CN1634657A - Catalyst for toluene gas-phase oxidation and preparation method and use thereof - Google Patents

Catalyst for toluene gas-phase oxidation and preparation method and use thereof Download PDF

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Publication number
CN1634657A
CN1634657A CN200410065322.0A CN200410065322A CN1634657A CN 1634657 A CN1634657 A CN 1634657A CN 200410065322 A CN200410065322 A CN 200410065322A CN 1634657 A CN1634657 A CN 1634657A
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toluene
concentration
catalyst
ratio
benzaldehyde
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CN100553767C (en
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沈俭一
薛明伟
戈加震
张惠良
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Nanjing University
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Nanjing University
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Abstract

This invention relates to toluene gas phase oxide catalyzer with its general formula as VaAgbMcOd, wherein M for Mn, Ni or Zr; a, b, c for relative element mass; when M is Mn, an and b proportion is 5: 1-1: 1; when M is Ni, b and c proportion is 1: 0.05-1:0.20 ; when M is Ni, b and c proportion is 1:1-1:0.5; when M is Zr, b and c proportion is 1:11-1: 1.5; d is the sum of each metal element oxide number. The catalyzer is characterized by the following: with air existing, it can make the cymene oxide of the benzene ring to generate oxide product with high selection rate.

Description

The catalyst of gas phase oxidation of toluene and method for making thereof and purposes
One, technical field
The present invention relates to catalyst and method for making and purposes with air gaseous oxidation toluene.
Two, background technology
Generating in the product of petroleum refining has a large amount of toluene, is very necessary and it is done profound processing conversion.Its basic step is the pendant methyl oxidation that makes on the phenyl ring, generate food, medicine, and the products such as benzaldehyde, benzoic acid or phenmethylol that need in a large number in producing such as daily chemical product, this has been to be a kind of very important chemical production process of raw material with toluene now, and its economic benefit and social benefit be highly significant all.And people are except that the liquid phase oxidation of adopting chlorination toluene hydrolysis and toluene in reaction, and for the requirement of production process and product quality, that is: reaction raw materials is single; Product is easy to separate with catalyst; Exempt the corrosion of chlorine to equipment; Product purity should reach no chlorine or chlorinity is lower than considerations such as ppm magnitude, and expectation can make the methyl gaseous oxidation on the phenyl ring prepare OXO products with air under catalyst action.
It is relevant that to make the methyl gaseous oxidation on the phenyl ring with air be the research of OXO products, existing report in the document, as: U.S.S.R.495,301 (1975); The catalysis journal, 4,210 (1983); J.Catal.129 in patents such as 426 (1991) and the document, has all reported employing V-Ag-O catalyst, makes its pendant methyl be converted into the work of aldehyde radical with air gaseous oxidation toluene.And patent Neth.Appl.6,514,682 (1967) and Neth.Appl.6,514,683 (1967) have also reported successively, adopt AgVO 3With Th or Pb vanadate, add SiO 2Make catalyst water flowing steam for carrier and carry out toluene oxidation; And employing AgVO 3And Ce (VO 3) 3, Dy (VO 3) 2, or La (VO 3) 3And SiO 2Make catalyst water flowing steam for carrier and carry out toluene oxidation; Ger.Offen.2730761 (1978) has reported with the catalyst water flowing steam that contains vanadic acid silver and ferric vandate and has carried out toluene oxidation; In addition, the report that is added with the 3rd component element and carrier etc. in V-Ag-O has: CN 1,068, and 755 (1993); J.Catal.131 350 (1991).
Three, summary of the invention
