CN106865706A - A kind of toluene oxidation method prepares the treatment and circulation utilization method in phenmethylol technique containing organic matter salt solution - Google Patents
A kind of toluene oxidation method prepares the treatment and circulation utilization method in phenmethylol technique containing organic matter salt solution Download PDFInfo
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- CN106865706A CN106865706A CN201710149305.2A CN201710149305A CN106865706A CN 106865706 A CN106865706 A CN 106865706A CN 201710149305 A CN201710149305 A CN 201710149305A CN 106865706 A CN106865706 A CN 106865706A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
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Abstract
Treatment and the circulation utilization method in phenmethylol technique containing organic matter salt solution are prepared the invention discloses a kind of toluene oxidation method.The sulfate ion and potassium ion or sodium ion, calcium ion prepared toluene air oxidation using bipolar membrane electrodialysis device in the salt solution containing organic matter produced in phenmethylol technique are combined with water power from the hydrogen ion and hydroxide ion for producing respectively, dilute sulfuric acid and corresponding dilute alkaline soln is converted into be recycled as pH value regulator, the weak brine containing organic matter is obtained rich in the salt-free water of organic matter after being distilled through MVR after desalination, it is back to use in former technique as process water, the strong brine without organic matter is used as the feed cycle of bipolar membrane electrodialysis device.The present invention realizes recycling for brine waste, and processing procedure no waste discharge belongs to a kind of green, circulation, environment-friendly treatment method, and process is simple, energy consumption is low, remarkable in economical benefits.
Description
Technical field
The present invention relates to a kind for the treatment of containing organic matter salt solution and circulation utilization method, particularly a kind of toluene oxidation legal system
The treatment containing organic matter salt solution and circulation utilization method, belong to organic chemical industry's production technical field in standby phenmethylol technique.
Background technology
Phenmethylol is a kind of important chemical industry organic intermediate, is widely used in textile auxiliary, photosensitive material, medicine, perfume (or spice)
Material and dye industry.About 33.12 ten thousand tons of the aggregated capacity in the phenmethylol whole world in 2015, China is global maximum phenmethylol producing country,
Account for the 39.61% of global aggregated capacity.China's phenmethylol production capacity is continuously increased in recent years, and yield also has certain growth.It is domestic at present
The method of outer production phenmethylol mainly has benzyl chloride Hydrolyze method and toluene oxidation method, and benzyl chloride Hydrolyze method is inevitably led because of it
It is chloride in cause product phenmethylol, gradually replaced by toluene oxidation method.Toluene oxidation method prepare phenmethylol have technological process it is short,
Low production cost, phenmethylol product without chlorine, the features such as product quality is high.This technique is, with toluene as raw material, in catalyst, to trigger
In the presence of agent and auxiliary agent liquid-phase oxidation of toluene reaction production benzyl peroxide, benzyl peroxide are carried out with the oxygen in air
Generation phenmethylol is decomposed under certain condition., it is necessary to treat decomposing materials during benzyl peroxide generation phenmethylol
Carry out acid-base value regulation and use the dilute alkaline soln of alkali metal as pH value regulator, the Acidic organic matter in material to be decomposed with
The dilute alkaline soln of addition is acted on and forms salt solution, simultaneously because partial alkaline or Neutral Organic Compound have certain dissolving in salt solution
Balance, so as to during benzyl peroxide controlled decomposition generation phenmethylol, a certain amount of salt containing organic matter can be produced
Water, this part salt solution contains cation K according to the difference of the alkali for using+Or Na+Or Ca2+And a small amount of organic matter phenmethylol,
Benzaldehyde etc., the salt in this salt solution is mainly the basic salt of Acidic organic matter, it is difficult to biochemical treatment, and its corresponding organic matter
There is added value higher, therefore, finding a kind of rational treatment and recycling the method containing organic matter salt solution has significantly
Economy and social effect.
