou, Shandong; Ammonium sulphite, reagent.
Consumption: prussic acid 8.14Kg (content 99.5%, pure 8.1Kg, 0.3kmol)
Formaldehyde 26.25Kg (content 37%, pure 9.45Kg, 0.315kmol)
Ammonium sulphite 174g (1.5mol)
In 501 glass reactors, add formaldehyde 26.25Kg, with 174g ammonium sulphite 1500g water dissolution, splash in the reactor, after stirring evenly, open the cooling of refrigeration cycle pump interlayer and make reaction mass to 15 ℃, the liquid hydrogen cyanic acid of freezing preservation is added drop-wise in the reaction flask by constant pressure funnel, keep temperature of reaction at 15～25 ℃ in the dropping process,, finish, maintain the temperature at 15～20 ℃, it is 0 that stirring reaction 3 hours, sampling are surveyed free cyanogen content, formaldehyde content 0.03%, surveying hydroxyacetonitrile content with sulfuric acid adjusting PH at last to 5.0. is 45.70%, weight 37.4Kg, scale 17.09Kg, yield are 99.94%.
(2) preparation iminodiacetonitrile
The hydroxyacetonitrile 36.0Kg that makes is added the powder mixing of 15g aluminum oxide and 40g mordenite, according to embodiment 1 procedure operation, is 4.5～5.0 with the sulfuric acid PH that neutralizes immediately under agitation at last, with the cooling of refrigeration system via interlayer, reaction finishes, reaction solution PH=4.5 simultaneously, cool to 20 ℃ under continuing to stir, crystallization 2 hours, blowing suction filtration, the shallow white iminodiacetonitrile that obtains, room temperature is dried, heavy 12.0Kg, content 98.6%, scale 11.83Kg.Mother liquor concentrates between 50～58 ℃ in temperature under the 0.09Mpa vacuum, finishes back cooling crystallization, filter, after drying light brown iminodiacetonitrile 0.45Kg, content 97.1%, twice of scale 0.44Kg altogether iminodiacetonitrile scale 12.27Kg.Yield 88.61% (theoretical amount 13.85Kg)
(3) preparation iminodiethanoic acid
Method one
In the 3000L reactor, add 1755kg water, carefully splash into the 450kg vitriol oil under the restir, be under 95 ℃ the iminodiacetonitrile gradation of 290.8kg98% to be joined in the reactor in temperature.After adding, be warmed up to 120～125 ℃, reacted 6 hours, be inserted in the mother liquor 750L (iminodiacetic acid (salt) acid content 4.35%) that reclaims behind the sulphur ammonium, under 65～70 ℃ with the ammonia neutralization, to PH 1.9.Drop to room temperature, stir insulation suction filtration after 1 hour. iminodiethanoic acid 395kg, with the ammonia PH=6.0 that neutralizes, normal pressure steams water under normal pressure for content 98.7%, yield 97.71%, mother liquor, when having solid to separate out till.Reduce to 15 ℃, filter out sulphur ammonium 1040kg, nitrogen content 21.2%.Residue mother liquor 7601 (iminodiacetic acid (salt) acid content 4.62%)
Method two
In the 3000L reactor, add 230kg water, carefully splash into the 750kg vitriol oil under the restir, be under 80 ℃ the iminodiacetonitrile gradation of 290.8kg98% to be joined in the reactor in temperature.After adding, be warmed up to 120～125 ℃, reacted 3 hours, be inserted in the mother liquor 750L (iminodiacetic acid (salt) acid content 4.35%) that reclaims behind the sulphur ammonium, under 65～70 ℃ with the ammonia neutralization, to PH 2.5.Drop to room temperature, stir insulation suction filtration after 2 hours, iminodiethanoic acid 400kg, with the ammonia PH=6.0 that neutralizes, normal pressure steams water under normal pressure for content 98.5%, yield 98.7%, mother liquor, when having solid to separate out till.Reduce to 15 ℃, filter out sulphur ammonium 1040kg, nitrogen content 21.2%.Residue mother liquor 760L (iminodiacetic acid (salt) acid content 4.62%)
(4) preparation N-phosphonomethyl iminodiethanoic acid
In the 3000L reactor, open cover, drop into 98.5% iminodiethanoic acid 4050kg earlier, first-class cover is opened the phosphorous acid 351.4kg of vacuum suction 70%, 31% hydrochloric acid 353.2kg.Stir down and slowly is warmed up to 110 ℃, begin to drip 37% formaldehyde 243.2kg then, regulate the speed, remain on 110 ℃, evenly add in 3 hours in temperature.After adding, continue to maintain the temperature at 110 ℃ of back flow reaction 2 hours.Drop to room temperature, filter, obtain pmida98, oven-dried weight 615kg, content 98.4%.Yield 90.06%.Mother liquid recycle is to following batch, and second batch is played the adding scale is the phosphorous acid of 350kg70%, content 98.5% iminodiethanoic acid 405Kg, and 31% hydrochloric acid 325kg is warmed up to the formaldehyde 243.2kg of 110 ℃ of droppings 37%; Repeat above operation, obtain pmida98 625kg.Content 98.3%, yield 91.43%.
Pmida98 is reflected to apply mechanically and will steams earlier before dripping formaldehyde behind the mother liquor more than the water to 108 ℃, repeats other operations then.Feeding quantity is all with second batch, and last pmida98 yield is respectively 89.53%, 90.18%, 89.82%, 90.47%.Be white crystalline powder, content is greater than 98%.

