CN100421797C - Preparation method of catalyst used for synthesizing glutaraldehyde by oxidation of cyclopentene - Google Patents
Preparation method of catalyst used for synthesizing glutaraldehyde by oxidation of cyclopentene Download PDFInfo
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- CN100421797C CN100421797C CNB2005100286048A CN200510028604A CN100421797C CN 100421797 C CN100421797 C CN 100421797C CN B2005100286048 A CNB2005100286048 A CN B2005100286048A CN 200510028604 A CN200510028604 A CN 200510028604A CN 100421797 C CN100421797 C CN 100421797C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000007254 oxidation reaction Methods 0.000 title description 11
- 230000003647 oxidation Effects 0.000 title description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000002808 molecular sieve Substances 0.000 claims abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000006184 cosolvent Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 229960000587 glutaral Drugs 0.000 claims description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 8
- 238000002803 maceration Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical group CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000012018 catalyst precursor Substances 0.000 abstract 1
- 150000003658 tungsten compounds Chemical class 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
The supported catalyst for synthesizing glutaraldehyde through oxidizing cyclopentene has mesoporous Ti-HMS molecular sieve of Si/Ti molar ratio of 10-50 as the carrier, and supported active component of tungsten oxide in the content of 5-50 wt%. The preparation process includes dissolving template agent in water solution of hydrochloric acid and adding tetraethyl silicate, isopropyl alcohol, butyl titanate and alcohol to compound mixed solution and form gel; ageing the gel for 2-12 hr, filtering, washing, drying and roasting for 2-6 hr to obtain the carrier; soaking the carrier in the soaking liquid comprising initial tungsten compound, co-solvent and water to obtain catalyst precursor; ageing at normal temperature, drying, roasting at 200-600 deg.c for2-4 and grinding to obtain 100-120 mesh catalyst. The catalyst has high reaction activity and high selectivity.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene, is carrier with the mesoporous molecular sieve particularly, is the preparation method of the loaded catalyst that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene of active component with the tungsten oxide.
Background technology
Glutaraldehyde is a kind of important chemical product, is widely used in fields such as oil exploitation, health care, protein chemistry, foods and cosmetics manufacturing.At present, the method for suitability for industrialized production glutaraldehyde mainly is two step of a methacrylaldehyde synthetic method, and the shortcoming of this method is raw materials used costing an arm and a leg, and equipment investment is big, and is seriously polluted, and the raw material boiling point is low, transportation inconvenience.Various countries competitively research and develop the new technology by oxidizing-synthesizing glutaric dialdehyde with cyclopentene in recent years, wherein are that oxidant is the most competitive with the hydrogen peroxide.Because of a large amount of cyclopentene of petrochemical industry by-product, and hydrogen peroxide is cheap and easy to get, and this greatly reduces the glutaraldehyde production cost, and the reaction condition gentleness that should react, and is pollution-free substantially, so cyclopentene oxidation preparing glutaric dialdehyde route has prospects for commercial application.
Cyclopentene oxidation preparing glutaric dialdehyde early adopts the homogeneous catalysis oxidation reaction, and its shortcoming is that catalyst separates the comparison difficulty with product.Existing research emphasis progressively turns to and adopts aqueous hydrogen peroxide and be the heterogeneous catalytic oxidation of representative with the support type tungsten-containing catalyst.As the disclosed technology of CN1425498 is to adopt homogeneous phase alcohol-hydro-thermal method, makes a kind of TiO through airtight crystallization
2Microballoon prepares tungsten-containing catalyst as carrier.The conversion ratio that adopts this catalyst rings amylene oxidation reaction is 95.2%, and the glutaraldehyde yield is 69.4%.The disclosed technology of CN1446631 is that original position is introduced the catalyst that the tungsten oxide component makes oxidation reaction in the process of synthetic SBA-15 type total silicon mesoporous molecular sieve, and adopting this catalyst glutaraldehyde yield is 78.9%.The disclosed technology of CN1380138 is that original position is introduced the catalyst that the tungsten component makes oxidation reaction in the process of synthetic MCM-41 type total silicon mesoporous molecular sieve, and the conversion ratio that adopts this catalyst rings amylene oxidation reaction is 100%, and the glutaraldehyde yield is 72%.The catalyst that these existent method make all can be obtained more satisfactory reaction effect, and the conversion ratio of cyclopentene substantially all is 100%, and the glutaraldehyde yield generally can both reach about 70%.But from the experimental data of introducing, the activity of such catalysts that these preparation methods obtained is generally not high, and this time that is reflected in oxidation reaction is all longer, is generally 12～60 hours.And the method for preparing catalyst carrier is all more loaded down with trivial details, need heating in confined conditions to carry out long-time crystallization or aging mostly, so the Preparation of Catalyst cycle is long, the manufacturing cost height.
