CN104693239B

CN104693239B - Preparation N, the waste water complete set technique of N-oxalic acid amino methane phosphoric acid

Info

Publication number: CN104693239B
Application number: CN201510102135.3A
Authority: CN
Inventors: 杨建华
Original assignee: Long-Range Chemical Co Ltd In Yueping City
Current assignee: Long-Range Chemical Co Ltd In Yueping City
Priority date: 2015-03-09
Filing date: 2015-03-09
Publication date: 2016-05-25
Anticipated expiration: 2035-03-09
Also published as: CN104693239A

Abstract

The present invention relates to one and prepare N, the waste water complete set technique of N-oxalic acid amino methane phosphoric acid, after condensation reaction, filtering reacting liquid, obtains PMIDA filter cake and filtrate; Rinse PMIDA filter cake, obtain PMIDA and flushing waste water; Described filtrate after treatment, pass into hydrogen chloride with precipitated sodium chloride, obtain the hydrochloric acid solution that can apply mechanically; Processing described flushing waste water uses in the alkaline hydrolysis step of iminodiacetonitrile with cover. Beneficial effect of the present invention is: respectively walk wastewater pH and the impurity situation of reaction according to IDA process route, it is overlapped respectively in the reactions steps of using other, reduce energy consumption, save human and material resources, realize energy-saving and emission-reduction; The consumption that reduces raw material, saves production cost, and can also improve certain yield, therefore, has taken into account Social benefit and economic benefit.

Description

Preparation N, the waste water complete set technique of N-oxalic acid amino methane phosphoric acid

Technical field

The invention belongs to PMIDA preparation field, be specifically related to one and prepare N, N-oxalic acid amino methane phosphorusThe waste water complete set technique of acid (PMIDA) PMIDA.

Background technology

N, N-oxalic acid amino methane phosphoric acid, is also called N-((phosphonomethyl)) imido-acetic acid and (is commonly called as twoSweet phosphine, english abbreviation is PMIDA), it is the important sweet ammonia of wide spectrum steriland herbicide phosphoryl methyl of preparationThe intermediate of acid (glyphosate). Traditional IDA route production technology is that iminodiacetonitrile is at hydroxideIn sodium solution, hydrolysis becomes the sodium salt of iminodiacetic acid (IDA), and then its acidifying is converted into imidoThe strong acid salt of base oxalic acid, then carries out phosphoryl methyl condensation reaction, and add phosphorous acid and drip formaldehyde,After dripping, then drip in liquid caustic soda and hydrochloric acid, stir, crystallization generates PMIDA. About Monsanto ChemicalsPatent (patent No.: US4724103) has solved the problem of iminodiacetic acid (IDA) that do not purify in production,And a large amount of waste water, waste gas substantially all cannot solve during PMIDA is produced.

The processing method (Granted publication CN102674589B) of patent N-(phosphonomethyl) iminodiacetic acid wastewater, discloses employingAbsorption method is isolated the iminodiacetonitrile in N-(phosphonomethyl) iminodiacetic acid wastewater, then utilizes complex scheme to make in waste water high denseThe method that the sodium chloride of degree is separated out. But this method is only to have reduced the salt content in waste water, preparation technologyIn but still exist the situations of a large amount of discharges of waste water, waste gas.

The cycle applications (Granted publication CN101607969B) of condensation evaporated water of N-phosphonomethyliminoacidetic acidetic, discloses twoThe method that steams water of recycling condensation workshop section in sweet phosphine production process, a part of waste water is for the preparation of AsiaPhosphoric acid, another part waste water is for absorbing hydrogen chloride waste gas. This method has solved technique to a certain extentWaste water, waste gas problem that middle condensation workshop section produces, but a large amount of waste water that other steps are produced, waste gas are notProvide rational solution.

Summary of the invention

The a large amount of the problems referred to above of discharging of waste water, waste gas that exist in order to solve prior art, the invention providesOne is prepared N, the waste water complete set technique of N-oxalic acid amino methane phosphoric acid, make PMIDA produce substantially withoutWaste water discharge, fully reuse the various chemical substances that contain in waste water, reach PMIDA cleaner production,Carry out production strictly in line with rules and regulations, resources circulation applies mechanically production.

The technical solution adopted in the present invention is:

One is prepared N, and the waste water complete set technique of N-oxalic acid amino methane phosphoric acid comprises the system of phosphorous acidStandby, alkaline hydrolysis, iminodiacetic acid disodium salt acidifying and condensation step, after described condensation reaction, filter anti-Answer liquid, obtain PMIDA filter cake and filtrate; Rinse PMIDA filter cake, obtain PMIDA and flushing waste water; InstituteState filtrate after treatment, pass into hydrogen chloride with precipitated sodium chloride, obtain the hydrochloric acid solution that can apply mechanically; Process instituteStating flushing waste water uses in the alkaline hydrolysis step of iminodiacetonitrile with cover.

