CN100402500C - Ethoxy chinoline production method - Google Patents
Ethoxy chinoline production method Download PDFInfo
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- CN100402500C CN100402500C CNB200510023419XA CN200510023419A CN100402500C CN 100402500 C CN100402500 C CN 100402500C CN B200510023419X A CNB200510023419X A CN B200510023419XA CN 200510023419 A CN200510023419 A CN 200510023419A CN 100402500 C CN100402500 C CN 100402500C
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- phenetidine
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- ethoxyquinoline
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Abstract
The present invention discloses a method for producing ethoxy quinoline. P-phenetidine and propanone are used as raw materials, and react for dehydration and condensation with the existence of an acid catalyst and a solvent in the condition of 140 DEG C to 160 DEG C. The solvent in a water separator is changed in the later period of the reaction so that the p-phenetidine is completely converted in one time reaction. The procedure of rectification can be omitted by adopting the method. Production efficiency is increased, the content of the p-phenetidine in the product ethoxy quinoline is smaller than 1 wt%, and the quality of the product reaches the standard of food additives.
Description
Technical field
The present invention relates to a kind of production method of organic compound, particularly a kind of production method that is used for the ethoxyquinoline of fodder additives.
Background technology
As everyone knows, ethoxyquinoline is widely used in the antioxidant addn of feed in fodder industry, and its chemical name is a 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihydroquinoline.
The production method of ethoxyquinoline is a raw material with p-phenetidine and acetone, in the presence of acid catalyst and solvent, under 120 ℃-240 ℃ condition, carry out dehydration condensation, in the production method as Chinese patent 92100074 introductions, after the primary first-order equation, wherein p-phenetidine does not transform fully, after so just causing reaction, rectifying separation to go out p-phenetidine, recirculation is used, reduced production efficiency, p-phenetidine content in the product ethoxyquinoline will surpass 1wt% simultaneously, has influence on the quality of ethoxyquinoline, because p-phenetidine is a kind of primary amine, toxicity is very big, and is a kind of carcinogenic substance.
Summary of the invention
The purpose of this invention is to provide a kind of p-phenetidine that makes and transform fully in primary first-order equation, the p-phenetidine content in the product ethoxyquinoline is less than 1wt% simultaneously.
The production method of ethoxyquinoline of the present invention is as follows:
A kind of production method of ethoxyquinoline is characterized in that its production method is as follows:
In reactor, drop into p-phenetidine, the p-phenetidine that a last still reclaims, solvent and acid catalyst, start and stir and heat temperature raising to 140 ℃-160 ℃, after the water in the reactive system is most by solvent bank, at this moment constantly add acetone by the spinner-type flowmeter dominant discharge, fast back is slow before the flow of acetone, at this moment reaction is constantly carried out, from water trap, constantly tell the water that reaction generates, solvent in the water trap is released after 22-24 hour in reaction, again change new solvent, continued to drip the acetone reaction again 8-10 hour, at this moment from the reactive system gas chromatography analysis for sampling, p-phenetidine content is less than 1wt% in the reactive system, and reaction just finishes; Then reaction solution is cooled off, the solubilizing agent dilution adds alkali lye and neutralizes, and is washed to neutrality again; Carry out underpressure distillation and remove and reclaim p-phenetidine, obtain ethoxyquinoline buttery liquid at last.
The solvent that the present invention uses is toluene or dimethylbenzene, and they are also as the band aqua simultaneously.
The acid catalyst that the present invention uses is tosic acid, Phenylsulfonic acid or hydrochloric acid.
In the production method of ethoxyquinoline of the present invention, key is the solvent in reaction later stage replacing water trap, at this moment because in the reaction later stage, contain acetone in the solvent in the water trap, and contain water in the acetone, at this moment the solvent in the water trap contains water, be back in the reactor again, can not in time take away the water of reactive system, according to the chemical reaction equilibrium principle, reaction will stop, and p-phenetidine can not transform in primary first-order equation fully, in water trap, change solvent after, the solvent that is back to like this in the reactor does not just contain water, on the contrary the water that generates in the reactive system is constantly brought out, just impel reaction to carry through to the end, p-phenetidine is transformed in primary first-order equation fully.
