CN104058541B - A kind of process for producing EDTA produces the method for waste water - Google Patents
A kind of process for producing EDTA produces the method for waste water Download PDFInfo
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Abstract
The invention belongs to technical field of waste water processing, particularly relate to a kind of method that process for producing EDTA produces waste water, comprise the following steps: (1) prepares Water in Oil emulsion film, the film of emulsion liquid film is made up of the flowing carrier of the tensio-active agent of 1��5wt%, 1��5wt% and the thinner of 90��98wt%, interior it is made up of the caustic soda solution of 0.2��30wt%, film phase is 1.5��5:1 with the composition mass ratio of interior phase, wherein tensio-active agent adopts tween-80 or span-80, flowing carrier adopts trioctylamine, and thinner is kerosene; (2) regulating the pH value of waste water, then emulsion liquid film obtained in step (1) is added waste water and extract, the waste water after extraction carries out evaporative crystallization process; (3) the emulsion liquid film breakdown of emulsion after extracting, again prepares emulsion liquid film and uses. The present invention takes out the organism in waste water, greatly improves evaporation effect, and production cost is low.
Description
Technical field
The invention belongs to technical field of waste water processing, particularly relate to a kind of method that process for producing EDTA produces waste water.
Background technology
Ethylenediamine tetraacetic acid (EDTA), ethylenediaminetetraacetic acid (EthyleneDiamineTetraaceticAcid), being important sequestrant, there is important application in the field such as, washing composition, textile auxiliary agent, leather chemicals, papermaking chemical product, medicine, synthetic rubber refining at Chemicals for Photograph, water conditioner, chemical (Gelucystine), micro-fertile production.
The industrial process of EDTA mainly contains chloroactic acid method and sodium cyanide method. Chloroactic acid method is eliminated substantially, and at present, EDTA produces and substantially adopts sodium cyanide method. Sodium cyanide method produces EDTA main raw material quadrol, formaldehyde, sodium cyanide, caustic soda, sulfuric acid or hydrochloric acid, owing to its raw materials for production sodium cyanide, formaldehyde, caustic soda, hydrochloric acid etc. are containing large quantity of moisture, therefore, produce EDTA and can produce a large amount of waste water, these waste water generally adopt the mode of single-effect evaporation or multiple-effect evaporation to process, and purify out by the sodium sulfate in waste water or sodium-chlor by evaporation. But owing to waste water containing large amount of organic, in evaporative process, organism constantly accumulates in vapo(u)rization system, evaporation material concentration is caused to continue to increase, viscosity constantly increases, thus evaporator heat exchange coefficient is constantly diminished, and greatly affects evaporation effect, this is had people processed by Ultraviolet Oxidation technology by waste water, but expense is too high.
Summary of the invention
It is an object of the invention to provide a kind of method that process for producing EDTA produces waste water, when being intended to solve existing production EDTA generation waste water single-action or multiple-effect evaporation, because containing large amount of organic, in evaporative process, evaporation material concentration is caused to continue to increase, viscosity constantly increases, and greatly affects the technical problem of evaporation effect.
The present invention realizes like this, and a kind of process for producing EDTA produces the method for waste water, comprises the following steps:
(1) system breast: preparation Water in Oil emulsion film, the film of described emulsion liquid film is made up of the flowing carrier of the tensio-active agent of 1��5wt%, 1��5wt% and the thinner of 90��98wt%, interior it is made up of the caustic soda solution of 0.2��30wt%, described film phase is 1.5��5:1 with the composition mass ratio of interior phase, wherein said tensio-active agent adopts tween-80 or span-80, described flowing carrier adopts trioctylamine, and described thinner is kerosene;
(2) extract: the pH value regulating waste water, then emulsion liquid film obtained in step (1) is added waste water and extract, the waste water after extraction is carried out evaporative crystallization process;
(3) the heavy reconstituted milk of breakdown of emulsion and emulsion liquid film: by the emulsion liquid film breakdown of emulsion after extraction, again prepare emulsion liquid film and reuse.
Improve as one, described step (2) uses caustic soda or soda ash the pH value of waste water is adjusted to 2��5.
Improving as one, when described step (2) extracts, the mass ratio of EDTA waste water and emulsion liquid film is 1��10:1.
