CN109369575A - A kind of clean preparation method of caustic soda saponification legal system propylene oxide - Google Patents
A kind of clean preparation method of caustic soda saponification legal system propylene oxide Download PDFInfo
- Publication number
- CN109369575A CN109369575A CN201811356330.9A CN201811356330A CN109369575A CN 109369575 A CN109369575 A CN 109369575A CN 201811356330 A CN201811356330 A CN 201811356330A CN 109369575 A CN109369575 A CN 109369575A
- Authority
- CN
- China
- Prior art keywords
- saponification
- propylene oxide
- waste water
- cod
- caustic soda
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
Proposed by the present invention is a kind of clean preparation method of caustic soda saponification legal system propylene oxide.Acidified, chlorohydrination and saponification, wastewater treatment and saline treatment process are completed.The present invention makees the saponification liquor of epoxy propane saponified reaction using caustic soda, replaces current milk of lime, so that the side reaction of epoxy propane saponified reaction is reduced, improves the conversion ratio of saponification；Saponification liquor is made using caustic soda, saponification waste liquid amount can be made to reduce, the other metal ions of saponification waste liquid are reduced, and the SS in waste water is greatly reduced.High-COD waste water containing NaCl first passes through biochemical treatment, it is ensured that waste water TOC is less than 7；Then COD and sodium ion and chloride ion are separated using electrodialysis, recycles the sodium chloride solution of 20% concentration, this solution returns to ionic exchange membrane caustic supplement salt water；Waste water containing COD uses reverse osmosis technology, removes COD and chloride ion, obtains clear water, realize the zero-emission of propylene oxide by chlorohydrination.It is suitable for the clean preparation method application as propylene oxide by chlorohydrination.
Description
Technical field
Proposed by the present invention is the method for the production field of chemical products, and specifically a kind of caustic soda is saponified legal system epoxy
The clean preparation method of propane.
Background technique
Propylene oxide is a kind of important Organic chemical products, is to be only second to polypropylene and acrylonitrile in Propylene Series product
The third-largest derivative and chlor-alkali industry in balance chlorine staple product.
Industrialized Synthesis of Propylene Oxide mainly has chlorohydrination, conjugated oxidation and the direct oxygen of hydrogen peroxide both at home and abroad at present
Change method.Conjugated oxidation includes ethylbenzene cooxidation and iso-butane conjugated oxidation, carries out cooxidation reaction by ethylbenzene and iso-butane respectively,
Generate styrene and the tert-butyl alcohol, coproduction propylene oxide.Conjugated oxidation process flow is long, and process operating pressure is high, and equipment investment is big,
Coproduction object amount is big.Hydrogen peroxide direct oxidation method product only has propylene oxide and water, and without joint product, pollution is small, is the life of environmental protection
Production method still wants the process units of mating hydrogen peroxide, invests larger；Production process energy consumption is high, and total cost of production is high.Chloropharin
Method propylene oxide is that water and chlorine carry out acidification reaction and generates hydrochloric acid and hypochlorous acid, and hypochlorous acid and propylene reaction generate chloropropyl alcohol,
Saponification agent is made with 17% lime milk solution and chloropropyl alcohol saponification generates crude propene oxide, then through rectifying up to product propylene.
The process production techniques are mature, and construction investment is few, and of less demanding to raw material propylene, product cost is low, have stronger market competing
Strive power.But propylene oxide by chlorohydrination water resources consumption is big, generates a large amount of high-salt wastewaters and waste residue, 1 ton of propylene oxide of every production
Generate 45 tons of high-COD waste waters and 2 tons of waste residue.Waste water chloride ion-containing height, COD high, it is difficult to handle, environmental protection pressure is big.
China produces propylene oxide based on chlorohydrination.Although the method production cost is low, high-quality, saponification waste-water and useless
Slag is difficult to handle, and becomes the bottleneck of chlorohydrination production.Therefore it is raw to be no longer satisfied current environmental protection for chlorohydrination production propylene oxide
The requirement of production.But if turning off propylene oxide by chlorohydrination manufacturer, the chlorine that not can guarantee chlor-alkali enterprises in the short time is flat
Weighing apparatus, will lead to the development of entire caustic soda and downstream industry.Entire propylene oxide by chlorohydrination production has been in awkward condition.
Extremely urgent degree has been arrived to the high pollution problem of propylene oxide by chlorohydrination, therefore, chlorohydrination epoxy third
The process for cleanly preparing of alkane be China's propylene oxide industry there is an urgent need to.
Summary of the invention
In order to realize the clean manufacturing of chlorohydrination production propylene oxide, the invention proposes a kind of caustic soda to be saponified legal system epoxy
The clean preparation method of propane.This method passes through acidification, chlorohydrination and saponifying process, wastewater treatment process and saline treatment work
The technical issues of sequence, solution propylene oxide clean manufacturing.
The solution adopted by the present invention to solve the technical problem is that:
1, acidification, chlorohydrination and saponifying process: chlorine is passed through generation hydrochloric acid and hypochlorous acid, propylene in industry water and is passed through above-mentioned molten
Chloropropyl alcohol solution is generated in liquid, so that chloropropyl alcohol solution and 32% sodium hydroxide is passed through saponification column in proportion by chlorohydrin action,
It is saponified by saponification；
2, it is useless greater than 88% crude propene oxide, COD and 5% sodium hydroxide that purity wastewater treatment process: is obtained by acidification reaction
Water；Make that waste water enters activated sludge tank and contact-oxidation pool is handled, reduce the COD of waste water, by filtered waste water into
Row electrodialysis plant carries out electrodialysis, and recycling obtains 20% salt water,
3, saline treatment process: passing through electrolysis with ion-exchange film for salt water, enters salt water by the hyposaline waste water of electrodialysis plant
Reverse osmosis unit, water outlet enter the acidification reaction of propylene oxide, recycle.
Good effect: the present invention makees the saponification liquor of epoxy propane saponified reaction using caustic soda, replaces current milk of lime, so that
The side reaction of epoxy propane saponified reaction is reduced, and improves the conversion ratio of saponification；Saponification liquor is made using caustic soda, can make to be saponified
Waste liquid amount is reduced, and the other metal ions of saponification waste liquid are reduced, and the SS in waste water is greatly reduced.High-COD waste water containing NaCl first leads to
Cross biochemical treatment, it is ensured that waste water TOC is less than 7；Then separate COD and sodium ion and chloride ion using electrodialysis, recycling 20% is dense
The sodium chloride solution of degree, this solution return to ionic exchange membrane caustic supplement salt water；Waste water containing COD uses reverse osmosis technology, goes
Except COD and chloride ion, COD≤30, CL -≤30ppm clear water are obtained, into propylene oxide acidification reaction system；By processing
Process realizes the zero-emission of propylene oxide by chlorohydrination.It is suitable for the clean preparation method application as propylene oxide by chlorohydrination.
Specific embodiment
Embodiment 1
Process:
1, acidification, chlorohydrination and saponifying process:
Chlorine is passed through in industry water and generates hydrochloric acid and hypochlorous acid, propylene is passed through generation chloropropyl alcohol solution in above-mentioned solution, passes through
Chlorohydrin action makes chloropropyl alcohol solution and 32% sodium hydroxide be passed through saponification column in proportion, is saponified by saponification；
2, wastewater treatment process:
Purity is obtained greater than 88% crude propene oxide, the waste water of COD and 5% sodium hydroxide by acidification reaction；Waste water is set to enter work
Property sludge-tank and contact-oxidation pool handled, reduce the COD of waste water, by filtered waste water carry out electrodialysis plant progress
Electrodialysis, recycling obtain 20% salt water,
3 saline treatment processes:
Salt water is passed through into electrolysis with ion-exchange film, salt water is made to enter reverse osmosis unit by the hyposaline waste water of electrodialysis plant, is discharged
Into the acidification reaction of propylene oxide, recycle.
Embodiment 2
This embodiment differs from embodiment 1 in that activated sludge process and catalytic oxidation are changed to hydrolysis acidification and catalytic oxidation work
Sequence combination.
Embodiment 3
Increase ozone oxidation on the basis of embodiment 2 and waste water COD is down to 30mg/L or less.
Embodiment 4
With 3 differences of embodiment be saponified concentration of caustic soda be 40%, acquired results as different from Example 3, postprocessing working procedures
Waste water COD is increased, but wastewater flow rate is reduced.
Advantage:
The present invention carries out electricity in the clean preparation method production process of sintering saponification legal system propylene oxide, by the salt water after reaction
Discharge was both reduced for recycling using the reverse osmosis clean water for obtaining low COD after dialysis processing, and had prevented to pollute ring
Border, but also can recycle, save water and save the energy.So that propylene oxide production process without sewage discharge, is realized clear
Clean production.
Claims (2)
1. a kind of clean preparation method of caustic soda saponification legal system propylene oxide, it is characterized in that:
1), acidification, chlorohydrination and saponifying process:
Chlorine is passed through in industry water and generates hydrochloric acid and hypochlorous acid, propylene is passed through generation chloropropyl alcohol solution in above-mentioned solution, passes through
Chlorohydrin action makes chloropropyl alcohol solution and 32% sodium hydroxide be passed through saponification column in proportion, is saponified by saponification；
2), wastewater treatment process:
Purity is obtained greater than 88% crude propene oxide, the waste water of COD and 5% sodium hydroxide by acidification reaction；Waste water is set to enter work
Property sludge-tank and contact-oxidation pool handled, reduce the COD of waste water, by filtered waste water carry out electrodialysis plant progress
Electrodialysis, recycling obtain 20% salt water,
3), saline treatment process:
Salt water is passed through into electrolysis with ion-exchange film, salt water is made to enter reverse osmosis unit by the hyposaline waste water of electrodialysis plant, is discharged
Into the acidification reaction of propylene oxide, recycle.
