CN1297332C - 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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- CN1297332C CN1297332C CNB2005100941010A CN200510094101A CN1297332C CN 1297332 C CN1297332 C CN 1297332C CN B2005100941010 A CNB2005100941010 A CN B2005100941010A CN 200510094101 A CN200510094101 A CN 200510094101A CN 1297332 C CN1297332 C CN 1297332C
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Abstract
The present invention discloses liquid and liquid extraction processing method for waste sulfuric acid containing acetochloral and trichloroacetic acid, which is used for eliminating acetochloral and trichloroacetic acid contained in waste sulfuric acid via liquid and liquid extraction. The present invention can effectively eliminate the acetochloral, the trichloroacetic acid and other organic substances in the waste sulfuric acid and has the advantage of easy operation without secondary pollution.
Description
Technical field:
The present invention relates to a kind of processing method of sulfur waste acid.
Background technology:
Trichloroacetaldehyde is a kind of important chemical, pesticide intermediate.China all adopt at present the dehydration of the chlorination of multi-stage stepwise ethanol, the concentrated sulfuric acid the trichloroacetaldehyde production process route, can produce a large amount of sulfur waste acid that contains organic impurities such as trichloroacetaldehyde, trichloroacetic acid in process of production.General sulfur acid 62%～70% contains trichloroacetaldehyde, trichloroacetic acid 1～3% in this sulfur waste acid, also contains organic matter and carbide such as ethyl-sulfate about 2%.Because trichloroacetaldehyde, trichloroacetic acid 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.Trichloroacetic acid is longer in the degradation in soil time in addition, the protein of plant is had precipitation, so the sulfur waste acid that contains trichloroacetaldehyde, trichloroacetic acid 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 trichloroacetaldehyde.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 crops even total crop failure incident.Former national Ministry of Agriculture, Animal Husbandry and Fisheries determines that in relevant the evaluation content that trichloroacetaldehyde in the phosphate fertilizer or trichloroacetic acid 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 trichloroacetaldehyde, the highest total content of trichloroacetic acid are lower than 400ppm in the sulfur waste acid, just can be used for making phosphate fertilizer, just can avoid crops are produced the poisoning effect.If effectively do not remove wherein trichloroacetaldehyde, trichloroacetic acid, this sulfur waste acid just can not obtain recycling, and also can cause serious environmental to pollute even enter water body after the neutralization dilution, wastes a large amount of renewable resources simultaneously.How processing and utilizing contains the sulfur waste acid of trichloroacetaldehyde, trichloroacetic acid, 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 processing methods such as the way of distillation, oxidizing process at present.Remove trichloroacetaldehyde, trichloroacetic acid in the sulfur waste acid as what Zhengzhou Polytechnical College proposed with the way of distillation, but practice shows technically and all exists economically defective.Fuyang Chemical Group Co., Ltd., Handan's invention " producing the processing method of the sulfur waste acid that produces in the trichloroacetaldehyde process " still belongs to simple distllation, this method is actually the way of distillation 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 thermic load of distillation still increase owing to increased the evaporating capacity of water, by mass 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, the way of distillation also exists operating 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 trichloroacetaldehyde, trichloroacetic acid that can effectively remove in the sulfur waste acid, and easy to operate, the liquid-liquid extraction processing method that contains trichloroacetaldehyde, the acid of trichloroacetic acid sulfur waste of non-secondary pollution.
Technical solution of the present invention is:
A kind of liquid-liquid extraction processing method that contains trichloroacetaldehyde, the acid of trichloroacetic acid sulfur waste, it is characterized in that: adopt continuous differential extraction method, remove trichloroacetaldehyde contained in the sulfur waste acid and trichloroacetic acid by liquid-liquid extraction, comprise the following steps: to add extractant successively, and be continuous phase with the extractant from extraction tower bottom; Add sulfur waste acid from the extraction tower top, and be decentralized photo with sulfur waste acid, the two-phase volume ratio is a continuous phase: carry out extracting operation under decentralized photo=1: 0.5～1, normal temperature, raffinate phase is the sulfuric acid that removes behind trichloroacetaldehyde, the trichloroacetic acid 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 decentralized photo; Strippant is sent into the back extraction tower from the back extraction top of tower, and as back extraction continuous phase, the two-phase volume ratio is a back extraction continuous phase: back extraction decentralized photo=1: 0.5～1, the operation of stripping under the normal temperature, the back extraction top of tower flows out is regenerating extracting agent, deliver to the extractant import of extraction tower bottom, enter extraction tower and carry out the extracting-back extraction circulation; Collect the NaOH solution that contains trichloroacetaldehyde and trichloroacetic acid from the back extraction tower bottom; Wherein said extractant is toluene or dimethylbenzene, and strippant is a sodium hydroxide solution, and the strippant concentration sodium hydroxide is 0.4～0.8mol/L.