Improving as one, in described step (3), emulsion liquid film breakdown of emulsion mode adopts electrostatic demulsifying or chemical demulsification.
As improving further, described chemical demulsification emulsion splitter used is sulfuric acid or hydrochloric acid.
Improving as one, the extraction temperature of described step (2) is 20��40 DEG C.
Improving as one, the extraction equipment of described step (2) adopts extraction tower or multi-floating bodies.
As improving further, when the described extraction described extraction tower of use or multi-floating bodies, emulsion liquid film and waste water all adopt reflux type to carry out.
As one improve, in described step (2) evaporative crystallization process after concentrated wastewater mother liquor re-start extraction treatment.
In the reaction process using sodium cyanide method to prepare EDTA, main reaction is:
NaCN+CH2O+H2N-CH2-CH2-NH2��EDTA-4Na+NH3
Also there is following side reaction in addition:
NaCN+2H2O��HCOONa+NH3
NaCN+CH2O+2H2O��HOCH2COONa+NH3
NaCN+CH2O��NaOCH2CN
NaOCH2CN+NH3�� NH2CH2 (NaO) C=NH
NH2CH2 (NaO) C=NH+H2O��H2NCH2COONa+NH3
NaCN+CH2O+H2NCH2COONa+H2O��HN(CH2COONa)2+NH3
NaCN+CH2O+HN(CH2COONa)2+H2O��HN(CH2COONa)3+NH3
Owing to formaldehyde in production process and sodium cyanide are excessive, therefore, H in reaction process2NCH2COONa and HN (CH2COONa)2Substantially HN (CH all it is converted into2COONa)3, after persulfuric acid or hcl acidifying, main containing following organism in waste water: EDTA, HCOOH, HOCH2COOH��HN(CH2COOH)3, also confirm waste water mainly contains this 4 kinds of materials through liquid chromatographic detection.
Before extracting operation, caustic soda or soda ash is added in waste water, the pH value of waste water is adjusted to 2��5, then extracting operation is carried out, the extraction environment of pH value 2��5 makes the stability that emulsion liquid film keeps suitable, and emulsion liquid film foreign minister be acid simultaneously, and interior phase is alkaline, being beneficial to carrying out smoothly of extraction process, in extraction process, flowing carrier trioctylamine is by organism EDTA, HCOOH, the HOCH in waste water2COOH��HN(CH2COOH)3Transfer to film mutually in, then transfer to again in interior phase, extraction efficiency height, these Acidic organic matter are reacted with caustic soda in the alkaline environment of interior phase, the organic acid being beneficial in foreign minister's waste water enters into interior phase, makes the pH value of interior phase solution be unlikely to too low simultaneously, is beneficial to the stability of film phase.
Through the waste water of extraction treatment, organic content reduces greatly, in single-action or Multi-effect Evaporation Processes, waste water boiling point no longer significantly raises, improve evaporation effect, and organic content reduces greatly in the sodium sulfate that obtains of crystallization or sodium-chlor, quality improves a lot, and can also re-start extraction treatment as foreign minister through the wastewater mother liquor that evaporation is concentrated further simultaneously.
When using chemical demulsifying process, suitable emulsion splitter is selected according to EDTA production process, production process uses the employing sulfuric acid breakdown of emulsion that sulfuric acid neutralizes, use the employing salt naphtenic acid of hydrochloric acid neutralization, the organism that breakdown of emulsion obtains concentrating can be separated further, is used for doing metal cleaner, boiler detergent after obtaining variant production or acidifying respectively.
Process for producing EDTA of the present invention produces the method for waste water, by the organic impurities extraction treatment in waste water, make organic impurities not at vapo(u)rization system internal recycle, greatly improve evaporation effect, and compared with by Ultraviolet Oxidation technology waste water being carried out process, greatly reduce production cost.
Embodiment
In order to make the object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated. It is to be understood that specific embodiment described herein is only in order to explain the present invention, it is not intended to limit the present invention.
Embodiment one
1. the preparation of emulsion liquid film: getting 100kg kerosene, 2kgtween-80 makes tensio-active agent, adds trioctylamine 3kg, 8wt% caustic soda 30kg, is traditionally prepared into emulsion liquid film under room temperature.
