CN100553767C - The catalyst of gas phase oxidation of toluene and method for making thereof and purposes - Google Patents
The catalyst of gas phase oxidation of toluene and method for making thereof and purposes Download PDFInfo
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- CN100553767C CN100553767C CNB2004100653220A CN200410065322A CN100553767C CN 100553767 C CN100553767 C CN 100553767C CN B2004100653220 A CNB2004100653220 A CN B2004100653220A CN 200410065322 A CN200410065322 A CN 200410065322A CN 100553767 C CN100553767 C CN 100553767C
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- Prior art keywords
- toluene
- catalyst
- benzaldehyde
- oxidation
- gas phase
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 230000003647 oxidation Effects 0.000 title claims abstract description 35
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 10
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 26
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 9
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
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 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.The invention discloses the method for making of catalyst.
Description
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 7500-9500mLh
-1G
-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 (4)
1. the catalyst of a gas phase oxidation of toluene, it is characterized in that: its general formula is V
aAg
bM
cO
d, M=Mn wherein, 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, 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 will be that the manganese nitrate solution that the ammonium metavanadate solution of 0.3-0.4mol/L, liquor argenti nitratis ophthalmicus that concentration is 0.3-0.4mol/L and concentration are 0.025-0.015mol/L mixes by the 100ml concentration of the described general formula of claim 1 metering, 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 described gas phase oxidation of toluene.
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 ℃, toluene vapor and air are fed reactor, 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.
4. the catalyst oxidation toluene of gas phase oxidation of toluene according to 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 320-420 ℃, toluene vapor and air are fed reactor, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100653220A CN100553767C (en) | 2004-11-26 | 2004-11-26 | The catalyst of gas phase oxidation of toluene and method for making thereof and purposes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100653220A CN100553767C (en) | 2004-11-26 | 2004-11-26 | The catalyst of gas phase oxidation of toluene and method for making thereof and purposes |
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| CNA2009101380153A Division CN101554582A (en) | 2004-11-26 | 2004-11-26 | Catalyst for vapor phase oxidation of toluene and preparation method and application thereof |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972646B (en) * | 2010-11-17 | 2012-10-31 | 西北大学 | Toluene liquid-phase selective oxidation catalyst and preparation method thereof |
| 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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Non-Patent Citations (4)
| Title |
|---|
| V2O5-AG2O催化剂上甲苯氧化剂制苯甲醛的研究. 毛丽秋等.分子催化，第17卷第2期. 2003 |
| V2O5-AG2O催化剂上甲苯氧化剂制苯甲醛的研究. 毛丽秋等.分子催化，第17卷第2期. 2003 * |
| V-SN氧化物催化甲苯气相氧化制苯甲醛. 毛丽秋等.北京理工大学学报，第23卷第1期. 2003 |
| V-SN氧化物催化甲苯气相氧化制苯甲醛. 毛丽秋等.北京理工大学学报，第23卷第1期. 2003 * |
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