The content of the invention
Contain organic matter salt solution in preparing phenmethylol technique it is an object of the invention to provide a kind of toluene oxidation method
Treatment and circulation utilization method, realize the treatment containing organic matter salt solution and rationally utilize.
The technical solution adopted by the present invention is such, and a kind of toluene oxidation method prepares salt containing organic matter in phenmethylol technique
The treatment of water and circulation utilization method, comprise the following steps：
(1) containing the desalination of organic matter salt solution
Toluene oxidation method is prepared the salt solution containing organic matter and process water feeding bipolar membrane electrodialysis dress produced in phenmethylol technique
In putting, under electric field action, the anion SO in salt solution4 2-With water power from the H for producing+With reference to the discharge of generation dilution heat of sulfuric acid is simultaneously
It is back to use during primitive nail benzene oxidatoin prepares phenmethylol production technology, cation potassium ion or sodium ion or calcium ion and water in salt solution
Ionize the OH for producing-Discharged with reference to, generation dilute alkaline soln and be back to use during primitive nail benzene oxidatoin prepares phenmethylol production technology, removal
The weak brine containing organic matter is obtained after zwitterion；
Wherein, salt mass concentration is that 10%~15%, organic matter mass concentration is 0.01%~0.5% in salt solution containing organic matter；Conversion
Into dilute sulfuric acid concentration be 8%~15%；The dilute alkaline soln concentration for changing into is 6%~12%；Contained after removal zwitterion
The μ s/cm of weak brine electrical conductivity ＜ 30 of machine thing；
(2) weak brine concentration and organic matter containing organic matter is separated
The weak brine containing organic matter that step (1) is obtained through MVR distill, organic matter azeotrope with water steam it is condensed after contained
The water of organic matter is recycled as a small amount of process water as step (1) of process water, and remaining is back to use the preparation of primitive nail benzene oxidatoin
In phenmethylol production technology, a small amount of strong brine without organic matter is circulated back to before bipolar membrane electrodialysis and needs after MVR concentrations
The salt solution containing organic matter for the treatment of is carried out except salt treatment together.
Bipolar membrane electrodialysis device in the present invention is conventional bipolar membrane electrodialysis device, belongs to known device.
MVR is the low distillation equipment of the energy consumption for generally using in recent years, also referred to as mechanical steam recompression technology.
The present invention obtains following beneficial effect：
(1) present invention uses bipolar membrane electrodialysis desalination, and the salt solution produced in phenmethylol production process is completely converted into diluted acid
And diluted alkaline, directly as pH adjusting agent fully recovering to original production process in, without waste gas, waste water, spent acid, salkali waste, waste residue row
Put, comprehensive benefit is notable；
(2) present invention using MVR distillation containing organic matter weak brine while separated organic matter, distill out containing organic matter
Water complete-reclaiming, while a small amount of strong brine for producing is used as the feedstock circulation of bipolar membrane electrodialysis, whole process is without useless
Gurry is produced and discharged, and realizes totally-enclosed, recycling, while operation processing cost is lower than conventional distillation energy consumption, warp
Ji remarkable benefit.
Specific embodiment
Following examples are used to illustrate the present invention.But, these embodiments are that the invention will be further described, without
It is interpreted as limitation of the scope of the invention.