2. measuring waste water composition: produce and use sulfuric acid to carry out acidifying in EDTA process, the waste water of generation measures wherein EDTA content 0.35wt%, nitrilotriacetic acid(NTA) 0.4wt%, oxyacetic acid 0.45wt%, formic acid 0.35wt% in EDTA waste water through liquid chromatography.
3. extract: in waste water, add pH value to 2��5 that soda ash solution regulates waste water, extraction carries out in small-sized extraction tower, extraction temperature remains on 20��40 DEG C, get waste water 1350kg to add from extraction tower top with the flow velocity of 30kg/h, emulsion liquid film adds bottom extraction tower with the speed of 20kg/h, extraction is completed in extraction tower, again waste water is measured: EDTA content 0.03% after extraction, nitrilotriacetic acid(NTA) 0.04%, oxyacetic acid 0.035%, formic acid 0.03%, it is seen that in waste water, organic removal rate can reach more than 90% after extraction.
4. the waste water after extraction is carried out evaporative crystallization process, adopt chemical demulsification mode to carry out breakdown of emulsion by the emulsion liquid film after extraction adds a large amount of sulphuric acid solns, again prepare emulsion liquid film and reuse.
Embodiment two
1. the preparation of emulsion liquid film: getting 100kg kerosene, 3kgspan-80 makes tensio-active agent, adds trioctylamine 5kg, 20wt% caustic soda 40kg, is traditionally prepared into emulsion liquid film under room temperature.
2. measure through concentrated waste water composition: measure EDTA content 0.65wt%, nitrilotriacetic acid(NTA) 0.6wt%, oxyacetic acid 0.95wt%, formic acid 0.7wt% in EDTA waste water through liquid chromatography.
3. extract: in waste water, add pH value to 2��5 that caustic soda solution regulates waste water, extraction carries out in small-sized extraction tower, extraction temperature remains on 20��40 DEG C, get waste water 450kg to add from extraction tower top with the flow velocity of 20kg/h, milk sap adds bottom extraction tower with the speed of 15kg/h, extraction is completed in extraction tower, again waste water is measured: EDTA content 0.05wt% after extraction, nitrilotriacetic acid(NTA) 0.055wt%, oxyacetic acid 0.07wt%, formic acid 0.064wt%, it is seen that in waste water, organic removal rate can reach more than 90% after extraction.
4. the waste water after extraction is carried out evaporative crystallization process, the emulsion liquid film after extraction is adopted electrostatic demulsifying mode breakdown of emulsion, again prepares emulsion liquid film and reuse.
Embodiment three
1. the preparation of emulsion liquid film: getting 90kg kerosene, 5kgtween-80 makes tensio-active agent, adds trioctylamine 5kg, 0.2wt% caustic soda 66.7kg, is traditionally prepared into emulsion liquid film under room temperature.
2. measure waste water composition: producing and use hydrochloric acid to carry out acidifying in EDTA process, the waste water of generation measures wherein EDTA content 0.4wt% through liquid chromatography, nitrilotriacetic acid(NTA) 0.45wt%, oxyacetic acid 0.5wt%, formic acid 0.35wt%.
3. extract: in waste water, add pH value to 3��4 that soda ash solution regulates waste water, extraction adopts multi-floating bodies mode to carry out, extraction temperature remains on 20��40 DEG C, get waste water 1000kg to add with the reactor of the flow velocity of 30kg/h from the first end of series connection, emulsion liquid film with the speed of 20kg/h from series connection tail end reactor add, extraction carries out in reactor, again waste water is measured: EDTA content 0.035wt% after extraction, nitrilotriacetic acid(NTA) 0.04wt%, oxyacetic acid 0.045wt%, formic acid 0.03wt%, visible after extraction in waste water organic removal rate can reach more than 90%.
4. the waste water after extraction is carried out evaporative crystallization process, in the emulsion liquid film after extraction, add a large amount of hydrochloric acid soln adopt chemical demulsification mode breakdown of emulsion, again prepare emulsion liquid film and reuse.
Embodiment four
1. the preparation of emulsion liquid film: getting 98kg kerosene, 1kgspan-80 makes tensio-active agent, adds trioctylamine 1kg, 30wt% caustic soda 20kg, is traditionally prepared into emulsion liquid film under room temperature.