The object of the present invention is to provide a kind of new catalyst, make the Benzyl Side-Chain methyl oxidation in the presence of air, do not need to feed water vapour in course of reaction, the oxygenatedchemicals selectivity of generation is higher.
Technical scheme of the present invention is as follows:
A kind of catalyst of gas phase oxidation of toluene, its general formula is: V aAg bM cO d, wherein M=Mn, Ni or Zr, in the formula: a, b, c are the amount of substance of respective element, the ratio of a and b can be 5: 1-1: 1, during M=Mn, the ratio of b and c can be 1: 0.05-1: 0.20; During M=Ni, the ratio of b and c can be 1: 1-1: 0.5; During M=Zr, the ratio of b and c can be 1: 11-1: 1.5; D is the summation of each metallic element oxidation numerical value.
The method for making of the catalyst of the invention described above, it is with the ammonium metavanadate solution (concentration: 0.3-0.4mol/L by above-mentioned general formula metering, 100ml), liquor argenti nitratis ophthalmicus (concentration: 0.3-0.4mol/L) with manganese nitrate solution (concentration: 0.025-0.015mol/L), or with nickel nitrate solution (concentration: 0.5-0.6mol/L) or with zirconium nitrate solution (concentration: 0.1-0.2mol/L) mix, add oxalic acid (5-10g) or citric acid (12-20g) and mix the back evaporate to dryness, roasting 4-9hr under 350-500 ℃ of air atmosphere promptly makes the catalyst of gas phase oxidation of toluene of the present invention.
The catalyst oxidation toluene of a kind of usefulness gas phase oxidation of toluene of the present invention, produce benzaldehyde, or produce the method for benzaldehyde, benzoic acid and phenmethylol mixture, it is that catalyst with gas phase oxidation of toluene of the present invention is seated in the reactor, at 300-450 ℃, preferred temperature is between 320-420 ℃, and toluene vapor and air are fed reactor, the ratio of the amount of substance of air and toluene can be 5: 1-20: 1, and the air speed of reaction is 7500-9500mL.h -1.g -1, promptly make benzaldehyde or benzaldehyde, benzoic acid and phenmethylol mixture.
The characteristics of the catalyst of gas phase oxidation of toluene of the present invention are: preparation is easy, and cost is low, and as catalyst, it can make the methyl oxidation on the phenyl ring in the presence of air, and generate the oxidation product of high selectivity: the selectivity as benzaldehyde reaches 94.4%; Or the overall selectivity that generates benzaldehyde, benzoic acid and phenmethylol can reach 89.3%.In course of reaction, do not need to add water vapour.
Four, the specific embodiment
Below be embodiments of the invention (agents useful for same is chemically pure reagent among the embodiment).
Embodiment one
With ammonium metavanadate solution (concentration: 0.4000mol/L, after adding oxalic acid 10.0g dissolving 100ml), press the ratio V of amount of substance: Ag: Mn=1.0: add liquor argenti nitratis ophthalmicus (concentration: 0.4000mol/L) and manganese nitrate solution (concentration: 0.0150mol/L) at 1.0: 0.05, after the mixing, evaporate to dryness, at 450 ℃ of roasting 5hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 7500mLh -1G -1Toluene conversion 8.2%, the selectivity 91.5% of benzaldehyde, CO xSelectivity 8.5%.
Embodiment two
With ammonium metavanadate solution (concentration: 0.3500mol/L, after adding oxalic acid 7.5g dissolving 100ml), press the ratio V of amount of substance: Ag: Mn=2.2: add liquor argenti nitratis ophthalmicus (concentration: 0.3500mol/L) and manganese nitrate solution (concentration: 0.0200mol/L) at 1.0: 0.14, after the mixing, evaporate to dryness, at 450 ℃ of roasting 5hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 8900mLh -1G -1Toluene conversion 7.8%, the selectivity 91.8% of benzaldehyde, CO xSelectivity 8.2%.
Embodiment three