A kind of toluene oxidation of embodiment 1 prepares the treatment in phenmethylol technique containing organic matter salt solution and recycles
Method, comprises the following steps：
(1) containing the desalination of organic matter salt solution
By the mass concentration that the mass concentration that toluene oxidation method prepares the salt produced in phenmethylol production technology is 12%, organic matter
It is 0.3% salt solution containing organic matter and process water（I.e. a small amount of step（2）The evaporation condensate of middle MVR）Feeding Bipolar Membrane electric osmose
In analysis apparatus, in the presence of electric field, the anion SO in salt solution4 2-With water power from the H for producing+It is 12% to be combined into mass concentration
Dilution heat of sulfuric acid discharge and be back to use during primitive nail benzene oxidatoin method prepares phenmethylol production technology；Cation K in salt solution+With water
Ionize the OH for producing-Dilute potassium hydroxide aqueous slkali that mass concentration is 8% is combined into discharge and be back to use the preparation of primitive nail benzene oxidatoin method
In phenmethylol production technology；Obtained after removal zwitterion containing the weak brine that organic matter and electrical conductivity are 18 μ s/cm；
(2) weak brine concentration and organic matter containing organic matter is separated
Step (1) is obtained to be distilled through MVR containing the weak brine that organic matter and electrical conductivity are 18 μ s/cm, organic matter azeotrope with water is steamed
Go out it is condensed after obtain the water containing organic matter as a small amount of process water recycling as step of the present invention (1) of process water, its
Remaining to be back to use during primitive nail benzene oxidatoin method prepares phenmethylol production technology, a small amount of strong brine without organic matter after MVR concentrations is followed
Before being looped back to bipolar membrane electrodialysis, carried out together with the salt solution containing organic matter processed the need for new except salt treatment, whole process without
Discarded object is outwards discharged.
Embodiment 2
（1）Desalination containing organic matter salt solution
By the mass concentration that the mass concentration that toluene oxidation method prepares the salt produced in phenmethylol production technology is 11%, organic matter
It is 0.2% salt solution containing organic matter and process water（I.e. a small amount of step（2）The evaporation condensate of middle MVR）Feeding Bipolar Membrane electric osmose
In analysis apparatus, in the presence of electric field, the anion SO42- in salt solution is combined into mass concentration and is with water power from the H+ for producing
10.7% dilution heat of sulfuric acid is discharged and is back to use during primitive nail benzene oxidatoin method prepares phenmethylol production technology；Cation in salt solution
Na+With water power from the OH for producing-The dilute sodium hydroxide aqueous slkali that mass concentration is 7.6% is combined into discharge and be back to use primitive nail benzene oxygen
Change method is prepared in phenmethylol production technology；Obtained after removal zwitterion containing the weak brine that organic matter and electrical conductivity are 16 μ s/cm；
(2) weak brine concentration and organic matter containing organic matter is separated
Step (1) is obtained to be distilled through MVR containing the weak brine that organic matter and electrical conductivity are 16 μ s/cm, organic matter azeotrope with water is steamed
Go out it is condensed after obtain the water containing organic matter as a small amount of process water recycling as step of the present invention (1) of process water, its
Remaining to be back to use during primitive nail benzene oxidatoin method prepares phenmethylol production technology, a small amount of strong brine without organic matter after MVR concentrations is followed
Before being looped back to bipolar membrane electrodialysis, carried out together with the salt solution containing organic matter processed the need for new except salt treatment, whole process without
Discarded object is outwards discharged.
Claims (2)
1. a kind of toluene oxidation method prepares the treatment in phenmethylol technique containing organic matter salt solution and circulation utilization method, and its feature exists
In comprising the following steps：
(1) containing the desalination of organic matter salt solution
Toluene oxidation method is prepared the salt solution containing organic matter and process water feeding bipolar membrane electrodialysis dress produced in phenmethylol technique
In putting, under electric field action, the anion SO in salt solution4 2-With water power from the H for producing+With reference to the discharge of generation dilution heat of sulfuric acid is simultaneously
It is back to use during primitive nail benzene oxidatoin prepares phenmethylol production technology, cation potassium ion or sodium ion or calcium ion and water in salt solution
Ionize the OH for producing-Discharged with reference to, generation dilute alkaline soln and be back to use during primitive nail benzene oxidatoin prepares phenmethylol production technology, removal
The weak brine containing organic matter is obtained after zwitterion；
(2) weak brine concentration and organic matter containing organic matter is separated
The weak brine containing organic matter that step (1) is obtained through MVR distill, organic matter azeotrope with water steam it is condensed after contained
The water of organic matter is recycled as a small amount of process water as step (1) of process water, and remaining is back to use the preparation of primitive nail benzene oxidatoin
In phenmethylol production technology, a small amount of strong brine without organic matter is circulated back to before bipolar membrane electrodialysis and needs after MVR concentrations
The salt solution containing organic matter for the treatment of is carried out except salt treatment together.