2. measure through concentrated waste water composition: measure EDTA content 0.75wt%, nitrilotriacetic acid(NTA) 0.7wt%, oxyacetic acid 0.95wt%, formic acid 0.8wt% in EDTA waste water through liquid chromatography.
3. extract: in waste water solution, add pH value to 3��4 that caustic soda solution regulates waste water, extraction adopts multi-floating bodies mode to carry out, extraction temperature remains on 20��40 DEG C, get waste water 120kg to add with the reactor of the flow velocity of 20kg/h from the first end of series connection, emulsion liquid film with the speed of 15kg/h from series connection tail end reactor add, extraction carries out in reactor, again waste water is measured: EDTA content 0.065wt% after extraction, nitrilotriacetic acid(NTA) 0.06wt%, oxyacetic acid 0.07wt%, formic acid 0.075wt%, visible after extraction in waste water organic removal rate can reach more than 90%.
4. the waste water after extraction being carried out evaporative crystallization process, the emulsion liquid film after extraction adopts electrostatic demulsifying mode to carry out breakdown of emulsion, again prepares emulsion liquid film and reuses.
The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. done within the spirit and principles in the present invention, all should be included within protection scope of the present invention.
Claims (5)
1. the method for a process for producing EDTA generation waste water, it is characterised in that, comprise the following steps:
(1) system breast: preparation Water in Oil emulsion film, the film of described emulsion liquid film is made up of the flowing carrier of the tensio-active agent of 1��5wt%, 1��5wt% and the thinner of 90��98wt%, interior it is made up of the caustic soda solution of 0.2��30wt%, described film phase is 1.5��5:1 with the composition mass ratio of interior phase, wherein said tensio-active agent adopts tween-80 or span-80, described flowing carrier adopts trioctylamine, and described thinner is kerosene;
(2) extract: the pH value regulating waste water, use caustic soda or soda ash that the pH value of waste water is adjusted to 2��5, then emulsion liquid film obtained in step (1) is added waste water to extract, during extraction, the mass ratio of EDTA waste water and emulsion liquid film is 1��10:1, extraction temperature is 20��40 DEG C, waste water after extraction is carried out evaporative crystallization process, and the concentrated wastewater mother liquor after evaporative crystallization process re-starts extraction treatment;
(3) the heavy reconstituted milk of breakdown of emulsion and emulsion liquid film: by the emulsion liquid film breakdown of emulsion after extraction, again prepare emulsion liquid film and reuse.
2. process for producing EDTA according to claim 1 produces the method for waste water, it is characterised in that, in described step (3), emulsion liquid film breakdown of emulsion mode adopts electrostatic demulsifying or chemical demulsification.
3. process for producing EDTA according to claim 2 produces the method for waste water, it is characterised in that, described chemical demulsification emulsion splitter used is sulfuric acid or hydrochloric acid.
4. process for producing EDTA according to claim 1 produces the method for waste water, it is characterised in that, the extraction equipment of described step (2) adopts extraction tower or multi-floating bodies.
5. process for producing EDTA according to claim 4 produces the method for waste water, it is characterised in that, when the described extraction described extraction tower of use or multi-floating bodies, emulsion liquid film and waste water all adopt reflux type to carry out.
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| CN106698574B (en) * | 2016-12-29 | 2019-09-20 | 南京悠谷知识产权服务有限公司 | A kind of recovery process of continous way emulsion liquid film extraction equipment and epoxychloropropane waste water |
| CN114181388B (en) * | 2021-11-30 | 2023-12-01 | 河北圣雪大成制药有限责任公司 | Method for extracting polylysine from fermentation liquor |
| CN115231646B (en) * | 2022-06-22 | 2023-07-14 | 陕西聚泰新材料科技有限公司 | Waste water phase loss organic phase on-line recovery process of hydrometallurgical extraction separation system |
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| CN1613546A (en) * | 2004-09-24 | 2005-05-11 | 陕西科技大学 | Method for separating chromiumin leather-making waste water by milked liquid and membrane separating method |
| CN101386916A (en) * | 2008-10-20 | 2009-03-18 | 长春黄金研究院 | Emulsion liquid membrane for gold extraction |
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