CN101396667B - V2O5 composite catalyst loaded by Ce-V-Ti-O meso-material - Google Patents
V2O5 composite catalyst loaded by Ce-V-Ti-O meso-material Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 229910003077 Ti−O Inorganic materials 0.000 title claims abstract description 33
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000013335 mesoporous material Substances 0.000 claims abstract description 33
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 24
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- -1 sulfate radical Chemical class 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000003786 synthesis reaction Methods 0.000 abstract 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- MXOSECBTSFQUJS-UHFFFAOYSA-N [O-2].[Ti+4].[V+5] Chemical compound [O-2].[Ti+4].[V+5] MXOSECBTSFQUJS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a V2O5 composite catalyst which is loaded by Ce-V-Ti-O meso-porous material. The catalyst comprises vanadium oxide and titanium sulfate which are loaded and measured by the Ce-V-Ti-O meso-porous material. The content of vanadium is counted as 10-30 percent in the weight of vanadium pentoxide, the priority range is 10-20 percent, and the loaded amount of the titanium sulfate is counted as 0.6-6 percent in the weight of sulfate. The catalyst can be used for the synthesis of methylal from the selective oxidation of methanol. The Ce-V-Ti-O meso-porous material, butyl titanate, V2O5, CeCl3 and template agent P123(PEO)20(PPO)70(PEO)20 (MW equal to 5800) are synthesized under hydrothermal condition. The prepared catalyst is applied to the synthesis of methylal from methanol in a one-step method. The conversion rate of methanol can reach 20-78 percent and the selectivity of the methylal can reach 85.0-97.9 percent.
Description
One, technical field
The present invention relates to the V of a kind of Ce-V-Ti-O mesoporous material load
2O
5Composite catalyst and preparation method thereof, this catalyst can be used for methanol oxidation and produce dimethoxym ethane.
Two, background technology
Since people such as the Beck of Mobile company found mesoporous MCM silicon series molecular sieve, mesoporous material was because can be in catalysis, adsorbing separation, and there is potential application in fields such as advanced material, and are subjected to paying close attention to widely.The TiO that wherein has semiconductor property
2Mesoporous material synthetic is one of focus of research field, mainly is because TiO
2Can be used as the carrier of catalyst, photochemical catalyst, sensor, energy accumulator.Yet the mesoporous TiO that is synthesized
2Heat endurance is not high mostly, and when being higher than 400 ℃, its meso-hole structure is subjected to heavy damage, has limited its application as catalyst carrier.At present, mesoporous TiO
2Several reports that heat endurance is higher adopt nonionic three block surfactants to synthesize the high mesoporous TiO of heat endurance as Yang Peidong
2(Nature,, 396 volumes, 152-155 page or leaf in 1998), the red mesoporous TiO that has reported the micro-Ce that mixes of happy English
2Can improve heat endurance (ChemicalCommunications,, 1755-1756 page or leaf in 2000).The synthetic higher high specific surface area and mesoporous Ce-V-Ti oxide of heat endurance does not appear in the newspapers as yet.
The load-type vanadium oxide is as TiO
2The V of load
2O
5, be a class important catalyst, can be widely used in reactions such as industrial hydro carbons selective oxidation, NOx selective reduction, ammoxidation and alkanes oxidative dehydrogenation.It is generally acknowledged, improve carrier (as TiO
2) surface area, increase the reducible vanadium species quantity under the individual layer dispersion capacity, can improve the reactivity worth of catalytic component based on vanadium.
Dimethoxym ethane chemically has another name called dimethoxymethane (CH
3OCH
2OCH
3), because of its toxicity very I be used to produce the solvent of spices and synthetic drug, hypotoxicity hydrogen content height can be used for replacing the high methyl alcohol of toxicity to carry out vapor reforming hydrogen production (Journal of Catalysis, 2007 the 1st volumes, 101-110 page or leaf; 2006 the 1st volumes, the 1-9 page or leaf), also can be used as the intermediate of producing polyformaldehyde, and polyformaldehyde is a kind of important engineering plastics, aspect auto industry, be widely used, in addition because dimethoxym ethane in the potential application in diesel fuel additives field, makes dimethoxym ethane more and more be subjected to people's attention.
