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CN1296358C - Method for composing ethoxy quinoline - Google Patents

Method for composing ethoxy quinoline Download PDF

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Publication number
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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synthesis reaction
catalyst
filtered
moo
tio
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CN1519232A (en
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赵传江
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TIANSHI FODDER CO Ltd YIXING CITY
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TIANSHI FODDER CO Ltd YIXING CITY
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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

A kind of method of synthesizing ethoxyquinoline
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)

1.一种合成乙氧基喹啉的方法，以对氨基苯乙醚、丙酮为原料，其特征在于合成反应以H2SO4-MoO3-TiO2固体超强酸为催化剂。1. a method for synthesizing ethoxyquinoline, take p-aminophenethyl ether, acetone as raw material, it is characterized in that synthetic reaction is with H 2 SO 4 -MoO 3 -TiO 2 solid super acid is catalyst. 2.根据权利要求1所述的方法，其特征在于H2SO4-MoO3-TiO2固体超强酸催化剂的制备方法为：将TiCl4溶于冰水中，冷却下用稀氨水中和至PH＝9-10，所得沉淀经陈化、过滤、洗涤、干燥得Ti(OH)4；取Ti(OH)4粉末，用0.5-1M的H2SO4浸泡、过滤后，再用0.5M的钼酸铵溶液浸泡、蒸干，加入酸性无定型硅胶搅匀至可造粒，通过造粒机整形至20-30目，500℃焙烧得催化剂。2. The method according to claim 1, characterized in that the preparation method of H 2 SO 4 -MoO 3 -TiO 2 solid superacid catalyst is: dissolving TiCl 4 in ice water, neutralizing it with dilute ammonia water under cooling to pH =9-10, the resulting precipitate was aged, filtered, washed, and dried to obtain Ti(OH) 4 ; Ti(OH) 4 powder was taken, soaked in 0.5-1M H 2 SO 4 , filtered, and then washed with 0.5M Soak in the ammonium molybdate solution, evaporate to dryness, add acidic amorphous silica gel and stir until it can be granulated, shape it to 20-30 mesh by a granulator, and roast at 500°C to obtain the catalyst. 3.根据权利要求2所述的方法，其特征在于合成反应的温度为115-160℃。3. The method according to claim 2, characterized in that the temperature of the synthesis reaction is 115-160°C. 4.根据权利要求2所述的方法，其特征在于合成反应的温度为150-160℃。4. The method according to claim 2, characterized in that the temperature of the synthesis reaction is 150-160°C. 5.根据权利要求2所述的方法，其特征在于合成反应的压力控制为0.05-0.15Mpa。5. The method according to claim 2, characterized in that the pressure control of the synthesis reaction is 0.05-0.15Mpa. 6.根据权利要求2所述的方法，其特征在于合成反应的时间为24-35h。6. The method according to claim 2, characterized in that the synthesis reaction time is 24-35h. 7.根据权利要求2所述的方法，其特征在于合成反应的对氨基苯乙醚与丙酮物料的摩尔配比为1∶2-2.2。7. The method according to claim 2, characterized in that the molar ratio of p-aminophenethyl ether and acetone material in the synthesis reaction is 1: 2-2.2. 8.根据权利要求3-7任一项所述的方法，其特征在于合成反应在立式固定床反应器内进行。8. The method according to any one of claims 3-7, characterized in that the synthesis reaction is carried out in a vertical fixed-bed reactor. 9.根据权利要求8所述的方法，其特征在于合成反应完成后的产物经过滤后蒸馏。9. The method according to claim 8, characterized in that the product after the synthesis reaction is completed is filtered and distilled.
CNB031320929A 2003-07-18 2003-07-18 Method for composing ethoxy quinoline Expired - Fee Related CN1296358C (en)

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
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 A kind of production method of ethoxyquinoline
CN100398206C (en) * 2006-08-09 2008-07-02 张丽丽 Catalyst for the production of ethoxyquinoline
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 Synergistic catalysis of WO3/AC/SO3H for the preparation of ethoxyquinoline
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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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