CN103483180A - Process for recovering white fumaric acid from phthalic anhydride wastewater - Google Patents
Process for recovering white fumaric acid from phthalic anhydride wastewater Download PDFInfo
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- CN103483180A CN103483180A CN201310477868.6A CN201310477868A CN103483180A CN 103483180 A CN103483180 A CN 103483180A CN 201310477868 A CN201310477868 A CN 201310477868A CN 103483180 A CN103483180 A CN 103483180A
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- extraction
- fumaric acid
- phthalic anhydride
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a process for recovering white fumaric acid from phthalic anhydride wastewater produced by taking 100% or a certain proportion of naphthalene as a raw material. The process comprises the steps of settling the phthalic anhydride wastewater to obtain a supernatant; decoloring by using an extraction method instead of an activated carbon decoloration or activated carbon decoloration and extraction combination method; adding sulfourea to react; isomerizing cis-butenedioic acid in the wastewater into fumaric acid, settling and drying to obtain a white fumaric acid product.
Description
Technical field
The present invention relates to the technique that reclaims fumaric acid in phthalic anhydride waste water.After the sedimentation of phthalic anhydride waste water, upper strata liquid, replace activated carbon decolorizing or activated carbon decolorizing in conjunction with increasing the extraction process decolouring with extraction process, add the thiocarbamide reaction, the maleic acid isomery in waste water turns to fumaric acid, precipitation, drying, obtain white fumaric acid product, reaches the requirement of feed fumaric acid.
Background technology
The raw materials for production of phthalic anhydride are o-Xylol or naphthalene, and another raw material is oxygen, in reaction process, can generate approximately the by product of 3% maleic acid, and follow other by products.These by products are sprayed by water in the tail gas tower of phthalic anhydride plant, are phthalic anhydride waste water.Take thiocarbamide as catalyzer, and maleic acid can turn to FUMARIC ACID TECH GRADE by isomery, is fumaric acid.Fumaric acid can be used as feed or foodstuff additive, has been widely used.Because containing other coloring matters in phthalic anhydride waste water, reclaim in emperor's son-in-law's process and need decolouring.The activated carbon decolorizing of wastewater flow rate 0.1% ~ 1% for the phthalic anhydride waste water that the o-Xylol of take is raw material, can obtain the feed grade fumaric acid.As patent 200710013398.2 discloses a kind of fumaric acid recovery process, phthalic anhydride waste water is after sedimentation, and supernatant liquid, utilize activated carbon decolorizing, and the decolouring of recycle silicon algae soil, obtain fumaric acid through the thiocarbamide isomerization.
Yet the naphthalene of take be take the phthalic anhydride waste water that naphthalene is raw material as raw material or part, activated carbon decolorizing only, the fumaric acid obtained is aobvious red or faint yellow, does not reach feed grade.This patent relates to extracting that decolouring replaces gac or increase the extraction process decolouring after activated carbon decolorizing, from take the phthalic anhydride waste water that naphthalene or part naphthalene be raw material, reclaims white fumaric acid, reaches the requirement of feed.
Summary of the invention
This paper relates to take 100% naphthalene or a certain proportion of naphthalene reclaim the technique of fumaric acid in raw material production phthalic anhydride waste water.After the sedimentation of phthalic anhydride waste water, upper strata liquid, replace activated carbon decolorizing or activated carbon decolorizing to decolour in conjunction with extraction process with extraction process, add the thiocarbamide reaction, the maleic acid isomery in waste water turns to fumaric acid, precipitation, drying, obtain white fumaric acid product, reaches the requirement of feed.
The sedimentation of phthalic anhydride waste water, after part phthalic acid, phthalic anhydride and other contamination precipitations, supernatant liquid enters the decolouring step.This precipitation step carries out usually at normal temperatures, and temperature is no more than 50 degrees centigrade.The decolouring step, stir decolouring with wastewater flow rate 0.1% ~ 1% gac, bleaching temperature from normal temperature to 90 degree centigrade all can, generally be no more than 100 degrees centigrade, churning time 10 ~ 60 minutes.