Dimethoxym ethane mainly is that dehydrating condensation on acidic catalyst forms by methyl alcohol and formaldehyde at present, and acidic catalyst commonly used has inorganic acid, acidic molecular sieve, macroporous cation acidic resins etc.Because formaldehyde can be made by methyl alcohol selective oxidation on money base or iron molybdenum catalyst series, therefore the direct catalytic oxidation of methyl alcohol is produced the concern that dimethoxym ethane has been subjected to academia and industrial quarters under suitable acid condition.The vanadium titanium oxide catalyst of a kind of sulfate radical modification that discloses as Chinese patent 200410065321.6, can be under temperate condition (150 ℃) obtain 48% methanol conversion and near 90% dimethoxym ethane selectivity, the catalyst system therefor surface area is about 90m
2/ g.Improve the surface area of carrier, increase available vanadium oxygen species quantity, can further strengthen the catalytic performance of catalyst.
Three, summary of the invention
Meso-pore Ce-V-Ti-O has the pore passage structure of higher surface area and homogeneous.As carrier, can be under the individual layer dispersion capacity further supported V
2O
5, the catalytic performance of raising catalyst.
The V that the purpose of this invention is to provide the load of a kind of Ce-V-Ti-O mesoporous material
2O
5Composite catalyst and preparation method thereof, this catalyst can be used for producing methylal by selective oxidation of methanol.
Technical scheme of the present invention is as follows:
The V of a kind of Ce-V-Ti-O mesoporous material load
2O
5Composite catalyst, it is to be made of barium oxide and titanium sulfate that the load of Ce-V-Ti-O mesoporous material is measured.Wherein the content of vanadium is counted 10-30% with the vanadic anhydride quality, and preferable range is 10-20%, and the load capacity of titanium sulfate is counted 0.6-6% with the sulfate radical quality.This catalyst can be used for the selective oxidation of methanol synthesizing dimethoxym ethane.
The V of above-mentioned Ce-V-Ti-O mesoporous material load
2O
5The preparation method of composite catalyst.It is characterized by: ammonium metavanadate is mixed with 1: 2 ratio of mass ratio with oxalic acid, be dissolved in water and obtain cyan solution, the Ce-V-Ti-O mesoporous material that in this solution, adds metering, the mass ratio that makes Ce-V-Ti-O mesoporous material and ammonium metavanadate is 1: 0-1: 0.55, mixture stirred 10 minutes, room temperature was dried 20-40 hour, got solid A.The titanium sulfate of metering is dissolved in the water, above-mentioned solid A be impregnated in this titanium sulfate solution, stirred 5-10 minute, drying at room temperature 20-40 hour, in 350-450 ℃ of air roasting 3-8 hour, promptly get the V of Ce-V-Ti-O mesoporous material load
2O
5Catalyst.
Above-mentioned Ce-V-Ti-O mesoporous material is by butyl titanate, V
2O
5, CeCl
3With molecular formula be (PEO)
20(PPO)
70(PEO)
20, the template agent P 123 of MW=5800, preparation as follows:
(1) with P123 and absolute ethyl alcohol by 1g: 30-50ml mixes, and stirs to dissolve fully to P123 in 20 minutes, adds the CeCl of metering
3, slowly drip butyl titanate, stirred 1-5 hour, get settled solution A, wherein Ce: the Ti mol ratio is 0.03-0.08: 1, the mol ratio of P123 and butyl titanate is 0.02-0.05: 1;
(2) under ice-water bath, be that 30% hydrogen peroxide is 1 with absolute ethyl alcohol by volume with concentration: 4-6 mixes, and under agitation, adds 1gV by every 10ml hydrogen peroxide
2O
5Ratio adds the V of metering
2O
5, continue to be stirred to dissolving fully, get solution B;
(3) solution B is joined in the solution A, stir fast, become gel after about 5 minutes, the water that then adds metering, transfer in the water heating kettle, 110-150 ℃ of following hydro-thermal synthesized 12-48 hour, and water heating kettle filling degree is 70-90%, wherein the mol ratio of water of Jia Ruing and titanium vanadium total amount is 80-105: 1, and V content is with V
2O
5Quality is counted 0-20%, and V content is not " 0 ", with the synthetic resulting precipitation of hydro-thermal after filtration, water washing 3 times, absolute ethanol washing 1 time, drying at room temperature 24-48 hour, 350-450 ℃ roasting 3-8 hour, promptly get the Ce-V-Ti-O mesoporous material.
