CN104313636A - Novel eco-friendly clean production technology of high-purity EDTA-2Na - Google Patents
Novel eco-friendly clean production technology of high-purity EDTA-2Na Download PDFInfo
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Abstract
The invention discloses a novel eco-friendly clean production technology of high-purity EDTA-2Na. The novel eco-friendly clean production technology comprises the following steps of 1, feeding an EDTA-4Na aqueous solution having a mass concentration of 5-30% as a raw material into a bipolar membrane electrodialysis system, and carrying out bipolar membrane electrodialysis treatment, wherein in a salt chamber, a pH value is controlled in a range of 4.0-5.0 and an EDTA-2Na solution is obtained and in an alkali chamber, a sodium hydroxide solution is obtained, and 2, separating EDTA-2Na from the EDTA-2Na solution. The bipolar membrane electrodialysis technology realizes direct conversion of EDTA-4Na into EDTA-2Na and sodium hydroxide recovery and is free of an acid for neutralization so that by-product such as sodium sulfate or common salt is completely eliminated, three waste pollution is avoided, a salt-containing waste water treatment cost is reduced, the high-purity product is obtained and a product yield is high.
Description
Technical field
The present invention relates to the production method of a kind of EDTA-2Na, be specifically related to the environment-protecting clean new process of production of a kind of high purity EDTA-2Na.
Background technology
Current EDTA-2Na production method is mainly divided into four kinds according to the variable raw materials used: chloroactic acid method, prussic acid method, sodium cyanide method and hydroxyacetonitrile method.But no matter which kind of method, all need the EDTA-4Na obtained to carry out acidifying, obtain EDTA, the EDTA obtained neutralizes through the sodium hydroxide of two equivalents again, obtains EDTA-2Na product.But, in order to obtain EDTA-2Na product, a large amount of waste water and waste residue will be produced, often produce 1 ton of EDTA-2Na product, the sodium sulfate of 1.5 ~ 2.5 tons can be produced, the reluctant saliferous of discharge, containing edta salt waste water 3 ~ 5 tons, the discharge of a large amount of waste water and dregs not only pollutes environment, but also brings the increase of EDTA-2Na production cost; And, in traditional EDTA-2Na separation and purification process, EDTA-2Na product can lose with the discharge of waste water and dregs, and therefore, the yield of EDTA-2Na product only has 85% ~ 88%, and the EDTA-2Na quality product obtained is poor, purity only has about 98.5%, and impurity main in its product is sodium sulfate or sodium-chlor, although can pass through recrystallization technology separation and purification EDTA-2Na and sodium sulfate, but its cost will increase greatly, this will be unfavorable for the production of EDTA-2Na.
Summary of the invention
In view of this, the object of the present invention is to provide the environment-protecting clean new process of production of a kind of high purity EDTA-2Na, can obtain highly purified product, and product yield is high, do not produce any by product, three-waste free pollution, production cost is low.
For achieving the above object, the invention provides following technical scheme:
The environment-protecting clean new process of production of high purity EDTA-2Na of the present invention, comprises the following steps:
1) with massfraction be the EDTA-4Na aqueous solution of 5% ~ 30% for raw material, enter bipolar membrane electrodialysis system and carry out bipolar membrane electrodialysis process, control pH=4.0 ~ 5.0, salt room obtain EDTA-2Na solution, and alkali room obtains sodium hydroxide solution;
2) from the EDTA-2Na solution that step 1) obtains, EDTA-2Na is isolated.
Further, in described step 1), the EDTA-4Na aqueous solution is the EDTA-4Na aqueous solution obtained for raw material reaction with sodium cyanide, formaldehyde, quadrol and sodium hydroxide or hydroxyacetonitrile, quadrol and sodium hydroxide.
