CN1296358C - Method for composing ethoxy quinoline - Google Patents
Method for composing ethoxy quinoline Download PDFInfo
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- CN1296358C CN1296358C CNB031320929A CN03132092A CN1296358C CN 1296358 C CN1296358 C CN 1296358C CN B031320929 A CNB031320929 A CN B031320929A CN 03132092 A CN03132092 A CN 03132092A CN 1296358 C CN1296358 C CN 1296358C
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- Prior art keywords
- reactions
- building
- catalyzer
- phenetidine
- moo
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract description 26
- AZJQQNWSSLCLJN-UHFFFAOYSA-N 2-ethoxyquinoline Chemical compound C1=CC=CC2=NC(OCC)=CC=C21 AZJQQNWSSLCLJN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 10
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000003930 superacid Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 238000003483 aging Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000007363 ring formation reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003039 volatile agent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- -1 washing etc. Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for synthesizing ethoxy quinoline. The method uses p-phenetidine and acetone as raw materials, and the synthesis reaction uses solid super acid H2SO4-MoO3-TiO2 as a catalyst. Because of the adoption of the new catalyst H2SO4-MoO3-TiO2, the present invention has the advantages of high speed of the synthesis reaction, high single-pass conversion rate, distillation without post treatment, low cost of the raw materials, and recycle of the catalyst.
Description
Technical field
The present invention relates to a kind of method of synthesizing ethoxyquinoline.
Technical background
Ethoxyquinoline is cheapness, the high-efficiency feed antioxidant of present consumption maximum, is that employing p-phenetidine, acetone are raw material, to be catalyzer to adding Phenylsulfonic acid, is solvent and band aqua synthetic with toluene, and its process flow sheet is referring to Fig. 1.The deficiency that this technology exists is that transformation efficiency is low, below 90%, need make solvent and band aqua with toluene, long reaction time (48-50 hour), because per pass conversion is low, need carry out the specification of quality that aftertreatment could be satisfied later process (distillation), not only cost height with soda ash, caustic soda, hydrochloric acid, washing etc., and waste water, exhausted air quantity are bigger, seriously polluted.
Summary of the invention
The present invention provides a kind of per pass conversion height, need not the synthesizing ethoxyquinoline method that aftertreatment directly enters distillation process just in order to overcome above-mentioned deficiency, and this technical process is simple, and cost is low, and speed of response is fast, the single rate height.The main improvement adopted H when being to synthesize
2SO
4-MoO
3-TiO
2Solid super-strong acid is made catalyzer, and specifically: a kind of method of synthesizing ethoxyquinoline is a raw material with p-phenetidine, acetone, it is characterized in that building-up reactions is with H
2SO
4-MoO
3-TiO
2Solid super-strong acid is a catalyzer.Owing to adopt this catalyzer, will foreshorten in the reaction times in 30 hours, speed is obviously accelerated, per pass conversion reaches more than 98%, has got rid of last handling processes such as toluene and acid, alkali, washing, does not have " three wastes " substantially and produces, and catalyzer can be recycled, and cost reduces about 1500 yuan/ton.
The H that the present invention is used
2SO
4-MoO
3-TiO
2Solid super acid catalyst, its preparation method is: with TiCl
4Be dissolved in the frozen water, cooling is neutralized to PH=9-10 with weak ammonia down, and the gained precipitation is through ageing, filtration, washing, the dry Ti (OH) 4 that gets; Get Ti (OH) 4 powder, with the H of 0.5-1M
2SO
4After soaking, filtering, with ammonium molybdate solution immersion, the evaporate to dryness of 0.5M, stir evenly to granulation but add acid unformed silica gel, to the 20-30 order, 500 ℃ of roastings get catalyzer by the tablets press shaping again.This catalyzer is reusable, during active the reduction, can carry out roasting regeneration.
