CN1876619A - Method for preparing benzaldehyde by catalytic reduction of composite oxide - Google Patents
Method for preparing benzaldehyde by catalytic reduction of composite oxide Download PDFInfo
- Publication number
- CN1876619A CN1876619A CN 200610052280 CN200610052280A CN1876619A CN 1876619 A CN1876619 A CN 1876619A CN 200610052280 CN200610052280 CN 200610052280 CN 200610052280 A CN200610052280 A CN 200610052280A CN 1876619 A CN1876619 A CN 1876619A
- Authority
- CN
- China
- Prior art keywords
- composite oxide
- catalytic reduction
- preparing benzaldehyde
- catalysts
- reaction
- 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.)
- Pending
Links
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 20
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims description 26
- 238000010531 catalytic reduction reaction Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006722 reduction reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 38
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- UVCBVNDFDCGFKI-UHFFFAOYSA-N benzene;carbonic acid Chemical compound OC(O)=O.C1=CC=CC=C1 UVCBVNDFDCGFKI-UHFFFAOYSA-N 0.000 abstract 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- -1 phenyl aldehyde Chemical class 0.000 description 12
- 230000009466 transformation Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the method of preparing benzaldehyde with benzene carbonic acid. The invention uses benzene carbonic acid as raw material, uses hydrogen gas as reducing agent, and uses ZrO2, TiO2 and Y2O3 as main accelerating agent. In solid-bed reactor the invention carries out hydrogenation reduction reaction. The reaction temperature is 340-450Deg.C, gas hourly space velocity is 600-4800h-1, hydracid mole rate is 20:1-160:1, the selectivity ratio of benzaldehyde is 96%, and the productivity is above 90%. The invention has the advantages of simple technology low cost and green environmental protection.
Description
Technical field
The present invention relates to a kind of method of preparing benzaldehyde by catalytic reduction of composite oxide.
Background technology
The traditional processing technology of phenyl aldehyde is a toluene catalytic oxidation, contains nuisances such as chlorine in the product of this technology, can not be used for the industries higher to product requirement such as food.For the raw material hydrogenating reduction prepares phenyl aldehyde, the few yield height of by product, and nuisance such as product is not chloride can be widely used in industries such as food, medicine, essence and flavoring agent and makeup, are the friendly process routes of a remarkable benefit with the phenylformic acid.
U.S. Pat P191053 (1988), US P4987265 (1991) and European patent EP 0290096 (1991), disclosing Mn respectively is the method for oxide compound catalytic hydrogenating reduction preparing benzaldehyde.Chinese patent CN 1473810A (2004) has reported that composite oxides such as Mn, Al are used for the phenylformic acid gas phase hydrogenation and prepare method of benzaldehyde.F.Dury, S.Meixner, D.Cl ' ement, E.M.Gaigneaux.Journal of Molecular Catalysis A:Chemical 237 (2005) 9 has reported that a kind of is the method for catalyst reduction preparing benzaldehyde with the cobalt molybdate.
Summary of the invention
The invention discloses a kind of method of preparing benzaldehyde by catalytic reduction of composite oxide.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of method of preparing benzaldehyde by catalytic reduction of composite oxide:
With composite oxides is catalyzer, is reaction raw materials with the phenylformic acid, is reductive agent with hydrogen, in fixed-bed reactor, carries out the vapour phase reduction reaction, and temperature of reaction is 340 ℃～450 ℃, and gas hourly space velocity is 600h
-1～4800h
-1, the hydracid mol ratio is 20: 1～160: 1.
The Primary Catalysts of described composite oxide catalysts is ZrO
2, TiO
2And Y
2O
3One or more, promotor is one or more of oxide compound of Mo, Mn, Zn, Ce, Cu and V.
The Primary Catalysts ZrO of described composite oxide catalysts
2The quality percentage composition be 0%～100%, TiO
2The quality percentage composition be 0%～100%, Y
2O
3The quality percentage composition be 0%～100%, the quality percentage composition of the oxide compound of promotor Mo, Mn, Zn, Ce, Cu and V is 0%～35%.