Summary of the invention
The invention provides a kind of Preparation of catalysts method of oxidizing-synthesizing glutaric dialdehyde with cyclopentene, the technical problem that it will solve is to make the catalyst that makes have better catalytic activity, and preparation process is also more easy, to reduce the manufacturing cost of catalyst.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of Preparation of catalysts method of oxidizing-synthesizing glutaric dialdehyde with cyclopentene, this catalyst is a carrier with the Ti-HMS mesoporous molecular sieve, wherein the mol ratio of silicon and titanium is 10～50, specific area 500～800m
2/ g, average pore size is 5～10nm, the active component tungsten oxide content of catalyst cupport is 5～50wt%.
This method comprises following process successively:
1) the template agent is dissolved in aqueous hydrochloric acid solution, adds the mixed solution that is made into by tetraethyl orthosilicate, isopropyl alcohol, tetrabutyl titanate and ethanol then forming gel, more than the weight proportion of each material be:
Tetraethyl orthosilicate: isopropyl alcohol: tetrabutyl titanate: ethanol: template agent: hydrochloric acid: water=1: (0.05～0.5): (0.01～0.3): (1～8): (0.1～0.5): (0.01～0.2): (1～6);
2) above-mentioned gel is aging 2～12 hours, after filtration, after washing and the drying, in 300～800 ℃ of roasting temperatures 2～6 hours, Ti-HMS mesoporous molecular sieve carrier;
3) above-mentioned carrier is inserted flood in the maceration extract that initial compounds, cosolvent and water by tungsten is mixed with catalyst precarsor, the dipping liquid measure is 95～110% of a carrier hygroscopicity value;
4) above-mentioned catalyst precarsor is in normal temperature aging 2～16 hours down, and is in addition dry under 70～150 ℃ of temperature again;
5) catalyst precarsor of drying was in 200～600 ℃ of roasting temperatures 2～4 hours;
6) get 100～120 purpose particles after the grinding and be catalyst prod.
Said process 1 described template agent can be lauryl amine or tetradecy lamine; The weight proportion of described each material is preferably: tetraethyl orthosilicate: isopropyl alcohol: tetrabutyl titanate: ethanol: template agent: hydrochloric acid: water=1: (0.1～0.4): (0.02～0.2): (1～5): (0.2～0.4): (0.05～0.15): (2～5).
The initial compounds of said process 3 described tungsten can be ammonium tungstate or sodium tungstate; Described cosolvent can be oxalic acid or ammoniacal liquor; The weight ratio of the initial compounds of tungsten and cosolvent can be 1 in the described maceration extract: (0.5～5).
Said process 5 described sintering temperatures are preferably 300～500 ℃.
Compared with prior art, key of the present invention is that catalyst carrier and preparation thereof are improved, and its process is easier, and raw material is easy to get, and manufacturing cycle is short, unlike need to carry out long-time crystallization in the prior art under air-tight state.Reduce the manufacturing cost of catalyst, thereby helped the large-scale industrial production of catalyst.The inventor found through experiments, and the catalyst that makes with this method has also showed very desirable reactivity and the selectivity of Geng Gao in the reaction that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene.Reaction time only needs 4～8 hours, and the conversion ratio of cyclopentene reaches 100%, and the yield of glutaraldehyde reaches about 80%.
Below will the invention will be further described by specific embodiment.