Building-up reactions of the present invention is at H
2SO
4-MoO
3-TiO
2Under the katalysis of solid super-strong acid, synthesis reaction temperature generally is controlled at 115-160 ℃, best synthesis reaction temperature is 150-160 ℃, pressure-controlling is at 0.05-0.15MPa, time is 24-35h, the mole proportioning of p-phenetidine and acetone material is 1: 2-2.2 can obtain the ideal transformation efficiency.
The present invention adopts new catalyzer H just
2SO
4-MoO
3-TiO
2, make building-up reactions have following advantage:
1. speed of response is fast, and the reaction times shortens nearly 20 hours than background technology technology;
2. per pass conversion height is than the high 8-10% of background technology technology;
3. last handling processes such as solvent and band aqua toluene, soda ash, hydrochloric acid, caustic soda, washing have been got rid of;
4. raw materials cost low (reducing about 1500 yuan/ton than existing technology) is pollution-free substantially;
5. catalyzer can recycle.
Description of drawings
Fig. 1 is the process flow sheet of background technology.
Fig. 2 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
The manufacturing of catalyzer: with TiCl
4Be dissolved in the frozen water, cooling down is neutralized to PH=9-10 with weak ammonia, and gained was precipitated ageing 10 hours, filter, with filter cake washing, 110 ℃ of dryings 24 hours, Ti (OH) 4; Get Ti (OH) 4 powder, with the H of 0.5-1M
2SO
4Soaked 20 minutes, and filtered, the ammonium molybdate solution with 0.5M soaked 60 minutes again, and 110-120 ℃ of evaporate to dryness stirs evenly to granulation but add acid unformed silica gel, and to the 20-30 order, 500 ℃ of roastings got catalyzer in 3 hours by the tablets press shaping.
Referring to process flow sheet shown in Figure 2, the acetone material that 1 mole p-phenetidine is equipped with 2.07 moles places in the vertical fixed-bed reactor, is filled with the H of 70% reactor volume in it
2SO
4-MoO
3-TiO
2Solid super acid catalyst, temperature about 150 ℃, 0.1Mpa about pressure under, about 30 hours of cyclization, product behind the cyclization distills after filtering and can obtain finished product, wherein 10% front-end volatiles redistillation gets finished product, and redistilled 5% front-end volatiles circulation enters fixed-bed reactor and carries out cyclization.
Embodiment 2
The manufacture method of catalyzer is with embodiment 1.
The acetone material that 1 mole p-phenetidine is equipped with 2.1 moles places in the vertical fixed-bed reactor, is filled with 78% volumetrical H in the reactor
2SO
4-MoO
3-TiO
2Solid super acid catalyst, temperature about 160 ℃, 0.08Mpa about pressure under, about 35 hours of cyclization, product behind the cyclization distills after filtering and can obtain finished product, wherein 10% front-end volatiles redistillation gets finished product, and redistilled 5% front-end volatiles circulation enters fixed-bed reactor and carries out cyclization.
Embodiment 3
The manufacture method of catalyzer is with embodiment 1.
The acetone material that 1 mole p-phenetidine is equipped with 2.2 moles places in the vertical fixed-bed reactor, is filled with 65% volumetrical H in the reactor
2SO
4-MoO
3-TiO
2Solid super acid catalyst, temperature about 120 ℃, 0.15Mpa about pressure under, about 25 hours of cyclization, product behind the cyclization distills after filtering and can obtain finished product, wherein 10% front-end volatiles redistillation gets finished product, and redistilled 5% front-end volatiles circulation enters fixed-bed reactor and carries out cyclization.
Claims (9)
1. the method for a synthesizing ethoxyquinoline is a raw material with p-phenetidine, acetone, it is characterized in that building-up reactions is with H
2SO
4-MoO
3-TiO
2Solid super-strong acid is a catalyzer.
2. method according to claim 1 is characterized in that H
2SO
4-MoO
3-TiO
2The preparation method of solid super acid catalyst is: with TiCl
4Be dissolved in the frozen water, cooling is neutralized to PH=9-10 with weak ammonia down, and the gained precipitation is through ageing, filtration, washing, the dry Ti (OH) that gets
4Get Ti (OH)
4Powder is with the H of 0.5-1M
2SO
4After soaking, filtering, with ammonium molybdate solution immersion, the evaporate to dryness of 0.5M, stir evenly to granulation but add acid unformed silica gel, to the 20-30 order, 500 ℃ of roastings get catalyzer by the tablets press shaping again.
