CN1749155A - Liquid-liquid extraction processing method for waste sulfuric acid containing acetochloral and trichloroacetic acid - Google Patents
Liquid-liquid extraction processing method for waste sulfuric acid containing acetochloral and trichloroacetic acid Download PDFInfo
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Abstract
The present invention discloses liquid-liquid extraction process for waste sulfuric acid containing acetochloral and trichloroaceteic acid. By means of the liquid-liquid extraction process, acetochloral, trichloroaceteic acid and other organic matters contained in waste sulfuric acid are eliminated effectively. The present invention has simple operation and no secondary pollution.
Description
Technical field:
The present invention relates to a kind of useless vitriolic treatment process.
Background technology:
Trichoro-aldehyde is a kind of important chemical, pesticide intermediate.China all adopt at present the dehydration of the chlorination of multi-step type ethanol, the vitriol oil the trichoro-aldehyde production process route, can produce a large amount of sulfur waste acid that contains organic impuritys such as trichoro-aldehyde, trichoroacetic acid(TCA) in process of production.General sulfur acid 62%～70% contains trichoro-aldehyde, trichoroacetic acid(TCA) 1～3% in this sulfur waste acid, also contains organism and carbide such as sulfovinic acid about 2%.Because trichoro-aldehyde, trichoroacetic acid(TCA) can destroy the polar structure and the Differentiation of phytoplasm, make the nucleus division disorderly, hinder the normal growth of plant, cause plant death when serious.Trichoroacetic acid(TCA) is longer in the degradation in soil time in addition, the protein of plant is had precipitating action, so the sulfur waste acid that contains trichoro-aldehyde, trichoroacetic acid(TCA) can't enter water system.When there are three county winter irrigation in Hebei province,, cause that 65536 mu of wheats and garlic are disaster-stricken, cause 1317.3 ten thousand yuan of agriculture direct economic losses altogether because of having used the sewage that contains trichoro-aldehyde.Some enterprises once utilized the acid of this sulfur waste to make phosphate fertilizer, but after the peasant uses this phosphate fertilizer, caused the serious underproduction of farm crop even total crop failure incident.Former national Ministry of Agriculture, Animal Husbandry and Fisheries determines that in relevant the evaluation content that trichoro-aldehyde in the phosphate fertilizer or trichoroacetic acid(TCA) cause harmful crop is more than 200～400ppm, and 1 kilogram of sulfuric acid can be produced 2 kilograms of phosphate fertilizer, therefore, have only that trichoro-aldehyde, the highest total content of trichoroacetic acid(TCA) are lower than 400ppm in the sulfur waste acid, just can be used for making phosphate fertilizer, just can avoid farm crop are produced the poisoning effect.If effective elimination trichoro-aldehyde, trichoroacetic acid(TCA) wherein not, this sulfur waste acid just can not obtain recycling, and also can cause the serious environmental pollution even enter water body after the neutralization dilution, wastes a large amount of renewable resourcess simultaneously.How processing and utilizing contains the sulfur waste acid of trichoro-aldehyde, trichoroacetic acid(TCA), is a technical barrier of puzzlement China pesticide industry in decades always.It is reported that more external countries as states such as the U.S., Japan employing burning method eliminate this type of refuse, but invest hugely, and can produce secondary pollution, be not suitable for China's national situation.Domestic enterprise still adopts treatment processs such as distillation method, oxidation style at present.Remove trichoro-aldehyde, trichoroacetic acid(TCA) in the sulfur waste acid as what Zhengzhou Polytechnical College proposed with distillation method, but practice shows technically and all exists economically defective.Fuyang Chemical Group Co., Ltd., Handan's invention " producing the useless vitriolic treatment process that produces in the trichoro-aldehyde process " still belongs to simple distillation, this method is actually the distillation method that Zhengzhou Polytechnical College is proposed and improves, especially before distillation beginning at first water sulfur waste acid dilution is produced a large amount of foams and overflow problem when solving distillation.Clearly, adding behind the water makes the thermal load of still kettle increase owing to increased the evaporating capacity of water, by material balance and heat balance, can calculate 1 ton of sulfur waste acid of the every distillation of this method, energy consumption reaches 3000 * 103kJ at least, also increased simultaneously the refrigeration duty of subsequent condensation device, the new problem that this has just brought energy consumption to increase greatly.In addition, distillation method also exists operational condition and badly and easily produces many disadvantages such as secondary pollution.