In traditional handicraft, at phosphoryl methyl (condensation reaction) afterwards, dilute alkaline soln is added in reactant liquor,Regulate the isopotential point of pH to PMIDA, to reduce the loss of PMIDA in water. The present invention has reduced oneRoad utilizes the operation of diluted alkaline neutralization, has both reduced the input of equipment and manpower, and has greatly reduced raw materialCost, the more important thing is, the wastewater problem that puzzlement PMIDA is produced has obtained solving comparatively thoroughly, filterLiquid is in order to obtain the hydrochloric acid solution that can apply mechanically, and flushing waste water cover is used in alkaline hydrolysis step. Excessive Asia in filtratePhosphoric acid, hydrochloric acid, formaldehyde etc. have obtained great utilization. Therefore, this technique possesses has on environmental protection and economyDouble dominant.

Preferably, described hydrogen chloride is to prepare the hydrogen chloride producing in phosphorous acid process. Phosphorous acid preparation processIn hydrogen chloride can be fully used.

Preferably, the intake of described hydrogen chloride be greater than described filtrate amount 31%. According to common-ion effect,Phosphorus trichloride and hydrochloric acid reaction are prepared to the hydrogen chloride gas of emitting in phosphorous acid process and be passed in filtrate, whenWhen hydrogen chloride content in filtrate reaches a certain amount of, while being preferably hydrogen chloride content > 31% (mass ratio),, while exceeding 31% critical point, 99% above sodium chloride in filtrate all can separate out, and can obtain after filteringHydrochloric acid solution and sodium chloride. Meanwhile, this process does not need to increase the energy, one ton of PMIDA of every production at least thanTraditional handicraft is saved two tons of steam, energy-saving and emission-reduction.

Further, the described hydrochloric acid solution cover of applying mechanically is used iminodiacetic acid disodium salt acidifying, contractingClose and the preparation process of phosphorous acid in. The hydrochloric acid solution of acquisition is used above in reactions steps, realize coverWith, reduce discharging of waste liquid.

Preferably, the treatment step of described filtrate comprises and first carries out adsorption reaction, refilters. Remove by absorptionRemove the foreign pigment in filtrate, be beneficial to and carry out applying mechanically of filtrate.

Preferably, process described flushing waste water with inorganic base, first regulate the pH of described flushing waste water for neutral,Waste water after treatment is made into the thin liquid alkali in water 20～22% with liquid caustic soda or sheet alkali, as iminodiacetonitrile alkaliThe reactant liquor of separating.

Further, the water steaming in described condensation reaction is for the flushing of Iminodiacetate hydrochlorate. ContractingClose reaction and can be divided into three steps and divide water, the first step is that a neutral sodium salt divides water, distills out a large amount of pH for neutralWater, be large point of water; Second step becomes after Iminodiacetate hydrochlorate and steams under acid condition for adding hcl acidifyingThe pH distillating is acid water, and its water yield is less, is little point of water; The 3rd step is by flushing iminodiacetic acid (salt)The water of acid hydrochloride filter cake is steamed out. The water steaming in condensation reaction is put into next group IminodiacetateIn the filtration of hydrochlorate, washing, thereby realize the recycled between acidifying, condensation two-step reaction.

Further, the water steaming before iminodiacetic acid one sodium salt acidifying is in order to absorb iminodiacetonitrile alkaliThe ammonia producing in solution or in order to rinse PMIDA filter cake; Iminodiacetic acid one sodium salt acidifying becomes iminodiacetic acid (salt)The water steaming in acid hydrochloride process prepares in order to absorb the hydrogen chloride producing in phosphorous acid process.

Preferably, the water that the insulation of iminodiacetonitrile alkaline hydrolysis steams after finishing is in order to absorb iminodiacetonitrile alkaliThe ammonia producing in solution.

Beneficial effect of the present invention is: according to IDA process route respectively walk reaction waste water (1, condensation courseIn great Fen Shui and little Fen Shui; 2, the water that alkaline hydrolysis insulation steams after finishing; 3, PMIDA filtrate; 4, two sweetThe flushing waste water of phosphine) pH and impurity situation, it is overlapped respectively in the reactions steps of using other, reduction energy consumption,Human and material resources, realize energy-saving and emission-reduction; The consumption that reduces raw material, saves production cost, and can also improve oneFixed yield, therefore, has taken into account Social benefit and economic benefit.