3. method according to claim 2, the temperature that it is characterized in that building-up reactions is 115-160 ℃.
4. method according to claim 2, the temperature that it is characterized in that building-up reactions is 150-160 ℃.
5. method according to claim 2, the pressure-controlling that it is characterized in that building-up reactions is 0.05-0.15Mpa.
6. method according to claim 2, the time that it is characterized in that building-up reactions is 24-35h.
7. method according to claim 2 is characterized in that the p-phenetidine of building-up reactions and the mole proportioning of acetone material are 1: 2-2.2.
8. according to each described method of claim 3-7, it is characterized in that building-up reactions carries out in vertical fixed-bed reactor.
9. method according to claim 8 is characterized in that the product after building-up reactions is finished distills after filtering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031320929A CN1296358C (en) | 2003-07-18 | 2003-07-18 | Method for composing ethoxy quinoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031320929A CN1296358C (en) | 2003-07-18 | 2003-07-18 | Method for composing ethoxy quinoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1519232A CN1519232A (en) | 2004-08-11 |
| CN1296358C true CN1296358C (en) | 2007-01-24 |
Family
ID=34286030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031320929A Expired - Fee Related CN1296358C (en) | 2003-07-18 | 2003-07-18 | Method for composing ethoxy quinoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1296358C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402500C (en) * | 2005-01-19 | 2008-07-16 | 上海福达精细化工有限公司 | Ethoxy chinoline production method |
| 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 |
| CN106749003B (en) * | 2016-12-08 | 2019-07-02 | 宜兴市天石饲料有限公司 | A kind of preparation method of ethoxyquinoline |
| CN108003096B (en) * | 2017-12-14 | 2021-07-20 | 淮阴师范学院 | Method for preparing ethoxyquinoline through WO3/AC/SO3H concerted catalysis |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2802630A1 (en) * | 1977-01-27 | 1978-08-03 | Abic Ltd | 6-ETHOXY-1,2-DIHYDRO-2,2,4-TRIMETHYLCHINOLINE DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF |
| PL207186A1 (en) * | 1978-05-29 | 1980-01-28 | Inst Przemyslu Organiczego | |
| PL237662A2 (en) * | 1982-07-27 | 1983-05-23 | Inst Przemyslu Organiczego | Process for preparing 1,2-dihydro-2,2,4-trimethylquinoline |
-
2003
- 2003-07-18 CN CNB031320929A patent/CN1296358C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2802630A1 (en) * | 1977-01-27 | 1978-08-03 | Abic Ltd | 6-ETHOXY-1,2-DIHYDRO-2,2,4-TRIMETHYLCHINOLINE DERIVATIVES AND METHOD FOR THE PRODUCTION THEREOF |
| PL207186A1 (en) * | 1978-05-29 | 1980-01-28 | Inst Przemyslu Organiczego | |
| PL237662A2 (en) * | 1982-07-27 | 1983-05-23 | Inst Przemyslu Organiczego | Process for preparing 1,2-dihydro-2,2,4-trimethylquinoline |
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| Publication number | Publication date |
|---|---|
| CN1519232A (en) | 2004-08-11 |
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Denomination of invention: Method for composing ethoxy quinoline Effective date of registration: 20120112 Granted publication date: 20070124 Pledgee: Bank of Jiangsu Limited by Share Ltd. Yixing branch Pledgor: SKYSTONE FEED (YIXING) CO.,LTD. Registration number: 2012990000021 |
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Denomination of invention: Method for composing ethoxy quinoline Effective date of registration: 20130419 Granted publication date: 20070124 Pledgee: Bank of Jiangsu Limited by Share Ltd. Yixing branch Pledgor: SKYSTONE FEED (YIXING) CO.,LTD. Registration number: 2013990000217 |
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