Further, the preparation method of the described EDTA-4Na aqueous solution is: the molar ratio of sodium cyanide, quadrol, formaldehyde, sodium hydroxide is 4.2 ~ 4.8:1.0:4.1 ~ 4.3:1.0 ~ 3, sodium cyanide and quadrol mixing temperature are lower than 50 DEG C, insulated and stirred 2 ~ 3 hours, then 100 DEG C are warming up to, slowly drip formalin, the time dripping formaldehyde remains on 1 ~ 1.5 hour, dropwise rear insulation 2 hours, and then add sodium hydroxide and water, obtain the EDTA-4Na aqueous solution, being diluted with water to massfraction is 5% ~ 30%.
Further, the preparation method of the described EDTA-4Na aqueous solution is: the molar ratio of hydroxyacetonitrile, quadrol, sodium hydroxide is 4.2 ~ 4.8:1.0:4.5 ~ 6.0, by quadrol and aqueous sodium hydroxide solution mixing, be warming up to 60 DEG C ~ 85 DEG C, in 3 ~ 6 hours, drip hydroxyl acetonitrile aqueous solution, after dropwising, be warming up to 90 DEG C ~ 120 DEG C reactions 0.5 ~ 1 hour, obtain the EDTA-4Na aqueous solution, being diluted with water to massfraction is 5% ~ 30%.
Further, in described step 1), the sodium hydroxide solution that alkali room obtains is through concentrated, then absorb prussic acid and prepare sodium cyanide, sodium cyanide gets back to EDTA-4Na aqueous solution preparation process, or the sodium hydroxide solution after concentrated be circulated to the reaction of hydroxyacetonitrile, quadrol and sodium hydroxide use alkali.
Further, in described step 1), the EDTA-4Na aqueous solution is first crossed and is filtered micron, submicron and macromole impurity, then enters bipolar membrane electrodialysis system and carry out bipolar membrane electrodialysis process.
Further, described step 2) in, concentrated by EDTA-2Na solution, be then cooled to-5 ~ 20 DEG C, separate out white EDTA-2Na solid, remaining mother liquor reconcentration, crystallisation by cooling, mother liquor is got back to crystallization or is got back to EDTA preparation process.
Further, described bipolar membrane electrodialysis system side and in addition side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with the anolyte compartment (II) of built-in anode, film pair is provided with between cathode compartment and anolyte compartment, one film forms by a spaced Bipolar Membrane (BP) and a cationic exchange membrane (C), the relative position of described film to Bipolar Membrane and cationic exchange membrane is that the anode of Bipolar Membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, a cationic exchange membrane is provided with between two Bipolar Membrane, described film forms alkali room (III) to the cathode direction of Bipolar Membrane and anode membrane, anode membrane and Bipolar Membrane anode direction form salt room (IV).
Further, described bipolar membrane electrodialysis process passes into the EDTA-4Na aqueous solution in salt room, and pass into rare sodium hydroxide solution in alkali room, negative electrode and anode pass into direct current.
Beneficial effect of the present invention is:
The present invention adopts bipolar membrane electrodialysis technology that EDTA-4Na is converted into EDTA-2Na, reclaim sodium hydroxide simultaneously, neutralize without the need to acid adding, thus completely eliminate by-product sodium sulfate or sodium-chlor, three-waste free pollution, reduce the processing cost of brine waste, and can obtain highly purified product, product yield is high.In addition, the sodium hydroxide that bipolar membrane electrodialysis process produces can recycle after concentrated, further saves the production cost of EDTA-2Na.
Accompanying drawing explanation
In order to make object of the present invention, technical scheme and beneficial effect clearly, the invention provides following accompanying drawing and being described:
Fig. 1 is the process flow sheet of the environment-protecting clean new process of production of the high purity EDTA-2Na of the embodiment of the present invention 1;
Fig. 2 is the process flow sheet of bipolar membrane electrodialysis process in the embodiment of the present invention 1;
Fig. 3 is the process flow sheet of the environment-protecting clean new process of production of the high purity EDTA-2Na of the embodiment of the present invention 2.
Embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
embodiment 1
The technical process of the environment-protecting clean new process of production of the high purity EDTA-2Na of the present embodiment is as shown in Figure 1:
Add the sodium cyanide solution of 718.7 gram 30.0% in the reactor, control temperature 50 DEG C, slowly drip the quadrol of 60.7 gram 99.0%, dropwised in 2 hours, then 100 DEG C are warming up to, slowly drip the formalin of 348.7 gram 37.0%, time for adding controls in 1.5 hours, dropwise follow-up continuous insulation reaction 2 hours, then add 60 grams, sodium hydroxide, after reaction terminates, add water and the massfraction of EDTA-4Na is diluted to 20%, obtain the EDTA-4Na aqueous solution 1872.3 grams, the yield of EDTA-4Na is that 98.5%(is in quadrol).
By the above-mentioned EDTA-4Na aqueous solution 1872.3 grams through air lift ammonia excretion, the content of ammonia is not higher than 50ppm; Then filtered by ultra-filtration membrane, nanofiltration membrane combination with the flow velocity of 20L/h by the EDTA-4Na aqueous solution, removing micron, submicron and macromole impurity thereof, the EDTA-4Na destainer obtained is weak yellow liquid, and the pH of feed liquid is 12.5.
Above-mentioned solution is entered bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis process, the technical process of bipolar membrane electrodialysis process as shown in Figure 2, bipolar membrane electrodialysis system side and in addition side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with the anolyte compartment (II) of built-in anode, film pair is provided with between cathode compartment and anolyte compartment, one film forms by a spaced Bipolar Membrane (BP) and a cationic exchange membrane (C), the relative position of described film to Bipolar Membrane and cationic exchange membrane is that the anode of Bipolar Membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, a cationic exchange membrane is provided with between two Bipolar Membrane, described film forms alkali room (III) to the cathode direction of Bipolar Membrane and anode membrane, anode membrane and Bipolar Membrane anode direction form salt room (IV), in salt room, pass into the EDTA-4Na aqueous solution, pass into the sodium hydroxide solution that massfraction is 0.3% in alkali room, negative electrode and anode pass into direct current, it is electrodialysis terminal that pH in salt room controls 4.5, and analyze the EDTA-2Na in salt room, its yield is that 100%(is in EDTA-4Na).
The sodium hydroxide of alkali room, through concentrated, analyzed wherein EDTA-4Na, is not detected, obtain the aqueous sodium hydroxide solution of 40%, and aqueous sodium hydroxide solution absorbs prussic acid and prepares sodium cyanide, and sodium cyanide gets back to EDTA-4Na aqueous solution preparation process.EDTA-2Na in salt room is through being concentrated into 40%, and be then cooled to 0 ~ 5 DEG C of crystallization, suction filtration obtains EDTA-2Na wet product, drying, obtains the EDTA-2Na.2H of content 99.5%
2o product; Suction filtration EDTA-2Na.2H
2the filtrate of O is concentrated into 40% again, and be then cooled to 0 ~ 5 DEG C of crystallization, suction filtration obtains EDTA-2Na wet product, drying, obtains the EDTA-2Na.2H of content 99.5%
2o product; The EDTA-2Na.2H that twice is obtained
2o product merges, and obtains EDTA-2Na.2H
2o product 355.4 grams, yield be 97%(in EDTA-4Na, as in the quadrol fed intake, EDTA-2Na.2H
2o yield is 95.55%).Crystalline mother solution mainly EDTA-2Na, hydroxy acid sodium, sodium formiate by analysis, wherein EDTA-2Na accounts for about 4% of total amount, through sulfuric acid acidation, can reclaim EDTA.
embodiment 2
The technical process of the environment-protecting clean new process of production of the high purity EDTA-2Na of the present embodiment is as shown in Figure 3:
Add the aqueous sodium hydroxide solution 666.7 grams mixing that the quadrol of 60.7 gram 99.0% and mass percentage are 30% in the reactor, be warming up to 85 DEG C, in 5 hours, drip the hydroxyacetonitrile 597.1 grams that mass percentage is 42%; Be warming up to 110 DEG C of reactions 0.5 hour after dropwising, then add water and the massfraction of EDTA-4Na is diluted to 20%, obtain the EDTA-4Na aqueous solution 1786.8 grams, the yield of EDTA-4Na is that 94%(is in quadrol).