The V of Ce-V-Ti-O mesoporous material of the present invention load
2O
5The method that composite catalyst is used for the selective oxidation of methanol synthesizing dimethoxym ethane is: catalyst of the present invention is seated in reactor, the control temperature of reactor is at 120-160 ℃, feeding is preheated to 120-160 ℃ the methanol vapor and the gaseous mixture of oxygen-containing gas, the mol ratio of methyl alcohol and oxygen is 5: 1 to 5: 15, the percentage by volume that methyl alcohol accounts for mist is 5%, and the overall flow rate that feeds gas is every gram catalyst 1.1 * 10
3Milliliter/hour, dimethoxym ethane promptly got.Wherein oxygen-containing gas can be pure O
2, air or contain molecule O
2Nitrogen or helium.
The V of Ce-V-Ti-O mesoporous material of the present invention load
2O
5Composite catalyst has high surface and meso-hole structure, uses this catalyst can be with producing methylal by selective oxidation of methanol, and conversion of methanol can reach 20-78% under 120-160 ℃ of temperature, and the dimethoxym ethane selectivity can reach 55.0-97.9%.
Four, the specific embodiment
The invention will be further described with following embodiment:
Embodiment 1:
6.0g P123 is dissolved in the 35ml ethanol solution, adds 0.9g CeCl again
3, stirring at room dropwise adds the 17.0g butyl titanate to dissolving fully, stirs 1 hour, gets solution A.4ml 30% hydrogen peroxide is dissolved in the 20ml ethanol, adds 0.4g V again
2O
5, get solution B fully after the dissolving.Solution B is added solution A, stir and form gel down.This gel is transferred in the autoclave, added 75ml water, hydro-thermal reaction is 24 hours in 120 ℃ of baking ovens.Be chilled to room temperature, filter, filter cake spends deionised water 3 times, and absolute ethyl alcohol is washed 1 time, and drying at room temperature 24 hours 400 ℃ of roastings 8 hours, obtains faint yellow Ce-V-Ti-O mesoporous material.Measuring its surface area is 162m
2/ g, aperture 5.0nm, pore volume 0.27ml/g, content of vanadium are 9.6% (in the vanadic anhydride mass percent).
Embodiment 2:
6.0g P123 is dissolved in the 35ml ethanol solution, adds 0.9g CeCl again
3, stirring at room dropwise adds the 17.0g butyl titanate to dissolving fully, stirs 1 hour, gets solution A.7ml 30% hydrogen peroxide is dissolved in the 20ml ethanol, adds 0.7g V again
2O
5, get solution B fully after the dissolving.Solution B is added solution A, stir and form gel down.This gel is transferred in the autoclave, added 72ml water, hydro-thermal reaction is 24 hours in 120 ℃ of baking ovens.Resulting precipitation spends deionised water 3 times after filtration, and absolute ethyl alcohol is washed 1 time, and drying at room temperature 24 hours at last 400 ℃ of roastings 6 hours, obtains faint yellow Ce-V-Ti-O mesoporous material.Measuring its surface area is 159m
2/ g, aperture 3.6nm, pore volume 0.2ml/g, content of vanadium are 19.8% (in the vanadic anhydride mass percent).
Embodiment 3:
In the 150ml crucible, add the 1.2g titanium sulfate, add 15ml distilled water and make its dissolving, the Ce-V-Ti-O mesoporous material that adds 14.2g embodiment 1 preparation again, stir into pasty state, drying at room temperature 400 ℃ of roastings 3.5 hours, obtains composite catalyst, record wherein that content of vanadium is 9.6% (in the vanadic anhydride mass percent), sulphur is 3.9% (in the sulfate radical mass percent).With the catalyst compressing tablet of preparation, smash, sieving is used for determination of activity for the 20-40 order.Adopting Φ 8mm U-shaped pipe reactor, is methyl alcohol 5% with volumn concentration, O
215%, N
280% mist is preheating to 120 ℃ and is passed in the reactor, and when reaction temperature was 150 ℃, analyzing methanol conversion was 25%, the dimethoxym ethane selectivity is 91.6%, the formaldehyde selectivity is 1.1%, and the selectivity 3.9% of dimethyl ether, the selectivity of methyl formate are 3.4%.