Its presoma of described composite oxide catalysts is oxide compound, oxyhydroxide, nitrate and carbonate.
The preparation method of described composite oxide catalysts is coprecipitation method, pickling process, Slurry mixing or dry mix.
The carrier of the loaded catalyst of described composite oxide catalysts is Al
2O
3Or SiO
2
The beneficial effect that the present invention has is:
At first, compare with the technology of traditional toluene oxidation producing benzaldehyde, materials safety is easy to get, environmental protection, and objectionable impurities such as product is not chloride can be widely used in industries such as medicine, food and makeup; Secondly, the catalytic hydrogenation reaction catalyzer, better active, the life-span is longer, and target product selectivity is higher; The 3rd, the reaction of phenylformic acid catalytic hydrogenating reduction has materials safety and is easy to get, the reaction conditions gentleness, and equipment is simple, and production cost is low, and technology is easy, characteristics such as easy handling.
Embodiment
Embodiment 1
The 30.0g zirconium hydroxide is dissolved in the 200ml aqueous nitric acid, adds 12.0g Y
2O
3With 2.0g ZnO, stir, make whole dissolvings, add 16.0g TiO again
2, fully stir, make suspension, evaporate to dryness behind 500 ℃ of roasting 5h, obtains containing 43.6%ZrO
2, 22.6%Y
2O
3And 30.1%TiO
2And the composite oxide catalysts 45.2g of 3.7%ZnO, adopt Ф=20mm crystal reaction tube, carry out active testing.Reaction conditions is, under atmospheric pressure state, and catalyst levels 6.5g, 340 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 20: 1, gas hourly space velocity is 600h
-1, phenylformic acid transformation efficiency 44.3%, the phenyl aldehyde selectivity reaches more than 99.5%.
Embodiment 2
Preparation of Catalyst and active testing equipment is with embodiment 1, and reaction conditions is, catalyst levels 6.5g, and 360 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 40: 1, gas hourly space velocity is 1200h
-1, phenylformic acid transformation efficiency 74.8%, the phenyl aldehyde selectivity can reach 99%.
Embodiment 3
Preparation of Catalyst and active testing equipment is with embodiment 1, and reaction conditions is, catalyst levels 6.5g, and 380 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 80: 1, gas hourly space velocity is 2400h
-1, phenylformic acid transformation efficiency 85.6%, the phenyl aldehyde selectivity can reach 95%.
Embodiment 4
Preparation of Catalyst and active testing equipment is with embodiment 1, and reaction conditions is, catalyst levels 6.5g, and 400 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 120: 1, gas hourly space velocity is 3600h
-1, phenylformic acid transformation efficiency 94.0%, the phenyl aldehyde selectivity can reach more than 90%.
Embodiment 5
Preparation of Catalyst and active testing equipment is with embodiment 1, and reaction conditions is, catalyst levels 6.5g, and temperature of reaction 430C, hydrogen and benzoic mol ratio are 140: 1, gas hourly space velocity is 4200h
-1, phenylformic acid transformation efficiency 96.7%, phenyl aldehyde selectivity 79.3%.
Embodiment 6
Preparation of Catalyst and active testing equipment is with embodiment 1, and reaction conditions is, catalyst levels 6.5g, and 450 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 160: 1, gas hourly space velocity is 4800h
-1, phenylformic acid transformation efficiency 99.0%, the phenyl aldehyde selectivity is 66.4%.
Embodiment 7
The 22.6g zirconium hydroxide is dissolved in the 200ml aqueous nitric acid, adds 10.0g ZnO and 7.5g CeO, fully stir and make its dissolving, add 15.0g TiO again
2, fully stir, make suspension, evaporate to dryness behind roasting 5h under 500 ℃ of conditions, obtains containing 35.0%ZrO
2, 30.0%TiO
2And the composite oxide catalysts 50.0g of 20.0%ZnO and 15.0%CeO, carry out active testing, the catalyst activity testing apparatus is with embodiment 1.Reaction conditions is, under the atmospheric pressure state, and catalyst levels 5.0g, 390 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 60: 1, gas hourly space velocity is 1800h
-1, phenylformic acid transformation efficiency 86.2%, the phenyl aldehyde selectivity can reach 95%.