Detailed description of the invention

One, production technology

1. alkaline hydrolysis: by the wash water charcoal absorption of the PMIDA filter cake after condensation reaction, by filteringAfter the flushing water that obtains, adjust pH to become neutral flushing water, then with liquid caustic soda or sheet alkali be made in water 20%～22% thin liquid alkali, drops into iminodiacetonitrile and carries out alkaline hydrolysis reaction, makes iminodiacetic acid disodium salt moltenLiquid. Wherein, the ammonia water that reaction produces absorbs and (comprises what water that the alkaline hydrolysis later stage steams and condensation steamed early stageNeutral water).

2. acidifying, one-level acidifying: by iminodiacetic acid disodium salt solution, add a hydrochloric acid, by imino groupThe acidifying of oxalic acid disodium salt becomes iminodiacetic acid one sodium salt. After acidifying finishes, throw active carbon and decolouredFilter, obtain the filtrate of imido-SDA salt. Two-stage acidulation: this filtrate distillation is separated to neutrality(wherein, a part of water is for absorbing the ammonia that iminodiacetonitrile alkaline hydrolysis process is emitted, another part for waterWater washing PMIDA), and then add hydrochloric acid and make Iminodiacetate hydrochlorate, esterification continued (nowFor the acid water containing certain hydrogen chloride, be used for absorbing and prepare the unnecessary hydrogen chloride of emitting in phosphorous acid process),Divide after water filtering reacting liquid while hot, filter cake hot wash, the filter cake after washing is sodium chloride, then with fullWith after salt water washing, can work as Nacl sell; Filtrate is Iminodiacetate acid salt solution.

3. condensation, Iminodiacetate hydrochlorate filtrate and washings are entered to condensation kettle, continue esterification(this point of water is also faintly acid, can be used to wash the filter cake in the two-stage acidulation of next group), drops into after having divided waterPhosphorous acid, and drip formaldehyde and carry out condensation reaction. After condensation finishes, by cooling reactant liquor, filter, washing,After oven dry, obtain PMIDA finished product. Also obtain in addition filtrate and flushing waste water. The flushing waste water of PMIDA filter cake firstCarry out sedimentation and hold back a small amount of PMIDA that washing process is taken out of, then with charcoal absorption decolouring, filter, thisTime filtrate main component be water, a small amount of sodium chloride, a small amount of hydrochloric acid, phosphorous acid etc., this washes is addedInorganic base, as NaOH, potassium hydroxide, sodium hydroxide solution or other alkaline matters, has few during this timeAmount sodium chloride is separated out, and after filtration, by this alkali lye, cover is used in the alkaline hydrolysis reaction of iminodiacetonitrile.

Filtrate, after charcoal absorption sedimentation decolouring, is used for absorbing and prepares the chlorine of releasing in phosphorous acid processChange hydrogen.

4. hydrogen chloride is emitted in the preparation of phosphorous acid: phosphorus trichloride reacts and obtains phosphorous acid with hydrochloric acid solution simultaneouslyGas. Wherein, the filtrate of condensation step can absorb most hydrogen chloride gas, precipitated sodium chloride simultaneously,Obtain after filtering hydrochloric acid solution (wherein, hydrochloric approximately 31.2%, containing phosphorous acid approximately 3.22%). RemainingHydrogen chloride gas can distill the acid water separating with the condensation later stage and absorb, thereby obtains hydrochloric acid.

It should be noted that, though the concrete input amount of unlisted each raw material in above reactions steps, this area skillArt personnel can derive raw material consumption according to reaction equation and traditional its preparation process, thereby realize wholeCover technological reaction.

Two, experimental data

In the present invention, the remaining salt in thin liquid alkali neutralization reaction liquid of the PMIDA suspension after condensation finishesAcid, does not neutralize PMIDA yield is not almost affected, and can greatly reduce amount of filtrate. To this weDone with in liquid caustic soda and 100% hydrochloric acid, in and 80% hydrochloric acid, in and 50% hydrochloric acid, in and 20% hydrochloric acid andNot and the experiment of hydrochloric acid, result contrast is as following table:

Calculate to drop into raw material iminodiacetonitrile (purity 95%) 150g, condensation finishes should in rear reactant liquorResidue hydrochloric acid 46g, neutralization need to be 336g by the amount of 15% liquid caustic soda completely. Above data are 10 batches of lab scalesMean value. As can be seen from the above data, need not neutralize and use in NaOH and gained PMIDA finished product containsThe result of amount and yield is basically identical. The PMIDA yield obtaining after the filtrate not neutralizing is applied mechanically, also has slightlyThere is rising, the more important thing is that mother liquor can apply mechanically completely, hydrochloric acid in mother liquor, phosphorous acid, dissolving twoSweet phosphine has all obtained utilization.