Methanol conversion and selectivity of product are calculated as follows:
Embodiment 4:
In the 150ml crucible, add the 1.7g titanium sulfate, adding 21ml distilled water fully dissolves it, the Ce-V-Ti-O mesoporous material that adds 17.2g embodiment 2 preparations again, stir into pasty state, drying at room temperature 30 hours 400 ℃ of roastings 4 hours, obtains composite catalyst, record wherein that content of vanadium is 19.6% (in the vanadic anhydride mass percent), sulphur is 2.3% (in the sulfate radical mass percent).With the composite catalyst compressing tablet of preparation, smash, sieving is used for determination of activity for the 20-40 order.Adopting Φ 8mm U-shaped pipe reactor, is methyl alcohol 5% with volumn concentration, O
215%, N
280% mist is preheating to 120 ℃ and is passed in the reactor, and when reaction temperature was 150 ℃, analyzing methanol conversion was 41%, the dimethoxym ethane selectivity is 92.0%, the formaldehyde selectivity is 1.0%, and the selectivity of dimethyl ether is 1.0%, and the selectivity of methyl formate is 6.0%.
Embodiment 5:
With the 2.3g ammonium metavanadate with add water 13ml after 4.8g oxalic acid mixes, stirring and dissolving obtains blackish green solution, and the Ce-V-Ti-O mesoporous material of 14.2g embodiment 1 preparation is joined in the solution, stirring at room becomes pasty state, drying at room temperature 40 hours obtains solid sample.The 1.4g titanium sulfate is dissolved in the 10ml water, adds above-mentioned solid sample, stirring at room becomes pasty state, drying at room temperature 30 hours, and roasting is 6 hours in 400 ℃ air, obtains the V of Ce-V-Ti-O mesoporous material load
2O
5Composite catalyst.Record wherein that content of vanadium is 19.2% (in the vanadic anhydride mass percent), sulphur is 5.0% (in the sulfate radical mass percent).With the composite catalyst compressing tablet of preparation, smash, sieve, get 20-40 order granularity and be used for active the detection.With Φ 8mm U-shaped pipe reactor, be methyl alcohol 5% with volumn concentration, O
215%, N
280% mist is preheating to 120 ℃ and is passed in the reactor, and when reaction temperature was 145 ℃, recording methanol conversion was 57%, the dimethoxym ethane selectivity is 92.0%, the formaldehyde selectivity is 0, and the selectivity of dimethyl ether is 0.3%, and the selectivity of methyl formate is 7.7%; When reaction temperature was 150 ℃, recording methanol conversion was 72%, and the dimethoxym ethane selectivity is 85.0%, and the formaldehyde selectivity is 0.4%, and the selectivity of dimethyl ether is 0.8%, and the selectivity of methyl formate is 13.8%.
Claims (3)
1. the V of Ce-V-Ti-O mesoporous material load
2O
5Composite catalyst, it is to be made of barium oxide and titanium sulfate that the load of Ce-V-Ti-O mesoporous material is measured, wherein the content of vanadium is counted 10-30% with the vanadic anhydride quality, the load capacity of titanium sulfate is counted 0.6-6% with the sulfate radical quality, and this catalyst can be used for the selective oxidation of methanol synthesizing dimethoxym ethane;
Described Ce-V-Ti-O mesoporous material is by butyl titanate, V
2O
5, CeCl
3With molecular formula be (PEO)
20(PPO)
70(PEO)
20, the template agent P123 of MW=5800, preparation as follows:
(1) with P123 and absolute ethyl alcohol by 1g: 30-50ml mixes, and stirs to dissolve fully to P123 in 20 minutes, adds the CeCl of metering
3, slowly drip butyl titanate, stirred 1-5 hour, get settled solution A, wherein Ce: the Ti mol ratio is 0.03-0.08: 1, the mol ratio of P123 and butyl titanate is 0.02-0.05: 1;
(2) under ice-water bath, be that 30% hydrogen peroxide is 1 with absolute ethyl alcohol by volume with concentration: 4-6 mixes, and under agitation, adds 1gV by every 10ml hydrogen peroxide
2O
5Ratio adds the V of metering
2O
5, continue to be stirred to dissolving fully, get solution B;
(3) solution B is joined in the solution A, stir fast, become gel after about 5 minutes, the water that then adds metering, transfer in the water heating kettle, 110-150 ℃ of following hydro-thermal synthesized 12-48 hour, and water heating kettle filling degree is 70-90%, wherein water of Jia Ruing and total titanium vanadium mol ratio are 80-105: 1, and V content is with V
2O
5Quality is counted 0-20%, and V content is not " 0 ", and resulting precipitation washes with water 3 times after filtration, absolute ethanol washing 1 time, drying at room temperature 24-48 hour, 350-450 ℃ roasting 3-8 hour, promptly get the Ce-V-Ti-O mesoporous material.