Embodiment 8
Preparation of Catalyst and active testing equipment is with embodiment 7, and reaction conditions is, under the atmospheric pressure state, and catalyst levels 5.0g, 410 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 80: 1, gas hourly space velocity is 2400h
-1, phenylformic acid transformation efficiency 96.0%, the phenyl aldehyde selectivity reaches more than 90%.
Embodiment 9
Preparation of Catalyst and active testing equipment is with embodiment 7, and reaction conditions is, under the atmospheric pressure state, and catalyst levels 5.0g, 430 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 100: 1, gas hourly space velocity is 3000h
-1, phenylformic acid transformation efficiency 98.8%, phenyl aldehyde selectivity 85.2%.
Embodiment 10
The 12.0g zirconium hydroxide is dissolved in the 80ml aqueous nitric acid, adds 42.0g carrier A l
2O
3, fully stir, make suspension, evaporate to dryness behind roasting 5h under 500 ℃ of conditions, gets Al
2O
3Load ZrO
2Catalyzer 51.3g, ZrO
2Charge capacity be 18.1%, carry out active testing, the catalyst activity testing apparatus is with embodiment 1.Reaction conditions is, under the atmospheric pressure state, and catalyst levels 5.6g, 420 ℃ of temperature of reaction, hydrogen and benzoic mol ratio are 60: 1, gas hourly space velocity is 1800h
-1, phenylformic acid transformation efficiency 82.6%, the phenyl aldehyde selectivity can reach more than 90%.
Claims (6)
1. the method for a preparing benzaldehyde by catalytic reduction of composite oxide, it is characterized in that with composite oxides being catalyzer, with the phenylformic acid is reaction raw materials, with hydrogen is reductive agent, in fixed-bed reactor, carry out the vapour phase reduction reaction, temperature of reaction is 340 ℃～450 ℃, and gas hourly space velocity is 600h
-1～4800h
-1, the hydracid mol ratio is 20: 1～160: 1.
2. the method for a kind of preparing benzaldehyde by catalytic reduction of composite oxide according to claim 1, it is characterized in that: the Primary Catalysts of described composite oxide catalysts is ZrO
2, TiO
2And Y
2O
3One or more, promotor is one or more of oxide compound of Mo, Mn, Zn, Ce, Cu and V.
3. the method for a kind of preparing benzaldehyde by catalytic reduction of composite oxide according to claim 1 and 2 is characterized in that: the Primary Catalysts ZrO of described composite oxide catalysts
2The quality percentage composition be 0%～100%, TiO
2The quality percentage composition be 0%～100%, Y
2O
3The quality percentage composition be 0%～100%, the quality percentage composition of the oxide compound of promotor Mo, Mn, Zn, Ce, Cu and V is 0%～35%.
4. the method for a kind of preparing benzaldehyde by catalytic reduction of composite oxide according to claim 1 and 2, it is characterized in that: its presoma of described composite oxide catalysts is oxide compound, oxyhydroxide, nitrate and carbonate.
5. the method for a kind of preparing benzaldehyde by catalytic reduction of composite oxide according to claim 1 and 2, it is characterized in that: the preparation method of described composite oxide catalysts is coprecipitation method, pickling process, Slurry mixing or dry mix.