By the above-mentioned EDTA-4Na aqueous solution 1786.8 grams through air lift ammonia excretion, the content of ammonia is not higher than 50ppm; Then filtered by ultra-filtration membrane, nanofiltration membrane combination with the flow velocity of 20L/h by the EDTA-4Na aqueous solution, removing micron, submicron and macromole impurity thereof, the EDTA-4Na destainer obtained is weak yellow liquid, and the pH of feed liquid is 12.5.
Above-mentioned solution is entered bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis process, the technical process of bipolar membrane electrodialysis process as shown in Figure 2, bipolar membrane electrodialysis system side and in addition side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with the anolyte compartment (II) of built-in anode, film pair is provided with between cathode compartment and anolyte compartment, one film forms by a spaced Bipolar Membrane (BP) and a cationic exchange membrane (C), the relative position of described film to Bipolar Membrane and cationic exchange membrane is that the anode of Bipolar Membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, a cationic exchange membrane is provided with between two Bipolar Membrane, described film forms alkali room (III) to the cathode direction of Bipolar Membrane and anode membrane, anode membrane and Bipolar Membrane anode direction form salt room (IV), in salt room, pass into the EDTA-4Na aqueous solution, pass into the sodium hydroxide solution that massfraction is 0.3% in alkali room, negative electrode and anode pass into direct current, it is electrodialysis terminal that pH in salt room controls 4.5, and analyze the EDTA-2Na in salt room, its yield is that 100%(is in EDTA-4Na).
The sodium hydroxide of alkali room, through concentrated, analyzed wherein EDTA-4Na, is not detected, obtain the aqueous sodium hydroxide solution of 30%, and what aqueous sodium hydroxide solution was circulated to the reaction of hydroxyacetonitrile, quadrol and sodium hydroxide uses alkali.EDTA-2Na in salt room is through being concentrated into 40%, and be then cooled to 0 ~ 5 DEG C of crystallization, suction filtration obtains EDTA-2Na wet product, drying, obtains the EDTA-2Na.2H of content 99.5%
2o product; Suction filtration EDTA-2Na.2H
2the filtrate of O is concentrated into 40% again, and be then cooled to 0 ~ 5 DEG C of crystallization, suction filtration obtains EDTA-2Na wet product, drying, obtains the EDTA-2Na.2H of content 99.5%
2o product; The EDTA-2Na.2H that twice is obtained
2o product merges, and obtains EDTA-2Na.2H
2o product 342.7 grams, yield be 98%(in EDTA-4Na, as in the quadrol fed intake, EDTA-2Na.2H
2o yield is 92.12%).Crystalline mother solution mainly EDTA-2Na, hydroxy acid sodium, sodium formiate by analysis, wherein EDTA-2Na accounts for about 4% of total amount, through sulfuric acid acidation, can reclaim EDTA.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (9)
1. an environment-protecting clean new process of production of high purity EDTA-2Na, is characterized in that: comprise the following steps:
1) with massfraction be the EDTA-4Na aqueous solution of 5% ~ 30% for raw material, enter bipolar membrane electrodialysis system and carry out bipolar membrane electrodialysis process, control pH=4.0 ~ 5.0, salt room obtain EDTA-2Na solution, and alkali room obtains sodium hydroxide solution;
2) from the EDTA-2Na solution that step 1) obtains, EDTA-2Na is isolated.
2. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 1, it is characterized in that: in described step 1), the EDTA-4Na aqueous solution is the EDTA-4Na aqueous solution obtained for raw material reaction with sodium cyanide, formaldehyde, quadrol and sodium hydroxide or hydroxyacetonitrile, quadrol and sodium hydroxide.
3. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 2, it is characterized in that: the preparation method of the described EDTA-4Na aqueous solution is: sodium cyanide, quadrol, formaldehyde, the molar ratio of sodium hydroxide is 4.2 ~ 4.8:1.0:4.1 ~ 4.3:1.0 ~ 3, sodium cyanide and quadrol mixing temperature are lower than 50 DEG C, insulated and stirred 2 ~ 3 hours, then 100 DEG C are warming up to, slowly drip formalin, the time dripping formaldehyde remains on 1 ~ 1.5 hour, dropwise rear insulation 2 hours, and then add sodium hydroxide and water, obtain the EDTA-4Na aqueous solution, being diluted with water to massfraction is 5% ~ 30%.
4. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 2, it is characterized in that: the preparation method of the described EDTA-4Na aqueous solution is: the molar ratio of hydroxyacetonitrile, quadrol, sodium hydroxide is 4.2 ~ 4.8:1.0:4.5 ~ 6.0, by quadrol and aqueous sodium hydroxide solution mixing, be warming up to 60 DEG C ~ 85 DEG C, hydroxyl acetonitrile aqueous solution is dripped in 3 ~ 6 hours, after dropwising, be warming up to 90 DEG C ~ 120 DEG C reactions 0.5 ~ 1 hour, obtain the EDTA-4Na aqueous solution, being diluted with water to massfraction is 5% ~ 30%.
5. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 2, it is characterized in that: in described step 1), the sodium hydroxide solution that alkali room obtains is through concentrated, then absorb prussic acid and prepare sodium cyanide, sodium cyanide gets back to EDTA-4Na aqueous solution preparation process, or the sodium hydroxide solution after concentrated be circulated to the reaction of hydroxyacetonitrile, quadrol and sodium hydroxide use alkali.
6. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 1, it is characterized in that: in described step 1), the EDTA-4Na aqueous solution is first crossed and is filtered micron, submicron and macromole impurity, then enters bipolar membrane electrodialysis system and carry out bipolar membrane electrodialysis process.
7. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 1, it is characterized in that: described step 2) in, EDTA-2Na solution is concentrated, then-5 ~ 20 DEG C are cooled to, separate out white EDTA-2Na solid, remaining mother liquor reconcentration, crystallisation by cooling, mother liquor is got back to crystallization or is got back to EDTA preparation process.
8. the environment-protecting clean new process of production of the high purity EDTA-2Na according to claim 1 to 7 any one, it is characterized in that: described bipolar membrane electrodialysis system side and in addition side are respectively equipped with the cathode compartment (I) of built-in negative electrode and are provided with the anolyte compartment (II) of built-in anode, film pair is provided with between cathode compartment and anolyte compartment, one film forms by a spaced Bipolar Membrane (BP) and a cationic exchange membrane (C), the relative position of described film to Bipolar Membrane and cationic exchange membrane is that the anode of Bipolar Membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, a cationic exchange membrane is provided with between two Bipolar Membrane, described film forms alkali room (III) to the cathode direction of Bipolar Membrane and anode membrane, anode membrane and Bipolar Membrane anode direction form salt room (IV).
9. the environment-protecting clean new process of production of high purity EDTA-2Na according to claim 8, it is characterized in that: described bipolar membrane electrodialysis process passes into the EDTA-4Na aqueous solution in salt room, pass into rare sodium hydroxide solution in alkali room, negative electrode and anode pass into direct current.
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| CN201410469672.7A Expired - Fee Related CN104327115B (en) | 2014-07-08 | 2014-09-16 | A kind of energy-saving clean production method of high-purity glufosinate-ammonium |
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| CN106518698A (en) * | 2016-09-20 | 2017-03-22 | 重庆紫光化工股份有限公司 | Environmental-protection clean production process for reducing ethylenediaminetetraacetic acid by-production inorganic acid sodium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262393B (en) | 2017-01-11 |
| CN104262391B (en) | 2016-08-24 |
| CN104327115A (en) | 2015-02-04 |
| CN104262394B (en) | 2016-08-24 |
| CN104262391A (en) | 2015-01-07 |
| CN104262394A (en) | 2015-01-07 |
| CN104313636B (en) | 2016-08-24 |
| CN104327115B (en) | 2016-08-24 |
| CN104262393A (en) | 2015-01-07 |
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