With ammonium metavanadate solution (concentration: 0.3000mol/L, after adding oxalic acid 5.0g dissolving 100ml), press the ratio V of amount of substance: Ag: Mn=5.0: add liquor argenti nitratis ophthalmicus (concentration: 0.3000mol/L) and manganese nitrate solution (concentration: 0.0250mol/L) at 1.0: 0.20, after the mixing, evaporate to dryness, at 450 ℃ of roasting 5hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 9500mLh -1G -1Toluene conversion 6.4%, the selectivity 77.2% of benzaldehyde, benzoic selectivity 16.9%, CO xSelectivity 5.9%.
Embodiment four
With ammonium metavanadate solution (concentration: 0.3500mol/L, after adding oxalic acid 9.0g dissolving 100ml), press the ratio V of amount of substance: Ag: Ni=2.2: add liquor argenti nitratis ophthalmicus (concentration: 0.3500mol/L) and nickel nitrate solution (concentration: 0.5500mol/L) at 1.0: 0.7, after the mixing, evaporate to dryness, at 450 ℃ of roasting 9hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 8900mLh -1G -1Toluene conversion 8.1%, the selectivity 94.4% of benzaldehyde, CO xSelectivity 5.6%.
Embodiment five
With ammonium metavanadate solution (concentration: 0.3000mol/L, after adding oxalic acid 5.0g dissolving 100ml), press the ratio V of amount of substance: Ag: Ni=1.0: add liquor argenti nitratis ophthalmicus (concentration: 0.4000mol/L) and nickel nitrate solution (concentration: 0.5000mol/L) at 1.0: 0.5, after the mixing, evaporate to dryness, at 450 ℃ of roasting 9hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 7500mLh -1G -1Toluene conversion 6.5%, the selectivity 95.5% of benzaldehyde, CO xSelectivity 4.5%.
Embodiment six
With ammonium metavanadate solution (concentration: 0.4000mol/L, after adding oxalic acid 10.0g dissolving 100ml), press the ratio V of amount of substance: Ag: Ni=5.0: add liquor argenti nitratis ophthalmicus (concentration: 0.3000mol/L) and nickel nitrate solution (concentration: 0.6000mol/L) at 1.0: 1.0, after the mixing, evaporate to dryness, at 450 ℃ of roasting 9hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 9500mLh -1G -1Toluene conversion 8.0%, the selectivity 94.0% of benzaldehyde, CO xSelectivity 6.0%.
Embodiment seven
With ammonium metavanadate solution (concentration: 0.3500mol/L, after adding citric acid 16.0g dissolves 100ml), press the ratio V of amount of substance: Ag: Zr=2.2: add liquor argenti nitratis ophthalmicus (concentration: 0.3500mol/L) and zirconium nitrate (concentration: 0.2000mol/L) solution at 1.0: 11.0, after the mixing, evaporate to dryness, at 450 ℃ of roasting 4hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 8900mLh -1G -1Toluene conversion 9.0%, the selectivity 67.1% of benzaldehyde, benzoic selectivity 20.3%, the selectivity 1.9% of phenmethylol, CO xSelectivity 10.7%.
Embodiment eight
With ammonium metavanadate solution (concentration: 0.3000mol/L, after adding citric acid 12.0g dissolves 100ml), press the ratio V of amount of substance: Ag: Zr=1.0: add liquor argenti nitratis ophthalmicus (concentration: 0.4000mol/L) and zirconium nitrate solution (concentration: 0.1000mol/L) at 1.0: 1.5, after the mixing, evaporate to dryness, at 450 ℃ of roasting 4hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 340 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 7500mLh -1G -1Toluene conversion 8.0%, the selectivity 80.5% of benzaldehyde, the selectivity 2.0% of phenmethylol, CO xSelectivity 17.5%.
Embodiment nine
With ammonium metavanadate solution (concentration: 0.4000mol/L, after adding citric acid 20.0g dissolves 100ml), press the ratio V of amount of substance: Ag: Zr=5.0: add liquor argenti nitratis ophthalmicus (concentration: 0.3000mol/L) and zirconium nitrate solution (concentration: 0.1500mol/L) at 1.0: 3.4, after the mixing, evaporate to dryness, at 450 ℃ of roasting 4hr, sieve is got 20-40 purpose particle and is carried out determination of activity, adopt the U-shaped pipe reactor of Φ=8mm, catalytic amount 0.500g, 360 ℃ of reaction temperatures, air: toluene=5: 1, air speed are 9500mLh -1G -1Toluene conversion 10.8%, the selectivity 72.6% of benzaldehyde, benzoic selectivity 7.6%, the selectivity 2.2% of phenmethylol, CO xSelectivity 17.6%.