The flushing waste water cover consumption of PMIDA is respectively 0,20%, 40%, 50%, 60%, 80%, 100%,Be used for joining the thin liquid alkali of 22% left and right, then throw 150g iminodiacetonitrile (95%) and carry out alkaline hydrolysis, then makeBecome PMIDA, its output and yield are as following table:

Above institute number of cases certificate is the mean value of 10 batches of lab scales. As can be seen here, slurry part is applied mechanically and allApply mechanically PMIDA yield and content are not almost affected.

Though liquid is applied mechanically the technological means of comparatively commonly using for chemical field, but IDA route is prepared PMIDA workSkill is never applied. The present invention is by the pH processing mode of creationary change condensation reaction solution,Realize technique waste water and apply mechanically, finally thoroughly solved the wastewater problem that puzzlement PMIDA is produced, and obtainedBeyond thought technique effect:

1. PMIDA production technology of the present invention can reach waste water and all applies mechanically, and realizes wastewater zero discharge;

2. the process from condensation esterification to filtrate absorbing hydrogen chloride, do not need additionally to increase the energy,Therefore, one ton of PMIDA of every production is at least saved two tons of steam than traditional handicraft, is conducive to environmental protection, jointCan reduce discharging, PMIDA and glyphosate industry are all had great significance;

3. the hydrochloric acid solution forming after filtrate absorbing hydrogen chloride can meet the demand of IDA route technique to hydrochloric acidAmount, therefore, without outsourcing, reduces discharging and reduces production costs simultaneously, and raw material consumption has larger decline, per tonEconomize in raw materials 400 to 500 yuan of costs of PMIDA, reach the bumper harvests of Social benefit and economic benefit;

4., after waste water is applied mechanically, the yield of PMIDA is slightly improved.

The present invention is not limited to above-mentioned preferred forms, and anyone can draw it under enlightenment of the present inventionHis various forms of products, no matter but on its method or composition, do any variation, every have and the applicationIdentical or akin technical scheme, within all dropping on protection scope of the present invention.

Claims

1. prepare a N, the waste water complete set technique of N-oxalic acid amino methane phosphoric acid, comprises phosphorous acidPreparation, alkaline hydrolysis, iminodiacetic acid disodium salt acidifying and condensation step, it is characterized in that: by imino groupDiacetin hydrochlorate filtrate and washings enter condensation kettle, and esterification drops into phosphorous acid after having divided water, andDrip formaldehyde and carry out condensation reaction; After described condensation reaction, filtering reacting liquid, obtain PMIDA filter cake andFiltrate; Rinse PMIDA filter cake, obtain PMIDA and flushing waste water; Described filtrate after treatment, passes into chlorineChange hydrogen with precipitated sodium chloride, obtain the hydrochloric acid solution that can apply mechanically; Process described flushing waste water, inhale with active carbonAttached, after filtration, obtain flushing water, the pH that regulates described flushing water is for neutral, then joins with liquid caustic soda or sheet alkaliClose the alkaline solution in water 20～22%, to overlap in the alkaline hydrolysis step of using iminodiacetonitrile.

2. waste water complete set technique according to claim 1, is characterized in that: described hydrogen chlorideIntake be greater than described filtrate amount 31%.

3. waste water complete set technique according to claim 2, is characterized in that: described hydrogen chloride isPrepare the hydrogen chloride producing in phosphorous acid process.

4. waste water complete set technique according to claim 1, is characterized in that: described applying mechanicallyHydrochloric acid solution cover is used the preparation of described iminodiacetic acid disodium salt acidifying, described condensation or described phosphorous acidIn process.

5. waste water complete set technique according to claim 1, is characterized in that: the locating of described filtrateReason comprises first carries out adsorption reaction, refilters.

6. according to the waste water complete set technique described in claim 1-5 any one, it is characterized in that: described contractingClose the flushing for Iminodiacetate hydrochlorate filter cake of the water that steams in reaction.

7. waste water complete set technique according to claim 6, is characterized in that: iminodiacetic acidThe water steaming before one sodium salt acidifying is in order to absorb the ammonia producing in iminodiacetonitrile alkaline hydrolysis and to rinse PMIDAFilter cake; Iminodiacetic acid one sodium salt acidifying becomes the water steaming in Iminodiacetate hydrochlorate process in order to inhaleReceipts are prepared the hydrogen chloride producing in phosphorous acid process.

8. waste water complete set technique according to claim 7, is characterized in that: iminodiacetonitrileThe water steaming after alkaline hydrolysis insulation finishes is in order to absorb the ammonia producing in iminodiacetonitrile alkaline hydrolysis.