Summary of the invention:
The object of the present invention is to provide a kind of can effective elimination trichoro-aldehyde, trichoroacetic acid(TCA) in the sulfur waste acid, and easy to operate, non-secondary pollution contain trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA).
Technical solution of the present invention is:
A kind of trichoro-aldehyde, useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing is characterized in that: remove trichoro-aldehyde contained in the sulfur waste acid, trichoroacetic acid(TCA) by liquid-liquid extraction.
Described trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing, it is that extraction agent removes trichoro-aldehyde contained in the sulfur waste acid, trichoroacetic acid(TCA) with toluene or dimethylbenzene, is strippant with the sodium hydroxide solution to the processing of stripping of the extraction agent after extraction.
The strippant concentration sodium hydroxide is 0.4～0.8mol/L.During extraction treatment, extraction agent and both volume ratios of sulfur waste acid are extraction agent: sulfur waste acid=0.5～1: 0.5～1, and during reextraction, the volume ratio of strippant and extraction agent is a strippant: extraction agent=0.5～1: 0.5～1.
Described trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing adopts the discrete stage contact extraction process, comprises the following steps: successively
(1) one-level extraction: add extraction agent and sulfur waste acid in first tempering tank respectively, the two-phase volume ratio is an extraction agent: sulfur waste acid=1: 0.5～1, and after abundant at normal temperatures stirring or the vibration, send into first subsider and leave standstill phase-splitting;
(2) secondary extraction: the extracting phase after one-level extracts phase-splitting is sent into second tempering tank, simultaneously in second tempering tank, add extraction agent, the two-phase volume ratio is an extraction agent: sulfur waste acid=0.5～1: 1, after abundant at normal temperatures stirring or the vibration, send into second subsider and leave standstill phase-splitting, get extracting phase in the groove, be the sulfuric acid that removes behind trichoro-aldehyde, the trichoroacetic acid(TCA);
(3) one-level is stripped: extraction phase in first, second subsider is sent into the first back extraction groove, add strippant, the volume ratio of strippant and the extraction agent after extracting is a strippant: extraction agent=1: 0.5～1 after extraction, after abundant at normal temperatures stirring or the vibration, send into the first back extraction subsider and leave standstill phase-splitting;
(4) secondary is stripped: the extracting phase in the first back extraction subsider is sent into the second back extraction groove, add strippant, strippant and one-level reextraction extracting phase volume ratio are strippant: one-level reextraction extracting phase=0.5～1: 0.5～1, after abundant at normal temperatures stirring or the vibration, send into the second back extraction subsider and leave standstill phase-splitting.
In the above-mentioned steps (4) in the second back extraction subsider extracting phase be regenerating extracting agent, loop back the extraction tempering tank acid extracts to sulfur waste.With regenerating extracting agent the extraction of secondary counter current contact is carried out in sulfur waste acid, promptly in second tempering tank, add regenerating extracting agent and at first carry out the secondary extraction, with the extraction phase of secondary extraction promptly the extraction phase in second subsider send in first tempering tank, as the one-level extraction agent, the one-level extraction is carried out in sulfur waste acid.After secondary extraction and strip stage, increase extraction and reextraction progression.