Claims (3)

1. the catalyst of a gas phase oxidation of toluene, it is characterized in that: its general formula is V aAg bM cO d, wherein M=Mn, Ni or Zr, in the formula: a, b, c are the amount of substance of respective element, the ratio of a and b is 5: 1-1: 1, during M=Mn, the ratio 1 of b and c: 0.05-1: 0.20; During M=Ni, the ratio of b and c is 1: 1-1: 0.5; During M=Zr, the ratio of b and c is 1: 11-1: 1.5; D is the summation of each metallic element oxidation numerical value.
2. the method for making of the described catalyst of claim 1, it is characterized in that: it is that the 100ml concentration of will measure by the described general formula of claim 1 is the ammonium metavanadate solution of 0.3-0.4mol/L, concentration is that liquor argenti nitratis ophthalmicus and the concentration of 0.3-0.4mol/L is the manganese nitrate solution of 0.025-0.015mol/L, or with concentration be the nickel nitrate solution of 0.5-0.6mol/L, or with concentration be that the zirconium nitrate solution of 0.1-0.2mol/L mixes, add 5-10g oxalic acid or 12-20g citric acid and mix the back evaporate to dryness, roasting 4-9hr under 350-500 ℃ of air atmosphere promptly makes the catalyst of gas phase oxidation of toluene of the present invention.
3. the catalyst oxidation toluene with the described gas phase oxidation of toluene of claim 1 is produced benzaldehyde, or produce the method for benzaldehyde, benzoic acid and phenmethylol mixture, it is characterized in that: the catalyst of the described gas phase oxidation of toluene of claim 1 is seated in the reactor, at 300-450 ℃, preferred temperature is between 320-420 ℃, toluene vapor and air are fed reactor, and the ratio of the amount of substance of air and toluene is 5: 1-20: 1, and the air speed of reaction is 7500-9500mLh -1G -1, promptly make benzaldehyde or benzaldehyde, benzoic acid and phenmethylol mixture.
CNB2004100653220A 2004-11-26 2004-11-26 The catalyst of gas phase oxidation of toluene and method for making thereof and purposes Expired - Fee Related CN100553767C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101972646A (en) * 2010-11-17 2011-02-16 西北大学 Toluene liquid-phase selective oxidation catalyst and preparation method thereof
CN105664926A (en) * 2016-03-09 2016-06-15 广东工业大学 Catalyst for preparing benzaldehyde through selective oxidation of phenylcarbinol and preparing method thereof
CN106552622A (en) * 2015-09-28 2017-04-05 中国石化扬子石油化工有限公司 A kind of V-Ag-Si-O catalyst, its preparation method and its application
CN109718754A (en) * 2017-10-31 2019-05-07 中国石油化工股份有限公司 A kind of vanadium silver nickel metal oxide catalyst, preparation method and applications
CN110961104A (en) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 Vanadium-silver-tungsten metal oxide catalyst, preparation method and application thereof
CN111790454A (en) * 2020-08-05 2020-10-20 南京大学 Bionic iron-based catalyst, preparation method and application

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101972646A (en) * 2010-11-17 2011-02-16 西北大学 Toluene liquid-phase selective oxidation catalyst and preparation method thereof
CN101972646B (en) * 2010-11-17 2012-10-31 西北大学 Toluene liquid-phase selective oxidation catalyst and preparation method thereof
CN106552622A (en) * 2015-09-28 2017-04-05 中国石化扬子石油化工有限公司 A kind of V-Ag-Si-O catalyst, its preparation method and its application
CN106552622B (en) * 2015-09-28 2019-12-17 中国石化扬子石油化工有限公司 V-Ag-Si-O catalyst, preparation method and application thereof
CN105664926A (en) * 2016-03-09 2016-06-15 广东工业大学 Catalyst for preparing benzaldehyde through selective oxidation of phenylcarbinol and preparing method thereof
CN109718754A (en) * 2017-10-31 2019-05-07 中国石油化工股份有限公司 A kind of vanadium silver nickel metal oxide catalyst, preparation method and applications
CN110961104A (en) * 2018-09-28 2020-04-07 中国石油化工股份有限公司 Vanadium-silver-tungsten metal oxide catalyst, preparation method and application thereof
CN111790454A (en) * 2020-08-05 2020-10-20 南京大学 Bionic iron-based catalyst, preparation method and application

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