6. the method for a kind of preparing benzaldehyde by catalytic reduction of composite oxide according to claim 1 and 2, it is characterized in that: the carrier of the loaded catalyst of described composite oxide catalysts is Al
2O
3Or SiO
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610052280 CN1876619A (en) | 2006-07-04 | 2006-07-04 | Method for preparing benzaldehyde by catalytic reduction of composite oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610052280 CN1876619A (en) | 2006-07-04 | 2006-07-04 | Method for preparing benzaldehyde by catalytic reduction of composite oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1876619A true CN1876619A (en) | 2006-12-13 |
Family
ID=37509208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610052280 Pending CN1876619A (en) | 2006-07-04 | 2006-07-04 | Method for preparing benzaldehyde by catalytic reduction of composite oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1876619A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927158A (en) * | 2010-07-12 | 2010-12-29 | 中国日用化学工业研究院 | Preparation method of nano ZnO/gamma-Al2O3 composite photocatalyst |
-
2006
- 2006-07-04 CN CN 200610052280 patent/CN1876619A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927158A (en) * | 2010-07-12 | 2010-12-29 | 中国日用化学工业研究院 | Preparation method of nano ZnO/gamma-Al2O3 composite photocatalyst |
| CN101927158B (en) * | 2010-07-12 | 2012-02-22 | 中国日用化学工业研究院 | Preparation method of nano ZnO/gamma-Al2O3 composite photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2342991C2 (en) | Catalytic composition for selectivity of transformation alkanes into unsaturated carbonic acids, method of obtaining composition and method of composition application | |
| US7211681B2 (en) | Ester production method by transesterification reaction using solid acid catalyst | |
| CN111108088B (en) | Catalyst for oxidative esterification of aldehydes to carboxylic esters | |
| JP2012524658A5 (en) | ||
| US20080103325A1 (en) | Mixed metal oxide catalysts for the ammoxidation of propane and isobutane | |
| CN1156425C (en) | Process for preparing cyclohexanone by dehydrogenating cyclohexanol | |
| JPWO2017099161A1 (en) | Alkyl aromatic compound dehydrogenation catalyst, production method thereof, and dehydrogenation method using the same | |
| KR20010060299A (en) | Catalyst for oxidizing methylbenzenes and method for producing aromatic aldehyde | |
| EP2401072B1 (en) | Catalyst for hydrogen chloride oxidation comprising ruthenium and silver and/or calcium | |
| CN1876619A (en) | Method for preparing benzaldehyde by catalytic reduction of composite oxide | |
| JP4182237B2 (en) | Catalyst for gas-phase catalytic oxidation reaction of isobutane and method for producing alkene and / or oxygen-containing compound using the same | |
| CN1150990C (en) | Catalyst for liquid-phase dehydogenation of cyclohexanol | |
| EP1052016B1 (en) | P- and Mo-based multimetallic catalyst, its preparation and its use for producing methacrylic acid | |
| KR101780840B1 (en) | Amide compound production catalyst, and process for production of amide compound | |
| US7531681B2 (en) | Process for the ammoxidation of propane and isobutane | |
| US20020188159A1 (en) | Oxidization catalyst for alkylbenzene and method for producing aromatic aldehyde | |
| US20080103326A1 (en) | Lithium containing mixed metal oxide catalysts for ammoxidation of propane and isobutane | |
| CN1876616A (en) | Method for preparing benzaldehyde by hydrogenated reduction of benzoic acid | |
| CN1876617A (en) | Method for preparing benzaldehyde by catalytic hydrogenated reduction of benzoic acid using CeO2 | |
| US20170246619A1 (en) | Solid state synthesis of oxidative dehydrogenation catalysts | |
| EP1201299B1 (en) | Use of catalysts for oxidative dehydrogenation of alkanes and a process for producing olefins | |
| CN1876618A (en) | Method for preparing benzaldehyde by catalytic hydrogenated reduction of benzoic acid using ZnO | |
| EP4052791A1 (en) | Method for preparing ceria-zirconia composite oxide, ceria-zirconia composite oxide, catalyst comprising same, and method for preparing butadiene | |
| JP2002212139A (en) | METHOD FOR PRODUCING alpha-KETO ACID ESTER | |
| EP0777639A1 (en) | Process for preparing aromatic aldehydes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |