CN107215984A - The technique for recycling sodium chlorate oxidative synthesis quinolinic acid waste water - Google Patents
The technique for recycling sodium chlorate oxidative synthesis quinolinic acid waste water Download PDFInfo
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- CN107215984A CN107215984A CN201710535407.8A CN201710535407A CN107215984A CN 107215984 A CN107215984 A CN 107215984A CN 201710535407 A CN201710535407 A CN 201710535407A CN 107215984 A CN107215984 A CN 107215984A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of technique for recycling sodium chlorate oxidative synthesis quinolinic acid waste water, waste water using the acid generation of sodium chlorate oxidizing process synthesis of quinoline is initiator, using quinoline, sodium chlorate, copper sulphate as raw material, quinolinic acid is made respectively through oxidation reaction, Basic fluxing raction and acidification reaction.Compared with prior art, the waste water that recoverable sodium chlorate oxidative synthesis quinolinic acid of the present invention is produced, technique is simple, environmental protection, and overall yield of reaction is up to more than 82%, and content is more than 99%.
Description
Technical field
The present invention relates to the recoverying and utilizing method that waste water is produced in a kind of sour technique of synthesis of quinoline, and in particular to one kind is reclaimed
Using the technique of sodium chlorate oxidative synthesis quinolinic acid waste water, belong to organic chemistry filed.
Background technology
Quinolinic acid, alias 2,3- pyridinedicarboxylic acids.It is also Copper Ion reagent as glucose synthesis is suppressed.Quinoline
Acid category niacin compound serving, is a kind of important agricultural chemicals, medicine and pressure sensitive dye intermediate, is mainly used in synthesis and contains pyridine or quinoline
The imidazolinone herbicide (such as Arsenal, Scepter) of quinoline ring, can be used for synthetic antibiotic.With 2,3- pyridine dicarboxyls
Acid is the herbicide of raw material, because its product has excellent performance and security, in recent years in the world by more
Pay attention to, the occupation rate of market in the U.S. in 2006 also begins to be widely applied up to 85% in China's most area, and
There is the trend of quick substitution traditional product.In medical product field, 2,3- pyridinedicarboxylic acids are largely used to synthesis of quinoline acid series
Medicine, is such as used to produce forth generation quinolione kind new medicine MOXIFLOXACIN.
Quinolinic acid main preparation methods currently on the market：Quinoline oxidizing process and synthetic method.Wherein, quinoline oxidizing process includes chlorine
Sour sodium oxidizing process, Ozonation and electrolytic oxidation.
Document one (Lu Qingqing Wang Chengyun Shen Yongjia, the synthesis and application of pyridinedicarboxylic acid), which is disclosed, uses one pot process
The method of quinolinic acid, i.e., sequentially add heating response after reactor by water, cupric sulfate pentahydrate, quinoline, the concentrated sulfuric acid and sodium chlorate, production
Rate 56.4%, the technique does not have catalyst initiation, causes to trigger overlong time, and one kettle way is easy to slug.(the Duan Xiang of document two
Raw Nie Ping, the study on the synthesis of quinolinic acid) disclose method using catalytic oxidation synthesis of quinoline acid, quinoline is in copper sulphate and dilute
Catalysis is complexed into quinolinic acid copper in sulfuric acid, then obtains quinolinic acid sodium with sodium hydroxide reaction, quinolinic acid is obtained so as to be acidified, produce
Rate 78.1%, content 98.3%, technique does not reclaim mantoquita, causes secondary three-waste pollution inadvisable.Document three (contains clean monarch
Non- star, the synthesis of 2,3- pyridinedicarboxylic acids) using raw material sulphuric acid copper, quinoline, sulfuric acid and sodium chlorate synthesis of quinoline acid, due to using
Oxidation mother liquor initiation reaction, it is very unstable, and copper sulphate does not carry out recovery, cost is larger.(the female quinoline of Huang Cheng of document four
Ozonisation-synthesis nicotinic acid) disclose the technique for preparing quinoline using ozone oxidation in glacial acetic acid, ethyl acetate and water, yield
66%, its defect is that yield is too low, and cost is too high.Document five (the long cherry of Su Yu will Zhu, the electro synthesis of quinolinic acid) discloses one kind
The method that quinoline is prepared using anodic oxidation, yield 91.4%, although yield is higher, but equipment investment is larger, containing heavy metal lead
The bad processing of waste water.
The content of the invention
It is an object of the invention to provide a kind of technique for recycling sodium chlorate oxidative synthesis quinolinic acid waste water, the technique
Overall yield of reaction up to more than 82%, content is more than 99%.
Its reaction equation is as follows：
Realizing the technical solution of the object of the invention is：
A kind of technique for recycling sodium chlorate oxidative synthesis quinolinic acid waste water, comprises the following steps：
(1) added water into reactor, open stirring, plus copper sulphate, (quality compares water to recovered liquid：Organic matter is 1000：4~
, and a small amount of catalyst aluminum trihalide 8)；45~60 DEG C slowly are warming up to, insulation is finished, quinoline, sodium chlorate are slowly added successively,
90~100 DEG C are warming up to, steam is closed, initiation reaction is waited；Finish, control at 98~103 DEG C to reaction since being reacted initiation
Insulation 8~10 hours, insulation is finished with circulating water cooling to 30~40 DEG C, and suction filtration, filter cake is oxide；
(2) added water and liquid caustic soda in alkaline hydrolysis kettle, open stirring, chuck leads to recirculated water；Finish unlatching vavuum pump to vacuumize, control
Temperature is at 35~45 DEG C, and slow oxygenates material, charging is finished, and heating, control is incubated 6~8 hours at 90~95 DEG C, has been incubated
Finish press filtration；Continue air pressure after having pressed, filter cake is gone out after pressing dry to the kettle that decolourizes, filtrate is applied mechanically；(3) in acidifying kettle, stirring is opened slow
It is slow that sulfuric acid is added dropwise, pH=1~3 are adjusted, with circulating water cooling to 20~45 DEG C, are then centrifuged for, it is wet that filter cake is obtained after being washed with water
Product, are dried.
Further, in reactions steps (1), quinoline：Sodium chlorate：The mol ratio of copper sulphate is 1：3.5:1.05~1.10.
Further, in reactions steps (1), it is useless that described recovered liquid refers to that sodium chlorate oxidizing process synthesis of quinoline acid is produced
Water.
Compared with prior art, the waste water that recoverable sodium chlorate oxidative synthesis quinolinic acid of the present invention is produced, technique letter
It is single, environmental protection, overall yield of reaction is up to more than 82%, and content is more than 99%.
Embodiment
With reference to embodiments, the present invention is further described in detail, but be not limited thereto；
Embodiment 1：
1st, aoxidize
In 5000L reactors plus recovered liquid 1500L (addition of recovered liquid can be according to the volume adjustment of reactor) and
600kg water, opens stirring, and copper sulphate 190kg, 300kg sulfuric acid is finished, then adds alchlor 0.5kg, is slowly warming up to 55~60
DEG C insulation 1 hour, insulation is finished, plus quinoline 300kg, sodium chlorate 800kg, is warming up to 98~100 DEG C, and be incubated 8 at 98~105 DEG C
Hour, with circulating water cooling to 30~40 DEG C, suction filtration, filter cake is oxide, and filtrate is discharged into collecting pit after being collected through storage tank, followed
Ring set is used.
2nd, alkaline hydrolysis
Added water in reactor, open stirring and chuck leads to recirculated water, plus 700kg water and liquid caustic soda 1600kg, finish unlatching true
Empty pump, oxygenates material (control temperature DEG C is at 35~45 DEG C), finishes, heats up, control is incubated 6 hours at 90~95 DEG C, insulation is finished,
The 1500kg that adds water is washed, and is pressed onto empty lower batch of the kettle work of alkaline hydrolysis and is fed intake.Continue press filtration after having pressed, filter cake bagging and weighing is gone out after pressing dry, cover
With.
3rd, it is acidified
Press filtration is being acidified in kettle after terminating, and sulfuric acid is added dropwise, pH=1 is adjusted, with circulating water cooling to 30~35 DEG C, Ran Houli
The heart, filter cake obtains wet product with 150 liter water washings, dries, and packaging obtains finished product 315.9kg, content 99.1%, yield
82.3%.Filtrate set uses oxidation reaction.
Embodiment 2
1st, aoxidize
Add recovered liquid 1500L and 600kg water in 5000L reactors, open stirring, wet copper sludge 240kg, 400kg sulfuric acid is complete
Finish, then add alchlor 0.5kg, be slowly warming up to 55~60 DEG C and be incubated 1 hour, insulation is finished, plus quinoline 300kg, sodium chlorate
800kg, is warming up to 95~98 DEG C, and is incubated 8 hours at 95~103 DEG C, with circulating water cooling to 30~40 DEG C, suction filtration, filter cake
For oxide, filtrate dump groove recovery.
2nd, alkaline hydrolysis
Added water in reactor, open stirring and chuck leads to recirculated water, plus 700kg water and liquid caustic soda 1600kg, finish unlatching true
Empty pump, oxygenates material (control temperature DEG C is at 35~45 DEG C), finishes, heats up, control is incubated 6 hours at 90~95 DEG C, insulation is finished,
The 1500kg that adds water is washed, and is pressed onto empty lower batch of the kettle work of alkaline hydrolysis and is fed intake.Continue pneumatics after having pressed, filter cake bagging and weighing is gone out after pressing dry, cover
With.