The described useless vitriolic liquid-liquid extraction treatment process of trichoro-aldehyde, trichoroacetic acid(TCA) that contains adopts continuous differential extraction method, comprises the following steps: successively to add extraction agent from the extraction tower bottom, and is external phase with the extraction agent; Add sulfur waste acid from the extraction tower top, and be disperse phase with sulfur waste acid, the two-phase volume ratio is an external phase: carry out extracting operation under disperse phase=1: 0.5～1, normal temperature, extracting phase is the sulfuric acid that removes behind trichoro-aldehyde, the trichoroacetic acid(TCA) and flows out from the extraction tower bottom; Extraction phase flows out from the extraction tower cat head, enters the back extraction tower from the back extraction tower bottom, and as the back extraction disperse phase; Strippant is sent into the back extraction tower from the back extraction top of tower, and as back extraction external phase, the two-phase volume ratio is a back extraction external phase: back extraction disperse phase=1: 0.5～1, the operation of stripping under the normal temperature, the effusive regenerating extracting agent that is of back extraction top of tower, deliver to the extraction agent import of extraction tower bottom, enter extraction tower and carry out the extracting-back extraction circulation; To collect in addition from the effusive NaOH that contains organic impuritys such as trichoro-aldehyde, trichoroacetic acid(TCA) of back extraction tower bottom and deal with.
Grooves such as described tempering tank, subsider, back extraction groove are containers such as cell body or jar, bottle, pipe.
The present invention adopts the method for liquid-liquid extraction, organic substances such as the trichoro-aldehyde in the acid of energy effective elimination sulfur waste, trichoroacetic acid(TCA), make sulfur waste acid be purified recovery, after the secondary extraction, organic content such as trichoro-aldehyde, trichoroacetic acid(TCA) is reduced to about 0.022% (220ppm) in the sulfuric acid, organic content such as trichoro-aldehyde, trichoroacetic acid(TCA) are reduced to below 0.001% after three grades of extractions, and sulfuric acid content is constant substantially.The present invention can solve the long-term sulfur waste acid treatment problem that perplexs China's pesticide industry, turns waste into wealth in the decontamination source, the protection environment; Greatly reduce the energy consumption in the sulfur waste acid treatment process, saved the production run cost; Extraction and stripping process equipment are simple, and processing ease is convenient to realize suitability for industrialized production; Non-secondary pollution; Less investment, instant effect, no matter large or small insecticide factory all can adopt, and has favorable social and economic benefits.
The invention will be further described below in conjunction with drawings and Examples.
Fig. 1 is the process flow sheet of discrete stage contact extraction process of the present invention.
Fig. 2 is the process flow sheet of the continuous differential extraction method of the present invention.
Embodiment:
Embodiment 1:
(1) add the sulfur waste acid of extraction agent dimethylbenzene and the 60mL of 60mL respectively in first separating funnel of 150mL, the vibration 2 minutes down of 20 ℃ of room temperatures was left standstill phase-splitting 6 minutes.This separating funnel lower floor extracting phase is put to second separating funnel of 150mL.
(2) the extraction agent dimethylbenzene of adding 60mL in second separating funnel, room temperature was vibrated 2 minutes down for 20 ℃, left standstill phase-splitting and after 6 minutes lower floor's extracting phase was put to the 100mL beaker.
(3) to the extracting phase in the beaker (sulfuric acid) sampling analysis, the content that records trichoro-aldehyde, trichoroacetic acid(TCA) in the sulfuric acid after the secondary extraction is 0.02106%, and the full gear rate is 99.10%
(4) the upper strata extraction phase that leaves standstill after the phase-splitting of step (1) is put to the separating funnel of another 150mL, the NaOH solution that adds the reverse-extraction agent 0.4mol/L of 60mL, carrying out one-level strips, promptly vibrated 2 minutes down for 20 ℃ in room temperature, left standstill phase-splitting 6 minutes, and then carry out secondary by one-level reextraction same steps as and strip.Acid extracts full gear to the regenerating extracting agent that obtains to sulfur waste with stripping through secondary, and extraction step is with embodiment 1.Record after secondary extraction full gear that the content of trichoro-aldehyde, trichoroacetic acid(TCA) is 0.02119% in the sulfuric acid, the full gear rate is 99.10%.