Claims (6)

1. environmental-friendly new method that utilizes vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid is characterized in that reaction was divided into for three steps:
The first step, vinyl cyanide coproduct hydrogen cyanic acid be the preparation hydroxyacetonitrile earlier; The refabrication iminodiacetonitrile;
Second step, the iminodiacetonitrile of acquisition, the acid system hydrolysis prepares iminodiethanoic acid;
The 3rd step, the iminodiethanoic acid of acquisition, preparation N-phosphonomethyl iminodiethanoic acid;
(1) processing condition of the described the first step are:
1. prepare hydroxyacetonitrile
Batching mol ratio: prussic acid: formaldehyde: catalyzer=1: 1.0～1.1: 0.001～0.015;
Add catalyzer in the formaldehyde under stirring, 10～25 ℃ add vinyl cyanide coproduct hydrogen cyanic acid, and again in 10～40 ℃, addition reaction 1～6h is adjusted to solution PH≤6 with mineral acid, obtain hydroxyacetonitrile;
2. prepare iminodiacetonitrile
Batching mol ratio: hydroxyacetonitrile: ammonia=2: 1
Enter gas liquid mixer continuously with the ammonia after the vaporization, again by internal and external casing formula reactor reaction, the tubular reactor outlet material cools to 85～100 ℃ immediately behind the mixing;
Regulate material that 2. step obtains to PH 3～6 with mineral acid, stir and drop to room temperature, crystallization, fractional crystallization; Mother liquor concentrates through vaporizer under the vacuum of 0.04～0.099Mpa, and concentrated mother liquor drops to room temperature crystallization, fractional crystallization again; The iminodiacetonitrile of twice acquisition merges;
(2) processing condition in described second step are:
The preparation iminodiethanoic acid
Batching mol ratio: iminodiacetonitrile: sulfuric acid=1: 1.5～3.0;
Stir down, in 50～95 ℃ 20%～80% dilute sulphuric acid, slowly add the iminodiacetonitrile that the first step obtains, 100～125 ℃ of back flow reaction 1～6h; Reaction is finished, and batch recovery set with ammonia or ammoniacal liquor PH=1.9～2.7 that neutralize, is reduced to room temperature with the mother liquor that steams behind water and the recovery sulphur ammonium addings in, stirring and crystallizing 1～3h, and separation obtaining iminodiethanoic acid;
Mother liquor with ammonia PH=4.0～6.0 that neutralize, steams water to there being solid to separate out once more again, reduces to below 10 ℃, separates by-product sulphur ammonium, steams water and centrifuge mother liquor by batch applying mechanically;
(3) processing condition in described the 3rd step are:
Preparation N-phosphonomethyl iminodiethanoic acid
Batching mol ratio: iminodiethanoic acid: hydrochloric acid: phosphorous acid: formaldehyde=1: 1～1.5: 1～1.5: 1～2.0;
To the iminodiethanoic acid that mixes, drip formaldehyde in phosphorous acid and the hydrochloric acid, 108～115 ℃ of stirring reaction 2～8h, the phosphine methylation reaction is finished, and obtains N-phosphonomethyl iminodiethanoic acid; Mother liquor is applied mechanically by criticizing.
2. according to the described method of claim 1, when it is characterized in that preparing hydroxyacetonitrile, described catalyzer is a sodium bisulfite, S-WAT, ammonium sulphite or ammonium bisulfite; Or their mixture.
3. in accordance with the method for claim 1, when it is characterized in that preparing iminodiacetonitrile, the batching mol ratio:
Hydroxyacetonitrile: ammonia=1.98～2.02: 1.
4. in accordance with the method for claim 1, when it is characterized in that preparing iminodiacetonitrile, the stablizer that adds in the described hydroxyl acetonitrile aqueous solution is an acidic alumina, natural zeolite, acid type ZSM5 zeolite or their mixture.
5. according to the described method of utilizing vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid of claim 1, sulfuric acid process hydrolysis when it is characterized in that preparing iminodiacetonitrile, mol ratio is: iminodiacetonitrile: sulfuric acid=1: 1.5～3.0;
100～125 ℃ of temperature of reaction, reaction 1～6h; While producing ammonium sulfate byproduct salt.
6. according to the described method of utilizing vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid of claim 1, salt acid system hydrolysis when it is characterized in that preparing iminodiacetonitrile, mol ratio is: iminodiacetonitrile: hydrochloric acid=1: 2.5～5.0; 100～125 ℃ of temperature of reaction, reaction 1～6h; While side product sodium chloride salt.
CN 201010011402 2010-01-05 2010-01-05 Method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid Expired - Fee Related CN101747369B (en)

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