The extraction process decolouring, add a certain amount of extraction agent in waste water, extraction agent is water-fast organism, the material that affects the fumaric acid color in waste water can distribute by a certain percentage in extraction agent (being oil phase) and waste water (water), through the one or many extraction, the amount that affects fumaric acid in waste water will greatly reduce, and the product obtained is white.
Equally, maleic acid distributes by a certain percentage at oil phase and water, so extraction agent can take away the part maleic acid, can reduce the rate of recovery of fumaric acid.So, in the extraction process decolouring, generally need to strip, water returns the maleic acid in the extraction oil phase.Hui Cui is the technique of recommending, optional.
The extraction agent used can be ethers.As dibutyl ether, second amyl ether, methyl-phenoxide, but be not limited to this three kinds of ethers.
The extraction agent used is the ester class.As methyl-butyrate, methyl acetate, ethyl acetate, ethyl butyrate, propyl propionate, butyl formate, but be not limited to this six kinds of esters
The extraction agent used is hydro carbons.As sherwood oil, normal hexane, octane-iso, methylene dichloride, chlorobutane, iodoethane, but be not limited to this six kinds of hydrocarbon.
The extraction agent used is the aromatics extraction agent.As toluene, dimethylbenzene, ethylbenzene, chlorobenzene, but be not limited to this four kinds of aromatic substances.
The mixture that the extraction agent used is above-mentioned ethers, ester class, hydro carbons, aromatics.
Extraction agent after the extraction decolouring is through distillation, and coloring matter separates with extraction agent, the extraction agent reuse.
Some extraction agent efficiency is high, and single extraction can obtain white fumaric acid, and some extraction agent needs repeatedly to extract.Extraction can periodical operation, also can operate continuously in an extraction tower, even in an extraction tower, realize extraction and Hui Cui.
Through the extraction decolouring, or, after activated carbon decolorizing+extraction decolouring, waste water, under 60 ~ 100 degrees centigrade, adds 0.1 ~ 1% thiocarbamide, react 5 ~ 60 minutes, maleic acid is converted into FUMARIC ACID TECH GRADE, through filtration or centrifugal, drying, obtain white fumaric acid, reaches the feed grade requirement.
The accompanying drawing explanation
By reading the following drawings and description, feature of the present invention will be more clear.
Accompanying drawing is phthalic anhydride waste water reclamation fumaric acid simple process figure, and its key is the part of decolouring.Traditional technology adopts activated carbon decolorizing, the present invention to increase the extraction decolouring or with extraction decolouring replacement activated carbon decolorizing, take and adapts to the phthalic anhydride waste water that naphthalene or part naphthalene are raw material.
Embodiment
The raw material of phthalic anhydride waste water has two kinds, respectively called after waste water A and waste water B, phthalic anhydride waste water, the naphthalene that the raw material of waste water B is 50% and 50% o-Xylol that wherein waste water A is raw material from 100% naphthalene.The type difference of phthalic anhydride plant tail gas absorber, in its waste water, the concentration of maleic acid is different, and the difficulty of its decolouring is also different, dense called after first, its maleic acid concentration 14 ~ 20%, light called after second, its maleic acid concentration is 8 ~ 14%.Waste water has four kinds of combinations, is respectively A-grade in the first class, B-grade in the first class, second A, second B.
Following case study on implementation is containing several contrast cases, the fumaric acid band color obtained.Following table is condition and the result of case.Extraction agent one hurdle " nothing " means not take extraction process, and gac one hurdle " nothing " means not take activated carbon decolorizing, the ratio of its numeral activated carbon dosage.Solvent quantity is 30% of the water yield, extracts 3 times.