2. the clean preparation method of a kind of caustic soda saponification legal system propylene oxide according to claim 1, it is characterized in that: described
Wastewater treatment process is combined using hydrolysis acidification and catalytic oxidation process, and increases ozone oxidation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811356330.9A CN109369575A (en) | 2018-11-15 | 2018-11-15 | A kind of clean preparation method of caustic soda saponification legal system propylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811356330.9A CN109369575A (en) | 2018-11-15 | 2018-11-15 | A kind of clean preparation method of caustic soda saponification legal system propylene oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109369575A true CN109369575A (en) | 2019-02-22 |
Family
ID=65389221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811356330.9A Pending CN109369575A (en) | 2018-11-15 | 2018-11-15 | A kind of clean preparation method of caustic soda saponification legal system propylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109369575A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075018A (en) * | 2021-10-20 | 2022-02-22 | 中蓝连海设计研究院有限公司 | Recycling treatment method of epoxy propane wastewater by caustic soda saponification method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2421893A1 (en) * | 1977-11-10 | 1979-11-02 | Naphtachimie Sa | Propylene oxide prepn. from propylene - involves (oxy)chlorination, hydrating prod. then saponifying with caustic soda |
| CN101735177A (en) * | 2009-12-07 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Method for producing propylene oxide |
| CN102952101A (en) * | 2012-10-12 | 2013-03-06 | 山东海化集团有限公司 | Process for producing epoxypropane by adopting caustic soda saponification method |
| CN104773928A (en) * | 2015-04-27 | 2015-07-15 | 南京环保产业创新中心有限公司 | Propylene epoxide production wastewater treatment method |
-
2018
- 2018-11-15 CN CN201811356330.9A patent/CN109369575A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2421893A1 (en) * | 1977-11-10 | 1979-11-02 | Naphtachimie Sa | Propylene oxide prepn. from propylene - involves (oxy)chlorination, hydrating prod. then saponifying with caustic soda |
| CN101735177A (en) * | 2009-12-07 | 2010-06-16 | 杭州水处理技术研究开发中心有限公司 | Method for producing propylene oxide |
| CN102952101A (en) * | 2012-10-12 | 2013-03-06 | 山东海化集团有限公司 | Process for producing epoxypropane by adopting caustic soda saponification method |
| CN104773928A (en) * | 2015-04-27 | 2015-07-15 | 南京环保产业创新中心有限公司 | Propylene epoxide production wastewater treatment method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114075018A (en) * | 2021-10-20 | 2022-02-22 | 中蓝连海设计研究院有限公司 | Recycling treatment method of epoxy propane wastewater by caustic soda saponification method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101735177B (en) | Method for producing propylene oxide | |
| CN104370394B (en) | A kind of processing method of surface water desalter by-product brine waste | |
| CN102320641B (en) | Resource utilization method for saponification waste water producing epoxypropane by chlorohydrination process | |
| CN108455680B (en) | Environment-friendly resource utilization method of steel pickling waste liquid | |
| CN101717162A (en) | Method for treating and recycling wastewater generated by processing surface of aluminum profile | |
| CN106957283B (en) | A kind of mono-acid method alcoholizing propenyl chloride Synthesis of Propylene Oxide | |
| CN105621764A (en) | Treatment process of epoxy chloropropane production wastewater | |
| CN103342434A (en) | Treatment method of wastewater generated in cyclization step in production process of epoxy chloropropane from glycerol | |
| CN102689999A (en) | Resourceful treatment method for silica gel waste water | |
| CN111485247A (en) | Resourceful treatment device and method for high-chlorine organic hazardous waste incineration fly ash | |
| CN109705062A (en) | A kind of chlorohydrination epoxides production technology of no solid slag and by-product chloropropane | |
| CN209411984U (en) | A kind of utilization of wastewater resource and salt production device | |
| CN108002607A (en) | A kind of chemical wastewater treatment technique | |
| CN109369575A (en) | A kind of clean preparation method of caustic soda saponification legal system propylene oxide | |
| CN212199433U (en) | Resourceful treatment device for incineration fly ash of high-chlorine organic hazardous waste | |
| CN107226572B (en) | Zero-emission system and method for advanced treatment of mercury-containing wastewater | |
| CN107602394A (en) | Bipolar membrane electrodialysis prepares N, N, the method for the adamantyl ammonium hydroxide of N trimethyls 1 | |
| CN102153224A (en) | Treatment technology for industrial sewage from sodium carboxymethylcellulose | |
| CN208378605U (en) | The special equipment of the separating technology of organic matter and salt in strong brine | |
| CN102241448A (en) | Comprehensive utilization method of sodium sulfate wastewater | |
| CN101092703A (en) | Method for producing electrolyte by using saponated waste liquor containing sodium chloride as raw material | |
| CN108716005B (en) | Method for preparing silica sol by pulping and electrolyzing silica micropowder | |
| CN217202410U (en) | Reclaimed water recycling system | |
| CN202988881U (en) | Waste acid and waste saline water treatment system combining inorganic synthesis with carbon absorption | |
| CN111362888B (en) | Production method and production system for propylene oxide by caustic soda saponification method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190222 |
|
| RJ01 | Rejection of invention patent application after publication |