3rd, it is acidified
Press filtration is being acidified in kettle after terminating, and sulfuric acid is added dropwise, pH=1 is adjusted, with circulating water cooling to 30~35 DEG C, Ran Houli
The heart, filter cake obtains wet product with 150 liter water washings, dries, and packaging obtains finished product 314.8kg, content 99.2%, yield
82.1%.Filtrate set uses oxidation reaction.
Claims (5)
1. recycle the technique of sodium chlorate oxidative synthesis quinolinic acid waste water, it is characterised in that comprise the following steps：
（1）Added water into reactor, open stirring, plus copper sulphate, recovered liquid, and a small amount of catalyst aluminum trihalide；It is slow to rise
Temperature is to 45~60 DEG C, and insulation is finished, and quinoline, sodium chlorate are slowly added successively, is warming up to 90~100 DEG C, closes steam, waits to be triggered anti-
Should；Finished since being reacted initiation to reaction, control is incubated 8~10 hours at 98~103 DEG C, insulation, which is finished, uses circulating water cooling
To 30~40 DEG C, suction filtration, filter cake is oxide；
（2）Added water in alkaline hydrolysis kettle and liquid caustic soda, open stirring, chuck leads to recirculated water；Finish unlatching vavuum pump to vacuumize, control temperature
Degree is at 35~45 DEG C, and slow oxygenates material, charging is finished, and heating, control is incubated 6~8 hours at 90~95 DEG C, and insulation is finished
Press filtration；Continue air pressure after having pressed, filter cake is gone out after pressing dry to the kettle that decolourizes, filtrate is applied mechanically；（3）In acidifying kettle, stirring is opened slow
Sulfuric acid is added dropwise, adjusts pH=1~3, with circulating water cooling to 20~45 DEG C, is then centrifuged for, the wet product that filter cake is obtained after being washed with water,
Dry.
2. technique as claimed in claim 1, it is characterised in that reactions steps（1）In, quinoline：Sodium chlorate：Mole of copper sulphate
Than for 1：3.5:1.05~1.10.
3. technique as claimed in claim 1, it is characterised in that reactions steps（1）In, described recovered liquid refers to sodium chlorate oxygen
The waste water that change method synthesis of quinoline acid is produced.
4. technique as claimed in claim 1, it is characterised in that reactions steps（1）In, in recovered liquid, by quality ratio, water：
Organic matter is 1000：4~8.
5. technique as claimed in claim 1, it is characterised in that reactions steps（1）In, aluminum trihalide quality accounts for quinoline quality
0.1~0.2%。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105271A (en) * | 2019-05-30 | 2019-08-09 | 福建泰丰医药化工有限公司 | A kind of method that copper purifying regeneration prepares quinolinic acid mantoquita in quinolinic acid oxidized waste water |
| CN115960044A (en) * | 2022-08-19 | 2023-04-14 | 泰安汉威集团有限公司 | Treatment method of copper quinolinate mother liquor |
Citations (3)
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|---|---|---|---|---|
| CN102399182A (en) * | 2010-09-08 | 2012-04-04 | 鞍钢股份有限公司 | Production method of quinaldinic acid |
| CN104370808A (en) * | 2014-10-28 | 2015-02-25 | 常州大学 | Synthesis method of 2,3-dipicolinic acid |
| CN106187877A (en) * | 2016-07-19 | 2016-12-07 | 湖北金玉兰医药科技有限公司 | A kind of production method of quinolinic acid |
-
2017
- 2017-07-04 CN CN201710535407.8A patent/CN107215984A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399182A (en) * | 2010-09-08 | 2012-04-04 | 鞍钢股份有限公司 | Production method of quinaldinic acid |
| CN104370808A (en) * | 2014-10-28 | 2015-02-25 | 常州大学 | Synthesis method of 2,3-dipicolinic acid |
| CN106187877A (en) * | 2016-07-19 | 2016-12-07 | 湖北金玉兰医药科技有限公司 | A kind of production method of quinolinic acid |
Non-Patent Citations (3)
| Title |
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| 叶勇: "《制药工艺学》", 28 February 2014, 华南理工大学出版社 * |
| 段湘生 等: ""喹啉酸的合成研究"", 《精细化工中间体》 * |
| 苏讯: ""喹啉酸的催化合成研究"", 《广东化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110105271A (en) * | 2019-05-30 | 2019-08-09 | 福建泰丰医药化工有限公司 | A kind of method that copper purifying regeneration prepares quinolinic acid mantoquita in quinolinic acid oxidized waste water |
| CN115960044A (en) * | 2022-08-19 | 2023-04-14 | 泰安汉威集团有限公司 | Treatment method of copper quinolinate mother liquor |
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Application publication date: 20170929 |