Use the production method of ethoxyquinoline of the present invention to enhance productivity, p-phenetidine is transformed in primary first-order equation fully, save this fractionating step of rectifying, make simultaneously in the product ethoxyquinoline to oxygen base phenyl ethyl ether content below 1wt%, can reach the requirement of foodstuff additive or higher feed grade requirement.
Embodiment:
Following embodiment is to the further specifying of the inventive method, rather than limitation of the scope of the invention.
Embodiment 1
In 2 cubic metres reactor, add 1000 kilograms of p-phenetidines, 200 kilograms of the p-phenetidines that reclaims, 125 kilograms of 100 kilograms of toluene and tosic acid, start stir and heat temperature raising to 140 ℃ after, begin to drip acetone by spinner-type flowmeter, acetone drips flow and is divided into four-stage:
Fs is 70 kilograms/hour, and the time is 6 hours
Subordinate phase is 50 kilograms/hour, and the time is 6 hours
Phase III is 30 kilograms/hour, and the time is 10 hours
The quadravalence section is 12 kilograms/hour, and the time is 10 hours
The entire reaction course time is 32 hours, temperature of reaction is controlled at 140 ℃～160 ℃, the total consumption of acetone is 1140 kilograms, the water that generates in the reaction is constantly discharged from water trap, after reaction 24 hours, at this moment change the toluene in the water trap, continue to drip acetone reaction 8 hours again, after reaction reaches 32 hours, extract reaction solution and do gas chromatographic analysis, at this moment in the reaction solution content of p-phenetidine when 1wt% is following, reaction just stops, and goes to then and is chilled to 100 ℃ in the cooling reactor, adds 800 kilograms of dilutions of toluene, add the alkali lye neutralization again, carry out underpressure distillation after the washing, steam toluene and reclaim use, then steam and reclaim 200 kilograms of p-phenetidines
Feeding intake as next still recycles, and steams 1300 kilograms of ethoxyquinoline crude oil at last, and wherein p-phenetidine content is 0.4wt%, and ethoxyquinoline content is 95.8wt%.
Claims (3)
1. the production method of an ethoxyquinoline is characterized in that its production method is as follows:
In reactor, drop into p-phenetidine, the p-phenetidine that a last still reclaims, solvent and acid catalyst, start and stir and heat temperature raising to 140 ℃-160 ℃, after the water in the reactive system is most by solvent bank, at this moment constantly add acetone by the spinner-type flowmeter dominant discharge, fast back is slow before the flow of acetone, at this moment reaction is constantly carried out, from water trap, constantly tell the water that reaction generates, solvent in the water trap is released after 22-24 hour in reaction, again change new solvent, continued to drip the acetone reaction again 8-10 hour, at this moment from the reactive system gas chromatography analysis for sampling, p-phenetidine content is less than 1wt% in the reactive system, and reaction just finishes; Then reaction solution is cooled off, the solubilizing agent dilution adds alkali lye and neutralizes, and is washed to neutrality again; Carry out underpressure distillation and remove and reclaim p-phenetidine, obtain ethoxyquinoline buttery liquid at last.
2. the production method of a kind of ethoxyquinoline according to claim 1 is characterized in that solvent is toluene or dimethylbenzene.
3. the production method of a kind of ethoxyquinoline according to claim 1 is characterized in that acid catalyst is tosic acid, Phenylsulfonic acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510023419XA CN100402500C (en) | 2005-01-19 | 2005-01-19 | Ethoxy chinoline production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510023419XA CN100402500C (en) | 2005-01-19 | 2005-01-19 | Ethoxy chinoline production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1807416A CN1807416A (en) | 2006-07-26 |
| CN100402500C true CN100402500C (en) | 2008-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB200510023419XA Expired - Fee Related CN100402500C (en) | 2005-01-19 | 2005-01-19 | Ethoxy chinoline production method |
Country Status (1)
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| CN (1) | CN100402500C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398206C (en) * | 2006-08-09 | 2008-07-02 | 张丽丽 | Catalyst for producing ethyoxyl quinoline |
| CN101823998B (en) * | 2010-05-05 | 2015-03-25 | 江苏利田科技股份有限公司 | Pollution-free production process for ethoxy quinoline by coupling reactor and simulation moving bed |
| CN107417610B (en) * | 2016-05-24 | 2021-09-10 | 华东理工大学 | Advanced high-purity ethoxyquinoline separation and purification process |
| CN107098854B (en) * | 2017-04-24 | 2019-10-15 | 朱大春 | Ethoxyquinoline continuous production method |
| CN109422678A (en) * | 2017-09-05 | 2019-03-05 | 泰兴瑞泰化工有限公司 | A kind of sulfonic group gemini ionic liquid is the method for catalyst synthesizing ethoxyquinoline |
| CN110963965B (en) * | 2018-09-30 | 2022-10-18 | 中国石油化工股份有限公司 | Recycling method of waste residue in antioxidant AW production |
| CN111253306A (en) * | 2020-03-17 | 2020-06-09 | 淮安市润龙科技有限公司 | Preparation method of ethoxyquinoline crude oil |
| CN114315714B (en) * | 2020-10-10 | 2024-01-30 | 中石化南京化工研究院有限公司 | Preparation method of anti-aging agent AW |
| CN115181063A (en) * | 2022-07-14 | 2022-10-14 | 宜兴市天石饲料有限公司 | Preparation method of high-efficiency nontoxic antioxidant ethoxyquinoline |
| CN116947755B (en) * | 2023-09-18 | 2024-01-23 | 天津凯莱英医药科技发展有限公司 | Continuous preparation method and device of ethoxyquinoline |
Citations (5)
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|---|---|---|---|---|
| NL7614183A (en) * | 1975-12-22 | 1977-06-24 | Canada Packers Ltd | PROCESS FOR PREPARING A COMPOSITION FOR TREATING MEAT, PROCESS FOR TREATING MEAT WITH THIS COMPOSITION AND PROCESSED MEAT SO OBTAINED. |
| JPS52116478A (en) * | 1976-03-23 | 1977-09-29 | Mitsubishi Monsanto Chem Co | Synthesis of 2,2,4-trimethyl-1,2-dihydroquinolines |
| EP0147378A1 (en) * | 1983-12-23 | 1985-07-03 | Monsanto Company | Liquid hydroquinoline-type antioxydants |
| CN1068818A (en) * | 1992-01-14 | 1993-02-10 | 上海市长征第二化工厂 | A kind of production method of antioxidant |
| CN1519232A (en) * | 2003-07-18 | 2004-08-11 | 宜兴市天石饲料有限公司 | Method for composing ethoxy quinoline |
-
2005
- 2005-01-19 CN CNB200510023419XA patent/CN100402500C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7614183A (en) * | 1975-12-22 | 1977-06-24 | Canada Packers Ltd | PROCESS FOR PREPARING A COMPOSITION FOR TREATING MEAT, PROCESS FOR TREATING MEAT WITH THIS COMPOSITION AND PROCESSED MEAT SO OBTAINED. |
| JPS52116478A (en) * | 1976-03-23 | 1977-09-29 | Mitsubishi Monsanto Chem Co | Synthesis of 2,2,4-trimethyl-1,2-dihydroquinolines |
| EP0147378A1 (en) * | 1983-12-23 | 1985-07-03 | Monsanto Company | Liquid hydroquinoline-type antioxydants |
| CN1068818A (en) * | 1992-01-14 | 1993-02-10 | 上海市长征第二化工厂 | A kind of production method of antioxidant |
| CN1519232A (en) * | 2003-07-18 | 2004-08-11 | 宜兴市天石饲料有限公司 | Method for composing ethoxy quinoline |
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| Title |
|---|
| Recirculating technological system for production oftechnical-grade6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (Quinol ED). Vaidanich, V. G.et al:.Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol.,,Vol.32 No.9. 1989 |
| Recirculating technological system for production oftechnical-grade6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (Quinol ED). Vaidanich, V. G.et al:.Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol.,,Vol.32 No.9. 1989 * |
| 新型抗氧剂乙氧基喹啉. 刑福静.广西化工，第3期. 1988 |
| 新型抗氧剂乙氧基喹啉. 刑福静.广西化工，第3期. 1988 * |
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| CN1807416A (en) | 2006-07-26 |
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