2. method according to claim 1, it is characterised in that the mass concentration of salt is in salt solution containing organic matter in step (1)
10%~15%, organic matter mass concentration is 0.01%~0.5%；The dilute sulfuric acid concentration for changing into is 8%~15%；What is changed into is dilute
Alkaline concentration is 6%~12%；The μ s/cm of weak brine electrical conductivity ＜ 30 containing organic matter are obtained after removal zwitterion.
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| CN201710149305.2A CN106865706A (en) | 2017-03-14 | 2017-03-14 | A kind of toluene oxidation method prepares the treatment and circulation utilization method in phenmethylol technique containing organic matter salt solution |
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| CN201710149305.2A CN106865706A (en) | 2017-03-14 | 2017-03-14 | A kind of toluene oxidation method prepares the treatment and circulation utilization method in phenmethylol technique containing organic matter salt solution |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354528A (en) * | 2021-06-07 | 2021-09-07 | 李乾华 | Production method of phenylacetic acid |
| CN114105754A (en) * | 2021-12-02 | 2022-03-01 | 湖北科林博伦新材料有限公司 | Organic sodium salt treatment process and device in toluene oxidation process |
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| CN102963960A (en) * | 2012-12-21 | 2013-03-13 | 南京大学 | Method for simultaneously recycling sulfuric acid and organic substances in m-cresol production wastewater |
| CN103936214A (en) * | 2013-08-02 | 2014-07-23 | 浙江赛特膜技术有限公司 | Method for bipolar membrane electrodialysis treatment of 3-aminopyrazole-4-carboxamide hemisulfate production wastewater and recycling of sulfuric acid |
| CN105084600A (en) * | 2015-08-28 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Method for efficiently treating salt-containing organic wastewater and application of method |
| CN105315177A (en) * | 2015-11-02 | 2016-02-10 | 浙江奇彩环境科技有限公司 | Synthesis process of DSD acid |
| CN105692996A (en) * | 2016-02-24 | 2016-06-22 | 湖北绿色家园精细化工股份有限公司 | Novel process for treating industrial wastewater with benzyl alcohol |
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2017
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10272494A (en) * | 1997-03-28 | 1998-10-13 | Ebara Corp | Treatment of organic waste water containing salts of high concentration |
| CN102963960A (en) * | 2012-12-21 | 2013-03-13 | 南京大学 | Method for simultaneously recycling sulfuric acid and organic substances in m-cresol production wastewater |
| CN103936214A (en) * | 2013-08-02 | 2014-07-23 | 浙江赛特膜技术有限公司 | Method for bipolar membrane electrodialysis treatment of 3-aminopyrazole-4-carboxamide hemisulfate production wastewater and recycling of sulfuric acid |
| CN105084600A (en) * | 2015-08-28 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Method for efficiently treating salt-containing organic wastewater and application of method |
| CN105315177A (en) * | 2015-11-02 | 2016-02-10 | 浙江奇彩环境科技有限公司 | Synthesis process of DSD acid |
| CN105692996A (en) * | 2016-02-24 | 2016-06-22 | 湖北绿色家园精细化工股份有限公司 | Novel process for treating industrial wastewater with benzyl alcohol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354528A (en) * | 2021-06-07 | 2021-09-07 | 李乾华 | Production method of phenylacetic acid |
| CN114105754A (en) * | 2021-12-02 | 2022-03-01 | 湖北科林博伦新材料有限公司 | Organic sodium salt treatment process and device in toluene oxidation process |
| CN114105754B (en) * | 2021-12-02 | 2024-02-27 | 湖北科林博伦新材料有限公司 | Organic sodium salt treatment process and device in toluene oxidation process |
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Application publication date: 20170620 |