| Case | Waste water | Gac | Extraction agent | Product colour |
| 1 | Second B | 1% | Nothing | Yellow |
| 2 | A-grade in the first class | 0.2% | Toluene | In vain |
| 3 | B-grade in the first class | 0.1% | Butyl formate | In vain |
| 4 | A-grade in the first class | 0.3% | Sherwood oil | In vain |
| 5 | Second B | Nothing | Butylacetate | In vain |
| 6 | A-grade in the first class | 0.2% | Ethyl acetate | In vain |
| 7 | B-grade in the first class | 0.1% | Dibutyl ether | In vain |
| 8 | A-grade in the first class | 0.3% | Chlorobenzene | In vain |
| 9 | Second A | Nothing | Methylene dichloride | In vain |
| 10 | Second B | Nothing | Toluene and ethyl acetate 1:1 mixed extractant | In vain |
Claims (10)
1. reclaim the technique of white fumaric acid in a phthalic anhydride waste water, it is characterized in that, after the sedimentation of phthalic anhydride waste water, upper strata liquid, replace activated carbon decolorizing or activated carbon decolorizing to decolour in conjunction with extraction process with extraction process, adds the thiocarbamide reaction, maleic acid isomery in waste water turns to fumaric acid, precipitation, drying, obtain white fumaric acid product.
2. extraction process according to claim 1, is characterized in that, the extraction agent used is ethers.
3. ether extration agent according to claim 2 is dibutyl ether, second amyl ether, methyl-phenoxide.
4. extraction process according to claim 1, is characterized in that, the extraction agent used is the ester class.
5. esters extractant according to claim 4 is methyl-butyrate, methyl acetate, ethyl acetate, ethyl butyrate, propyl propionate, butyl formate.
6. extraction process according to claim 1, is characterized in that, the extraction agent used is hydro carbons.
7. hydro carbons extraction agent according to claim 6 is sherwood oil, normal hexane, octane-iso, methylene dichloride, chlorobutane, iodoethane.
8. extraction process according to claim 1, is characterized in that, the extraction agent used is the aromatics extraction agent.
9. aromatics kind of extractants according to claim 8 is toluene, dimethylbenzene, ethylbenzene, chlorobenzene.
10. extraction process according to claim 1, is characterized in that, the mixture that the extraction agent used is above-mentioned ethers, ester class, hydro carbons, aromatics.
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| CN201310477868.6A CN103483180A (en) | 2013-10-14 | 2013-10-14 | Process for recovering white fumaric acid from phthalic anhydride wastewater |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262136A (en) * | 2014-08-28 | 2015-01-07 | 铜陵化工集团有机化工有限责任公司 | Method for recycling fumaric acid from phthalic anhydride production wastewater |
| CN106854006A (en) * | 2016-12-21 | 2017-06-16 | 华南理工大学 | The extractant and extracting process of a kind of efficient removal COD and polyhydric phenols |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4935324A (en) * | 1972-08-02 | 1974-04-01 | ||
| RU1838291C (en) * | 1990-07-12 | 1993-08-30 | Армянский Научно-Исследовательский Институт Прикладной Химии "Ариак" | Method of fumaric acid synthesis |
| CN101024608A (en) * | 2007-03-15 | 2007-08-29 | 山东宏信化工股份有限公司 | Process for preparing fumaric acid by spraying acid water to benzene anhydride oxidized tail gas |
-
2013
- 2013-10-14 CN CN201310477868.6A patent/CN103483180A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4935324A (en) * | 1972-08-02 | 1974-04-01 | ||
| RU1838291C (en) * | 1990-07-12 | 1993-08-30 | Армянский Научно-Исследовательский Институт Прикладной Химии "Ариак" | Method of fumaric acid synthesis |
| CN101024608A (en) * | 2007-03-15 | 2007-08-29 | 山东宏信化工股份有限公司 | Process for preparing fumaric acid by spraying acid water to benzene anhydride oxidized tail gas |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262136A (en) * | 2014-08-28 | 2015-01-07 | 铜陵化工集团有机化工有限责任公司 | Method for recycling fumaric acid from phthalic anhydride production wastewater |
| CN104262136B (en) * | 2014-08-28 | 2016-07-06 | 铜陵化工集团有机化工有限责任公司 | Phthalic anhydride produces the method for waste water reclamation fumaric acid |
| CN106854006A (en) * | 2016-12-21 | 2017-06-16 | 华南理工大学 | The extractant and extracting process of a kind of efficient removal COD and polyhydric phenols |
| CN106854006B (en) * | 2016-12-21 | 2020-08-18 | 华南理工大学 | Extracting agent for efficiently removing COD (chemical oxygen demand) and polyphenol and extracting method |
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Application publication date: 20140101 |