When extraction was handled, extractant and both volume ratios of sulfur waste acid were extractant: sulfur waste acid=0.5～1: 0.5～1, and during reextraction, the volume ratio of strippant and extractant is a strippant: extractant=0.5～1: 0.5～1.
The described liquid-liquid extraction processing method that contains trichloroacetaldehyde, the acid of trichloroacetic acid sulfur waste adopts classification contact extraction, comprises the following steps: successively
(1) one-level extraction: add extractant and sulfur waste acid in first mixing channel respectively, the two-phase volume ratio is an extractant: sulfur waste acid=1: 0.5～1, and after abundant at normal temperatures stirring or the vibration, send into first settling tank and leave standstill phase-splitting;
(2) secondary extraction: the raffinate phase after one-level extracts phase-splitting is sent into second mixing channel, simultaneously in second mixing channel, add extractant, the two-phase volume ratio is an extractant: sulfur waste acid=0.5～1: 1, after abundant at normal temperatures stirring or the vibration, send into second settling tank and leave standstill phase-splitting, get raffinate phase in the groove, be the sulfuric acid that removes behind trichloroacetaldehyde, the trichloroacetic acid;
(3) one-level is stripped: extraction phase in first, second settling tank is sent into the first back extraction groove, add strippant, the volume ratio of strippant and the extractant after extracting is a strippant: extractant=1: 0.5～1 after extraction, after abundant at normal temperatures stirring or the vibration, send into the first back extraction settling tank and leave standstill phase-splitting;
(4) secondary is stripped: the raffinate phase in the first back extraction settling tank is sent into the second back extraction groove, add strippant, strippant and one-level reextraction raffinate phase volume ratio are strippant: one-level reextraction raffinate phase=0.5～1: 0.5～1, after abundant at normal temperatures stirring or the vibration, send into the second back extraction settling tank and leave standstill phase-splitting.
In the above-mentioned steps (4) in the second back extraction settling tank raffinate phase be regenerating extracting agent, loop back the extraction mixing channel acid extracts to sulfur waste.With regenerating extracting agent the extraction of secondary counter current contacting is carried out in sulfur waste acid, promptly in second mixing channel, 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 settling tank send in first mixing channel, as the one-level extractant, the one-level extraction is carried out in sulfur waste acid.After secondary extraction and strip stage, increase extraction and reextraction progression.
Grooves such as described mixing channel, settling tank, back extraction groove are containers such as cell body or jar, bottle, pipe.
The present invention adopts the method for liquid-liquid extraction, can effectively remove organic substances such as trichloroacetaldehyde in the sulfur waste acid, trichloroacetic acid, make sulfur waste acid be purified recovery, after the secondary extraction, organic content such as trichloroacetaldehyde, trichloroacetic acid is reduced to about 0.022% (220ppm) in the sulfuric acid, organic content such as trichloroacetaldehyde, trichloroacetic acid 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 pollution abatement 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; Small 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 chart of classification contact extraction of the present invention.
Fig. 2 is the process chart of the continuous differential extraction method of the present invention.
The specific embodiment:
Embodiment 1:
(1) add the sulfur waste acid of extractant dimethylbenzene and the 60mL of 60mL respectively in first separatory funnel of 150mL, the vibration 2 minutes down of 20 ℃ of room temperatures was left standstill phase-splitting 6 minutes.This separatory funnel lower floor raffinate phase is put to second separatory funnel of 150mL.
(2) the extractant dimethylbenzene of adding 60mL in second separatory funnel, room temperature was vibrated 2 minutes down for 20 ℃, left standstill phase-splitting and after 6 minutes lower floor's raffinate phase was put to the 100mL beaker.
(3) to the raffinate phase in the beaker (sulfuric acid) sample analysis, the content that records trichloroacetaldehyde, trichloroacetic acid 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 separatory funnel of another 150mL, the NaOH solution that adds the back washing 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 trichloroacetaldehyde, trichloroacetic acid is 0.02119% in the sulfuric acid, the full gear rate is 99.10%.
Embodiment 2:
Change the extractant of embodiment 1 into toluene, other step is with embodiment 1.The content that records trichloroacetaldehyde, trichloroacetic acid 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 mixing channel 1, adds the sulfur waste acid of extractant dimethylbenzene and the 2000mL of 2000mL respectively, stir under the room temperature and send into first settling tank 2 after 10 minutes and left standstill phase-splitting 15 minutes, lower floor's raffinate phase in first settling tank 2 is sent into second mixing channel 3, and the upper strata extraction phase is then delivered to the first back extraction groove 4.
(2) add extractant dimethylbenzene 2000mL in second mixing channel 3, stir at normal temperatures and send into second settling tank 5 after 10 minutes and left standstill phase-splitting 15 minutes, lower floor's raffinate phase of getting in second settling tank 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 trichloroacetaldehyde in the sulfuric acid, trichloroacetic acid is 0.02085%, and the full gear rate is 99.11%.
