CN100421796C - Load type catalyst used for synthesizing glutaraldehyde by oxidation of cyclopentene - Google Patents
Load type catalyst used for synthesizing glutaraldehyde by oxidation of cyclopentene Download PDFInfo
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- CN100421796C CN100421796C CNB200510028600XA CN200510028600A CN100421796C CN 100421796 C CN100421796 C CN 100421796C CN B200510028600X A CNB200510028600X A CN B200510028600XA CN 200510028600 A CN200510028600 A CN 200510028600A CN 100421796 C CN100421796 C CN 100421796C
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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, specific surface area of 500-800 sq m/g and average pore size of 5-10 nm as the carrier, and supported active component of tungsten oxide in the content of 5-50 wt%. The catalyst is used in synthesizing glutaraldehyde through oxidizing cyclopentene and has ideal reaction activity and high selectivity, and the reaction period of 4-8 hr reaches cyclopentene converting rate up to 100 % and glutaraldehyde yield up to 80 %. It has simple preparation process, facile material, short preparation period and low preparation cost, and is suitable for use in industrial production.
Description
Technical field
The present invention relates to a kind of loaded catalyst that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene, is carrier with the mesoporous molecular sieve particularly, is 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%.These existing catalyst 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, these activity of such catalysts are generally not high, and this time that is reflected in oxidation reaction is all longer, is generally 12～60 hours.And the preparing carriers of these catalyst 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 loaded catalyst that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene, the technical problem that it will solve is further to improve the catalytic activity of catalyst, and make Preparation of catalysts more easy, reduce the manufacturing cost of catalyst, thereby overcome the existing in prior technology defective.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of loaded catalyst that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene.This catalyst is a carrier with the Ti-HMS mesoporous molecular sieve, and 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 of load is a tungsten oxide in the catalyst, and its content is 5～50wt%.
The mol ratio of silicon and titanium is preferably 20～40 in the above-mentioned carrier; The content of active component tungsten oxide is preferably 10～40wt% in the catalyst.
The granularity of catalyst is preferably 100～120 orders.
Carrier material Ti-HMS mesoporous molecular sieve is ℃ following synthesizing in normal temperature～50, concrete steps are: the template agent is dissolved in the aqueous hydrochloric acid solution, stirs, drip the mixed solution that is made into by tetraethyl orthosilicate, isopropyl alcohol, tetrabutyl titanate and ethanol, make it become white gels, through aging, filtration.Successively with ethanol and water washing, under 80～120 ℃ of temperature dry 2～5 hours, 300～800 ℃ of roasting temperatures 2～6 hours, promptly obtain Ti-HMS mesoporous molecular sieve carrier again.
In the above-mentioned preparing carriers process, the template agent can be lauryl amine or tetradecy lamine, is preferably lauryl amine, and its consumption is 10～50% of a tetraethyl orthosilicate weight, is preferably 20～40%.The consumption of hydrochloric acid is 1～20% of a tetraethyl orthosilicate weight, is preferably 5～15%.Water consumption is 1～5 times of tetraethyl orthosilicate weight in the aqueous hydrochloric acid solution, is preferably 2～4 times.The consumption of isopropyl alcohol is 5～50% of a tetraethyl orthosilicate weight, is preferably 10～40%.Consumption of ethanol is 1～8 times of tetraethyl orthosilicate weight, is preferably 1～5 times.The consumption of tetrabutyl titanate decides according to the mol ratio of silicon and titanium in the desired molecular sieve.
The active component tungsten oxide can adopt infusion process to load to carrier to get on, and concrete steps are: the initial compounds and the cosolvent of tungsten are added in the hot water, stir to clarify, add the Ti-HMS molecular sieve carrier of preparation as stated above again, and through aging, drying and roasting.After promptly get catalyst prod after grinding the granularity that reaches required.