In an embodiment, cyclopentene conversion ratio and glutaraldehyde yield are defined as:
The specific embodiment
[embodiment 1～10]
At room temperature the template agent lauryl amine with aequum is dissolved in aqueous hydrochloric acid solution, imposes stirring, adds the mixed solution that is made into by tetraethyl orthosilicate, isopropyl alcohol, tetrabutyl titanate and ethanol then to form gel.The weight proportion of above each material of each embodiment sees Table 1;
Aging 2～12 hours of above-mentioned gel, after filtration, washing and dry, more in addition after the roasting Ti-HMS mesoporous molecular sieve carrier.Roasting time and sintering temperature that each embodiment is concrete see Table 1;
In 70～90 ℃ oil bath, the ammonium tungstate of aequum is dissolved in deionized water, stir the oxalic acid that adds aequum down, continue to stir 20 minutes, treat to be maceration extract after the solution clarification.Above-mentioned carrier inserted obtain catalyst precarsor in the maceration extract.The dipping liquid measure is 95～110% of a carrier hygroscopicity value, and the amount of ammonium tungstate then decides according to the required load capacity of catalyst activity component tungsten oxide in the maceration extract, and the maceration extract preparation composition of each embodiment sees Table 2;
Above-mentioned catalyst precarsor is in normal temperature aging 2～16 hours down, and is in addition dry under 70～150 ℃ of temperature again;
The roasting in addition of the catalyst precarsor of drying, roasting time that each embodiment is concrete and sintering temperature see Table 2;
Get 100～120 purpose particles after the grinding and be catalyst prod.
Measure the physical index of the catalyst that each embodiment makes, data see Table 3.
Table 1.
| The weight proportion of each material in the gel | Roasting time (hr) | Sintering temperature (℃) | |
| Embodiment 1 | 1/0.35/0.15/1.4/0.24/0.05/2.3 | 3 | 500 |
| Embodiment 2 | 1/0.35/0.05/1.4/0.24/0.05/2.3 | 3 | 500 |
| Embodiment 3 | 1/0.31/0.08/1.6/0.24/0.10/4.5 | 4 | 300 |
| Embodiment 4 | 1/0.31/0.04/2.5/0.19/0.10/3.3 | 2 | 600 |
| Embodiment 5 | 1/0.26/0.05/2.5/0.24/0.15/3.3 | 2 | 600 |
| Embodiment 6 | 1/0.26/0.08/1.6/0.24/0.15/6.0 | 3 | 300 |
| Embodiment 7 | 1/0.16/0.04/4.5/0.19/0.15/6.0 | 3 | 400 |
| Embodiment 8 | 1/0.16/0.05/1.6/0.24/0.07/4.5 | 3 | 700 |
| Embodiment 9 | 1/0.16/0.04/4.5/0.35/0.07/4.5 | 4 | 500 |
| Embodiment 10 | 1/0.16/0.04/1.2/0.35/0.07/3.3 | 4 | 500 |
Annotate: the weight proportion=tetraethyl orthosilicate of each material/isopropyl alcohol/tetrabutyl titanate in the gel/ethanol/template agent/hydrochloric acid/water
Table 2.
| Ammonium tungstate/oxalic acid (weight ratio) | Ammonium tungstate content (wt%) | Roasting time (hr) | Sintering temperature (℃) | |
| Embodiment 1 | 1/0.56 | 8 | 4 | 300 |
| Embodiment 2 | 1/0.56 | 8 | 4 | 200 |
| Embodiment 3 | 1/0.56 | 8 | 4 | 300 |
| Embodiment 4 | 1/0.60 | 11 | 3 | 400 |
| Embodiment 5 | 1/0.60 | 11 | 3 | 400 |
| Embodiment 6 | 1/2.0 | 12 | 3 | 400 |
| Embodiment 7 | 1/2.0 | 8 | 2 | 500 |
| Embodiment 8 | 1/4.0 | 10 | 2 | 600 |
| Embodiment 9 | 1/3.0 | 10 | 2 | 500 |
| Embodiment 10 | 1/3.0 | 10 | 2 | 500 |
Table 3.
| Specific area (m 2/g) | Average pore size (nm) | Silicon/titanium in the carrier (mol ratio) | Tungsten oxide content (wt%) | |
| Embodiment 1 | 705.9 | 6.3 | 30 | 30 |
| Embodiment 2 | 759.3 | 5.8 | 30 | 30 |
| Embodiment 3 | 781.5 | 5.2 | 10 | 30 |
| Embodiment 4 | 762.8 | 5.4 | 40 | 30 |
| Embodiment 5 | 713.4 | 7.1 | 30 | 20 |
| Embodiment 6 | 679.5 | 7.8 | 20 | 20 |
| Embodiment 7 | 664.9 | 7.3 | 40 | 20 |
| Embodiment 8 | 668.3 | 7.3 | 30 | 40 |
| Embodiment 9 | 615.7 | 9.6 | 40 | 40 |
| Embodiment 10 | 651.4 | 9.8 | 40 | 40 |
The catalyst that the various embodiments described above obtain carries out activity rating with following condition:
Being reflected in three mouthfuls of round-bottomed flasks of cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde carried out, and adopts electromagnetic agitation.Reaction condition is: 35～40 ℃ of water-baths, adding 15ml concentration is 50% hydrogen peroxide in the 60ml tert-butyl alcohol, adds 4.0g catalyst and 10ml cyclopentene then.React while stirring, reaction finishes the back and adopts gas-chromatography internal standard method analytical reactions liquid to form, thus the conversion ratio of ring amylene and glutaraldehyde yield.