(3) the lower floor's raffinate phase in second settling tank 5 of step (2) is put to another mixing channel carried out three grades of extractions, promptly add extractant dimethylbenzene 2000mL, stir at normal temperatures and send into another settling tank after 10 minutes and left standstill phase-splitting 15 minutes, take off a layer acid analysis, the content that records trichloroacetaldehyde in the sulfuric acid, trichloroacetic acid is 0.00093%, and the full gear rate is 99.96%.
(4) extraction phase from first, second settling tank 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 settling tank 6 after 10 minutes and left standstill phase-splitting 15 minutes, the raffinate phase in the first back extraction settling tank 6 is delivered to the second back extraction groove 7.
(5) raffinate phase from the first back extraction settling tank 6 in the second back extraction groove 7 is carried out the secondary reextraction by one-level reextraction same steps as.
(6) raffinate phase of getting in the second back extraction settling tank 8 is a regenerating extracting agent.With regenerating extracting agent the extraction of secondary counter current contacting is carried out in sulfur waste acid then.Promptly in second mixing channel, 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 settling tank send in first mixing channel, as the one-level extractant, 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 trichloroacetaldehyde, trichloroacetic acid is 0.02172% in the sulfuric acid, the full gear rate is 99.08%.
Embodiment 4:
Change the extractant of embodiment 3 into toluene, other step is with embodiment 4 and embodiment 6.The content that records trichloroacetaldehyde, trichloroacetic acid 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
Extractant 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 packed height 1200mm,) and be continuous phase with the extractant, 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 decentralized photo with sulfur waste acid, the two-phase volume ratio is a continuous phase: decentralized photo=1: 0.5～1, regulate the oil phase outlet valve then, make two-phase keep stable in last settling section centre position, when the tower inner fluid flow stable after, carry out extracting operation at normal temperatures.The sulfuric acid that raffinate phase promptly removes behind the trichloroacetaldehyde (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 decentralized photo, 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 continuous phase, the two-phase volume ratio is a continuous phase: decentralized photo=1: 0.5～1, regulate the water outlet valve, make two-phase interface keep stable in last settling section centre position, treat back extraction tower inner fluid flow stable after, the operation of stripping under the normal temperature, the back extraction top of tower flows out is regenerating extracting agent, be recycled to entering in the extraction tower of extraction tower bottom, after the extracting-back extraction cycling is stable, sulfuric acid sample analysis to flow out the extraction tower bottom records trichloroacetaldehyde in the sulfuric acid, the content of trichloroacetic acid is 0.02208%, and the full gear rate is 99.06%.
Claims (1)
1, a kind of liquid-liquid extraction processing method that contains trichloroacetaldehyde, the acid of trichloroacetic acid sulfur waste, it is characterized in that: adopt continuous differential extraction method, remove trichloroacetaldehyde contained in the sulfur waste acid and trichloroacetic acid by liquid-liquid extraction, comprise the following steps: to add extractant successively, and be continuous phase with the extractant from extraction tower bottom; Add sulfur waste acid from the extraction tower top, and be decentralized photo with sulfur waste acid, the two-phase volume ratio is a continuous phase: carry out extracting operation under decentralized photo=1: 0.5～1, normal temperature, raffinate phase is the sulfuric acid that removes behind trichloroacetaldehyde, the trichloroacetic acid 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 decentralized photo; Strippant is sent into the back extraction tower from the back extraction top of tower, and as back extraction continuous phase, the two-phase volume ratio is a back extraction continuous phase: back extraction decentralized photo=1: 0.5～1, the operation of stripping under the normal temperature, the back extraction top of tower flows out is regenerating extracting agent, deliver to the extractant import of extraction tower bottom, enter extraction tower and carry out the extracting-back extraction circulation; Collect the NaOH solution that contains trichloroacetaldehyde and trichloroacetic acid from the back extraction tower bottom; Wherein said extractant is toluene or dimethylbenzene, and strippant is a sodium hydroxide solution, and the strippant concentration sodium hydroxide is 0.4～0.8mol/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100941010A CN1297332C (en) | 2005-08-26 | 2005-08-26 | Liquid-liquid extraction processing method for waste sulfuric acid containing acetochloral and trichloroacetic acid |
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| CNB2005100941010A CN1297332C (en) | 2005-08-26 | 2005-08-26 | Liquid-liquid extraction processing method for waste sulfuric acid containing acetochloral and trichloroacetic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1864533B (en) * | 2005-04-29 | 2011-03-09 | 卡夫食品环球品牌有限责任公司 | Production of whole grain shredded products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270612A (en) * | 1997-09-16 | 2000-10-18 | 三菱丽阳株式会社 | Acrylic films and acrylic laminates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1270612A (en) * | 1997-09-16 | 2000-10-18 | 三菱丽阳株式会社 | Acrylic films and acrylic laminates |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1864533B (en) * | 2005-04-29 | 2011-03-09 | 卡夫食品环球品牌有限责任公司 | Production of whole grain shredded products |
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