2. the V of the described Ce-V-Ti-O mesoporous material of claim 1 load
2O
5The preparation method of composite catalyst, it is characterized by: ammonium metavanadate is mixed with 1: 2 ratio of mass ratio with oxalic acid, be dissolved in water and obtain cyan solution, the Ce-V-Ti-O mesoporous material that in this solution, adds metering, the mass ratio that makes Ce-V-Ti-O mesoporous material and ammonium metavanadate is 1: 0-1: 0.55, mixture stirred 10 minutes, room temperature was dried 20-40 hour, get solid A, the titanium sulfate that measures is dissolved in the water, above-mentioned solid A be impregnated in this titanium sulfate solution, stirred 5-10 minute, drying at room temperature 20-40 hour, in 350-450 ℃ of air roasting 3-8 hour, promptly get the V of Ce-V-Ti-O mesoporous material load
2O
5Catalyst.
3. V with the load of the described Ce-V-Ti-O mesoporous material of claim 1
2O
5Composite catalyst is produced the method for dimethoxym ethane, it is characterized in that: catalyst is seated in the reactor, the control temperature of reactor is at 120-160 ℃, feeding is preheated to 120-160 ℃ the methanol vapor and the gaseous mixture of oxygen-containing gas, the mol ratio of methyl alcohol and oxygen is 5: 1 to 5: 15, the percentage by volume that methyl alcohol accounts for mist is 5%, and the overall flow rate that feeds gas is every gram catalyst 1.1 * 10
3Milliliter/hour, promptly get dimethoxym ethane, wherein oxygen-containing gas is pure O
2, air or contain molecule O
2Nitrogen or helium.
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| CN107008249B (en) * | 2016-01-28 | 2019-12-24 | 中国科学院上海高等研究院 | Catalyst for preparing methylal by one-step oxidation of methanol and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247190A (en) * | 1998-09-01 | 2000-03-15 | 底古萨－胡尔斯股份公司 | Method for preparing nicotinic acid |
| CN1634655A (en) * | 2004-11-26 | 2005-07-06 | 南京大学 | Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247190A (en) * | 1998-09-01 | 2000-03-15 | 底古萨－胡尔斯股份公司 | Method for preparing nicotinic acid |
| CN1634655A (en) * | 2004-11-26 | 2005-07-06 | 南京大学 | Catalyst for producing methylal by selective oxidation of methanol and preparation method and use thereof |
Non-Patent Citations (4)
| Title |
|---|
| JP特开2001-353443A 2001.12.25 |
| Yinghong Yue et al..Synthesis of mesoporous TiO2 with a crystalline framework.Chem. Commun..2000,1755-1756. * |
| 金明善等.改性杂多酸催化剂的制备及其在甲缩醛合成中的催化活性.复旦学报（自然科学版）42 3.2003,42(3),280-284. |
| 金明善等.改性杂多酸催化剂的制备及其在甲缩醛合成中的催化活性.复旦学报(自然科学版)42 3.2003,42(3),280-284. * |
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Assignee: Anhui Lixing Chemical Co.,Ltd. Assignor: Nanjing University Contract record no.: 2011340000121 Denomination of invention: V[sub]2[/sub]O[sub]5[/sub] composite catalyst supported by Ce-V-Ti-O mesoporous material Granted publication date: 20101222 License type: Exclusive License Open date: 20090401 Record date: 20110714 |
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