Embodiment 2:
Change the extraction agent of embodiment 1 into toluene, other step is with embodiment 1.The content that records trichoro-aldehyde, trichoroacetic acid(TCA) in the sulfuric acid after the secondary extraction is 0.02212%, and the full gear rate is 99.06%.
Embodiment 3:
With reference to Fig. 1
(1) in first tempering tank 1, adds the sulfur waste acid of extraction agent dimethylbenzene and the 2000mL of 2000mL respectively, stir under the room temperature and send into first subsider 2 after 10 minutes and left standstill phase-splitting 15 minutes, lower floor's extracting phase in first subsider 2 is sent into second tempering tank 3, and the upper strata extraction phase is then delivered to the first back extraction groove 4.
(2) add extraction agent dimethylbenzene 2000mL in second tempering tank 3, stir at normal temperatures and send into second subsider 5 after 10 minutes and left standstill phase-splitting 15 minutes, lower floor's extracting phase of getting in second subsider 5 is sulfuric acid, and the upper strata extraction phase is then delivered to the first back extraction groove 4.The content that analysis records trichoro-aldehyde in the sulfuric acid, trichoroacetic acid(TCA) is 0.02085%, and the full gear rate is 99.11%.
(3) the lower floor's extracting phase in second subsider 5 of step (2) is put to another tempering tank carried out three grades of extractions, promptly add extraction agent dimethylbenzene 2000mL, stir at normal temperatures and send into another subsider after 10 minutes and left standstill phase-splitting 15 minutes, take off a layer acid analysis, the content that records trichoro-aldehyde in the sulfuric acid, trichoroacetic acid(TCA) is 0.00093%, and the full gear rate is 99.96%.
(4) extraction phase from first, second subsider 2,5 in the first back extraction groove 4 is carried out the one-level reextraction, be about to 4000mL concentration and be in the adding first back extraction groove of NaOH solution of 0.5mol/L, stir under the room temperature and send into the first back extraction subsider 6 after 10 minutes and left standstill phase-splitting 15 minutes, the extracting phase in the first back extraction subsider 6 is delivered to the second back extraction groove 7.
(5) extracting phase from the first back extraction subsider 6 in the second back extraction groove 7 is carried out the secondary reextraction by one-level reextraction same steps as.
(6) extracting phase of getting in the second back extraction subsider 8 is a regenerating extracting agent.With regenerating extracting agent the extraction of secondary counter current contact is carried out in sulfur waste acid then.Promptly in second tempering tank, add regenerating extracting agent and at first carry out the secondary extraction, with the extraction phase of secondary extraction promptly the extraction phase in second subsider send in first tempering tank, as the one-level extraction agent, the one-level extraction is carried out in sulfur waste acid.Usage ratio is with above-mentioned one-level, secondary extraction step.Record after secondary extraction full gear that the content of trichoro-aldehyde, trichoroacetic acid(TCA) is 0.02172% in the sulfuric acid, the full gear rate is 99.08%.
Embodiment 4:
Change the extraction agent of embodiment 3 into toluene, other step is with embodiment 4 and embodiment 6.The content that records trichoro-aldehyde, trichoroacetic acid(TCA) in the sulfuric acid after the secondary extraction is 0.02256%, and the full gear rate is 99.04%
Embodiment 5:
With reference to Fig. 2
Extraction agent dimethylbenzene (oil phase) pumped into from tower bottom with the flow about 150L/h (the tower internal diameter is 120mm in the extraction tower, filler packing height 1200mm,) and be external phase with the extraction agent, after oil phase volume in the tower is near full tower, again sulfur waste acid (water) is pumped in the extraction tower from top of tower by the flow about 130L/h, and be disperse phase with sulfur waste acid, the two-phase volume ratio is an external phase: disperse phase=1: 0.5～1, regulate the oil phase outlet valve then, make two-phase keep stable in last settling section mid-way, when the tower inner fluid flow stable after, carry out extracting operation at normal temperatures.The sulfuric acid that extracting phase promptly removes behind the trichoro-aldehyde (acid) flows out from the extraction tower bottom, extraction phase pumps into the back extraction tower from the outflow of extraction tower cat head and from the back extraction tower bottom, and as the back extraction disperse phase, with the flow of 150L/h the NaOH solution (water) of strippant 0.5mol/L is pumped into the back extraction tower from the back extraction top of tower, and as back extraction external phase, the two-phase volume ratio is an external phase: disperse phase=1: 0.5～1, regulate the water outlet valve, make two-phase interface keep stable in last settling section mid-way, treat back extraction tower inner fluid flow stable after, the operation of stripping under the normal temperature, the effusive regenerating extracting agent that is of back extraction top of tower, be recycled to entering in the extraction tower of extraction tower bottom, after the extracting-back extraction cyclical operation is stable, to the effusive sulfuric acid sampling analysis in extraction tower bottom, record trichoro-aldehyde in the sulfuric acid, the content of trichoroacetic acid(TCA) is 0.02208%, and the full gear rate is 99.06%.
Claims (9)
1, a kind of trichoro-aldehyde, useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing is characterized in that: remove trichoro-aldehyde contained in the sulfur waste acid, trichoroacetic acid(TCA) by liquid-liquid extraction.
2, trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing according to claim 1, it is characterized in that: with toluene or dimethylbenzene is that extraction agent removes trichoro-aldehyde contained in the sulfur waste acid, trichoroacetic acid(TCA), is strippant with the sodium hydroxide solution to the processing of stripping of the extraction agent after extraction.
3, trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing according to claim 2, it is characterized in that: the strippant concentration sodium hydroxide is 0.4～0.8mol/L.
4, according to claim 1,2 or 3 described trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment processs of trichoroacetic acid(TCA) of containing, it is characterized in that: during extraction treatment, extraction agent and both volume ratios of sulfur waste acid are extraction agent: sulfur waste acid=0.5～1: 0.5～1, during reextraction, the volume ratio of strippant and extraction agent is a strippant: extraction agent=0.5～1: 0.5～1.
5, according to claim 1,2 or 3 described trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment processs of trichoroacetic acid(TCA) of containing, it is characterized in that: adopt the discrete stage contact extraction process, comprise the following steps: successively
(1) one-level extraction: add extraction agent and sulfur waste acid in first tempering tank respectively, the two-phase volume ratio is an extraction agent: sulfur waste acid=1: 0.5～1, and after abundant at normal temperatures stirring or the vibration, send into first subsider and leave standstill phase-splitting;
(2) secondary extraction: the extracting phase after one-level extracts phase-splitting is sent into second tempering tank, simultaneously in second tempering tank, add extraction agent, the two-phase volume ratio is an extraction agent: sulfur waste acid=0.5～1: 1, after abundant at normal temperatures stirring or the vibration, send into second subsider and leave standstill phase-splitting, get extracting phase in the groove, be the sulfuric acid that removes behind trichoro-aldehyde, the trichoroacetic acid(TCA);
(3) one-level is stripped: extraction phase in first, second subsider is sent into the first back extraction groove, add strippant, the volume ratio of strippant and the extraction agent after extracting is a strippant: extraction agent=1: 0.5～1 after extraction, after abundant at normal temperatures stirring or the vibration, send into the first back extraction subsider and leave standstill phase-splitting;
(4) secondary is stripped: the extracting phase in the first back extraction subsider is sent into the second back extraction groove, add strippant, strippant and one-level reextraction extracting phase volume ratio are strippant: one-level reextraction extracting phase=0.5～1: 0.5～1, after abundant at normal temperatures stirring or the vibration, send into the second back extraction subsider and leave standstill phase-splitting.
6, the useless vitriolic liquid-liquid extraction treatment process of trichoro-aldehyde, trichoroacetic acid(TCA) that contains according to claim 5 is characterized in that: get in the step (4) that extracting phase is a regenerating extracting agent in the second back extraction subsider, acid extracts to sulfur waste to loop back the extraction tempering tank.
7, trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing according to claim 6, it is characterized in that: the extraction of secondary counter current contact is carried out in sulfur waste acid with regenerating extracting agent, promptly in second tempering tank, add regenerating extracting agent and at first carry out the secondary extraction, with the extraction phase of secondary extraction promptly the extraction phase in second subsider send in first tempering tank, as the one-level extraction agent, the one-level extraction is carried out in sulfur waste acid.
8, trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment process of trichoroacetic acid(TCA) of containing according to claim 5 is characterized in that: increase extraction and reextraction progression after secondary extraction and strip stage.
9, according to claim 1,2 or 3 described trichoro-aldehyde, the useless vitriolic liquid-liquid extraction treatment processs of trichoroacetic acid(TCA) of containing, it is characterized in that: adopt continuous differential extraction method, comprise the following steps: to add extraction agent successively, and be external phase with the extraction agent from extraction tower bottom; Add sulfur waste acid from the extraction tower top, and be disperse phase with sulfur waste acid, the two-phase volume ratio is an external phase: carry out extracting operation under disperse phase=1: 0.5～1, normal temperature, extracting phase is the sulfuric acid that removes behind trichoro-aldehyde, the trichoroacetic acid(TCA) and flows out from the extraction tower bottom; Extraction phase flows out from the extraction tower cat head, enters the back extraction tower from the back extraction tower bottom, and as the back extraction disperse phase; Strippant is sent into the back extraction tower from the back extraction top of tower, and as back extraction external phase, the two-phase volume ratio is a back extraction external phase: back extraction disperse phase=1: 0.5～1, the operation of stripping under the normal temperature, the effusive regenerating extracting agent that is of back extraction top of tower, deliver to the extraction agent import of extraction tower bottom, enter extraction tower and carry out the extracting-back extraction circulation; To collect in addition from the effusive NaOH that contains organic impuritys such as trichoro-aldehyde, trichoroacetic acid(TCA) of back extraction tower bottom and deal with.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751317A (en) * | 2018-07-25 | 2018-11-06 | 合肥中亚环保科技有限公司 | A kind of novel extraction dephenolize system |
| CN110694300A (en) * | 2019-10-23 | 2020-01-17 | 金川集团股份有限公司 | Platinum-palladium efficient extraction and separation system and extraction and separation method thereof |
| CN110732159A (en) * | 2019-11-05 | 2020-01-31 | 大连大学 | continuous grading type high-efficiency extraction device |
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| US7964233B2 (en) * | 2005-04-29 | 2011-06-21 | Kraft Foods Global Brands Llc. | Production of whole grain shredded products |
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| JP3433892B2 (en) * | 1997-09-16 | 2003-08-04 | 三菱レイヨン株式会社 | Acrylic film with good processability and molded products laminated with the acrylic film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108751317A (en) * | 2018-07-25 | 2018-11-06 | 合肥中亚环保科技有限公司 | A kind of novel extraction dephenolize system |
| CN110694300A (en) * | 2019-10-23 | 2020-01-17 | 金川集团股份有限公司 | Platinum-palladium efficient extraction and separation system and extraction and separation method thereof |
| CN110694300B (en) * | 2019-10-23 | 2021-08-27 | 金川集团股份有限公司 | Platinum-palladium efficient extraction and separation system and extraction and separation method thereof |
| CN110732159A (en) * | 2019-11-05 | 2020-01-31 | 大连大学 | continuous grading type high-efficiency extraction device |
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