In the active component tungsten oxide loaded to process on the carrier, the initial compounds of tungsten can be soluble tungstate salt such as ammonium tungstate, sodium tungstate, preferably ammonium tungstate.Solution temperature is 50～100 ℃, and solution temperature is 70～90 ℃ preferably.Cosolvent can be oxalic acid, ammoniacal liquor, preferably oxalic acid.The cosolvent addition is 0.5～5 times of initial compounds of tungsten.Ageing time is 2～24 hours, is preferably 2～16 hours.Baking temperature is 70～150 ℃, is preferably 90～120 ℃.Sintering temperature is 200～600 ℃, is preferably 300～500 ℃.
Compared with prior art, key of the present invention is that catalyst has used a kind of more suitable carriers, and this is a kind of novel mesoporous molecular sieve that embeds transition metal Ti.The inventor found through experiments, and this catalyst has 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%.And used carrier and the catalyst preparation process of catalyst is easy, and raw material is easy to get, and manufacturing cycle is short, unlike need carry out long-time crystallization in the prior art under air-tight state.Therefore the catalyst low cost of manufacture helps large-scale industrial production.
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]
The preparation of catalyst carrier:
At room temperature, the adding of 5g lauryl amine is contained in the 70mL aqueous solution of 1.5g hydrochloric acid, mechanical agitation drips the mixed solution that is made into by 21g tetraethyl orthosilicate, 3.4g isopropyl alcohol, 30g ethanol and 1.7g tetrabutyl titanate, stirs 2 hours.Aging 12 hours then, filter the back successively with ethanol and water washing.Under 80～120 ℃ of temperature dry 2～5 hours, again 400～800 ℃ of roasting temperatures 2～6 hours.Getting 100～120 order powder after the grinding, to obtain white Ti-HMS mesoporous molecular sieve be catalyst carrier.
Preparation of Catalyst:
In 70～90 ℃ oil bath, the 1.6g ammonium tungstate is dissolved in the 15ml deionized water, stir adding 0.9g oxalic acid down, continue to stir 20 minutes, treat solution clarification back adding 3g said catalyst carrier.Room temperature left standstill 12 hours, in 90～120 ℃ of dryings 3 hours, promptly got catalyst prod after 2 hours in 400～700 ℃ of roastings.
[embodiment 2～10]
Change the consumption of each catalyst carrier starting material and tungsten oxide starting material ammonium tungstate, all the other are with embodiment 1.
Measure the physical index of the catalyst that each embodiment makes, data see Table 1.
Table 1.
| 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 2.
Table 2.
| 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 (4)
1. a loaded catalyst that is used for oxidizing-synthesizing glutaric dialdehyde with cyclopentene is characterized in that this catalyst is a carrier with the Ti-HMS mesoporous molecular sieve, and 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 of load is a tungsten oxide in the catalyst, and its content is 5～50wt%.
2. loaded catalyst according to claim 1 is characterized in that the mol ratio of silicon and titanium is 20～40 in the described carrier.
3. loaded catalyst according to claim 1, the content that it is characterized in that active component tungsten oxide in the described catalyst is 10～40wt%.
4. loaded catalyst according to claim 1, the granularity that it is characterized in that described catalyst is 100～120 orders.
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| CN100421796C true CN100421796C (en) | 2008-10-01 |
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| CN107694601B (en) * | 2017-10-31 | 2020-05-19 | 湖北荟煌科技股份有限公司 | High-selectivity and high-conversion-rate catalyst and preparation method thereof |
| CN110372483B (en) * | 2019-07-17 | 2022-11-15 | 上海应用技术大学 | Process method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
| CN111138256B (en) * | 2019-12-16 | 2021-07-13 | 中国科学院大连化学物理研究所 | A kind of preparation method of adipaldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1425498A (en) * | 2003-01-03 | 2003-06-25 | 复旦大学 | Supported tungstic acid catalyst for synthesizing glutaraldehyde and its producing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1425498A (en) * | 2003-01-03 | 2003-06-25 | 复旦大学 | Supported tungstic acid catalyst for synthesizing glutaraldehyde and its producing method |
Non-Patent Citations (2)
| Title |
|---|
| Ti-HMS分子筛的合成与表征. 李钢等.催化学报，第25卷第4期. 2004 |
| Ti-HMS分子筛的合成与表征. 李钢等.催化学报，第25卷第4期. 2004 * |
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