Each embodiment activity of such catalysts evaluation result sees Table 4.
Table 4.
| Reaction time (hr) | Cyclopentene conversion ratio (%) | Glutaraldehyde yield (%) | |
| Embodiment 1 | 4 | 99.2 | 72.6 |
| Embodiment 2 | 6 | 100 | 74.0 |
| Embodiment 3 | 6 | 100 | 76.1 |
| Embodiment 4 | 6 | 100 | 78.8 |
| Embodiment 5 | 8 | 100 | 83.7 |
| Embodiment 6 | 8 | 100 | 79.3 |
| Embodiment 7 | 8 | 100 | 80.7 |
| Embodiment 8 | 8 | 100 | 79.6 |
| Embodiment 9 | 6 | 100 | 82.8 |
| Embodiment 10 | 8 | 100 | 78.5 |
Claims (7)
1. the Preparation of catalysts method of an oxidizing-synthesizing glutaric dialdehyde with cyclopentene, this catalyst is a carrier with the Ti-HMS mesoporous molecular sieve, wherein the mol ratio of silicon and titanium is 10～50, specific area 500～800m
2/ g, average pore size is 5～10nm, and the active component tungsten oxide content of catalyst cupport is 5～50wt%, and this method comprises following process successively:
1) the template agent is dissolved in aqueous hydrochloric acid solution, adds the mixed solution that is made into by tetraethyl orthosilicate, isopropyl alcohol, tetrabutyl titanate and ethanol then forming gel, more than the weight proportion of each material be:
Tetraethyl orthosilicate: isopropyl alcohol: tetrabutyl titanate: ethanol: template agent: hydrochloric acid: water=1: (0.05～0.5): (0.01～0.3): (1～8): (0.1～0.5): (0.01～0.2): (1～6);
2) above-mentioned gel is aging 2～12 hours, after filtration, after washing and the drying, in 300～800 ℃ of roasting temperatures 2～6 hours, Ti-HMS mesoporous molecular sieve carrier;
3) above-mentioned carrier is inserted flood in the maceration extract that initial compounds, cosolvent and water by tungsten is mixed with catalyst precarsor, the dipping liquid measure is 95～110% of a carrier hygroscopicity value;
4) above-mentioned catalyst precarsor is in normal temperature aging 2～16 hours down, and is in addition dry under 70～150 ℃ of temperature again;
5) catalyst precarsor of drying was in 200～600 ℃ of roasting temperatures 2～4 hours;
6) get 100～120 purpose particles after the grinding and be catalyst prod.
2. Preparation of catalysts method according to claim 1 is characterized in that process 1 described template agent is lauryl amine or tetradecy lamine.
3. Preparation of catalysts method according to claim 1 and 2 is characterized in that the weight proportion of process 1 described each material is:
Tetraethyl orthosilicate: isopropyl alcohol: tetrabutyl titanate: ethanol: template agent: hydrochloric acid: water=1: (0.1～0.4): (0.02～0.2): (1～5): (0.2～0.4): (0.05～0.15): (2～5).
4. Preparation of catalysts method according to claim 1, the initial compounds that it is characterized in that process 3 described tungsten is ammonium tungstate or sodium tungstate.
5. Preparation of catalysts method according to claim 1 is characterized in that process 3 described cosolvents are oxalic acid or ammoniacal liquor.
6. according to claim 1,4 or 5 described Preparation of catalysts methods, it is characterized in that the initial compounds of tungsten in the process 3 described maceration extracts and the weight ratio of cosolvent are 1: (0.5～5).
7. Preparation of catalysts method according to claim 1 is characterized in that process 5 described sintering temperatures are 300～500 ℃.
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| CN1589968A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst |
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2005
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|---|---|---|---|---|
| EP0152112A2 (en) * | 1984-02-15 | 1985-08-21 | Phillips Petroleum Company | Olefin conversion |
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