CN101112690A - Catalyzer for preparing glutaraldehyde by the catalytic oxidation of cyclopentene - Google Patents
Catalyzer for preparing glutaraldehyde by the catalytic oxidation of cyclopentene Download PDFInfo
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- CN101112690A CN101112690A CNA200610029427XA CN200610029427A CN101112690A CN 101112690 A CN101112690 A CN 101112690A CN A200610029427X A CNA200610029427X A CN A200610029427XA CN 200610029427 A CN200610029427 A CN 200610029427A CN 101112690 A CN101112690 A CN 101112690A
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- cyclopentene
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Abstract
A catalyst for preparing the glutaraldehyde by the catalytic oxidation of the cyclopentene is characterized in that the catalyst takes the tungsten modified HMS middle hole molecular sieve as the carrier where the mol ratio between the silicon and the tungsten is (10- 80): 1, the specific surface ranges from 700m2/g to 1200m2/g and the average hole diameter ranges from 3 nm to 6 nm; the active component in the carrier is WO3 and the content of the WO3 in the catalyst ranges from 2 wt percent to 20 wt percent. The catalyst is used for the oxidation and synthesis of glutaraldehyde by the cyclopentene; particularly when the hydrogen peroxide is taken as the oxidant, the catalyst has extremely perfect reaction activity and selection, and the yield of the glutaraldehyde ranges from 70 percent to 80 percent. The catalyst has long service life and can keep good reaction activity after repeatedly used more than 5 times.
Description
Technical field
The present invention relates to a kind of catalyst that the cyclopentene catalytic oxidation prepares glutaraldehyde that is used for, particularly a kind of is carrier with the HMS mesoporous molecular sieve, and active component is the loaded catalyst that the cyclopentene catalytic oxidation prepares glutaraldehyde that is used for of Tungstenic compound.
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, ripe suitability for industrialized production glutaraldehyde method 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.By oxidizing-synthesizing glutaric dialdehyde with cyclopentene is the glutaraldehyde new preparation process that is born in recent years, wherein is 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.
At present, with the hydrogen peroxide be oxidant by the more employing heterogeneous catalytic oxidation of oxidizing-synthesizing glutaric dialdehyde with cyclopentene, catalyst is generally the solid-phase catalyst that contains W elements.Introduce the airtight crystallization of process as CN1425498 and make a kind of TiO
2Microballoon prepares tungsten-containing catalyst as carrier, and the glutaraldehyde yield is up to 69.4%, and minimum is 60.3%, and average 65.4%.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 glutaraldehyde yield is up to 72%, and minimum is 50%, average 66.5%.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 the glutaraldehyde yield is minimum to be 47.0%, is up to 78.9%, average 63.1%.The disclosed technology of CN1680032A is that original position is introduced the catalyst that the tungsten component prepares oxidation reaction in the process of synthetic HMS type total silicon mesoporous molecular sieve, and the glutaraldehyde yield is up to 76.2%, and minimum is 56.9%, average 68.6%.These are existing to be used for its performance of this catalyst for reaction to show as the conversion ratio of cyclopentene all more satisfactory, but that defective is the selectivity of target product is all lower, and the glutaraldehyde average yield is generally all below 70%.
Summary of the invention
The invention provides a kind of catalyst that the cyclopentene catalytic oxidation prepares glutaraldehyde that is used for, it is relatively poor to the selectivity of target product that it can solve existing similar catalyst effectively, low this technical problem of glutaraldehyde average yield.
Below be the detailed technical scheme of the present invention:
A kind ofly be used for the catalyst that the cyclopentene catalytic oxidation prepares glutaraldehyde, this catalyst is a carrier with tungsten modification HMS mesoporous molecular sieve, and the mol ratio of silicon and tungsten is (10～80) in the carrier: 1, and specific area is 700～1200m
2/ g, average pore size is 3～6nm, load active component WO
3, WO in the catalyst
3Content be 2～20wt%.
The mol ratio of silicon and tungsten is preferably (20～50) in the said catalyst carrier: 1; WO in the catalyst
3Content be preferably 5～15wt%; The granularity of catalyst is generally 100～120 orders.
Preparation of catalysts comprises preparation and two processes of load active component of carrier.
Carry out the preparation of carrier earlier, in preparation HMS mesoporous molecular sieve, the W elements introducing is wherein made tungsten modification HMS mesoporous molecular sieve.The template agent is dissolved in the aqueous hydrochloric acid solution, adds following two kinds of solution under stirring simultaneously: by tetraethyl orthosilicate and the ethanol solution that is made into and the wolframic acid or the tungstates aqueous solution that contain cosolvent.Continuous stirring makes it become gel, through overaging, filtration.Successively with ethanol and water washing.Above process can be carried out at normal temperatures.Under 80～120 ℃ of temperature dry 2～5 hours,, promptly obtain tungsten modification HMS mesoporous molecular sieve as carrier in 300～800 ℃ of roasting temperatures 2～6 hours.
In 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 1～10 times of tetraethyl orthosilicate weight in the aqueous hydrochloric acid solution, is preferably 2～6 times.Consumption of ethanol is 1～8 times of tetraethyl orthosilicate weight, is preferably 1～5 times.Tungstenic compound can be wolframic acid, ammonium tungstate or sodium tungstate, and best is wolframic acid, and its consumption depends on the mol ratio of silicon and tungsten in the molecular sieve.Cosolvent can be oxalic acid, ammoniacal liquor or hydrogen peroxide, preferably oxalic acid or hydrogen peroxide.The cosolvent addition is 0.1～2.0 times of Tungstenic compound, is preferably 0.3～1.5 times.Mixing time is 5～45 minutes, is preferably 15～30 minutes.Ageing time is 9～24 hours, and the time is 12～18 hours preferably.
Adopt infusion process that active constituent loading is obtained the catalyst finished product then to carrier.Tungstenic compound and cosolvent are added in the hot water, stir to clarify, add carrier more in proportion,, grind screening and obtain catalyst prod through aging, drying and roasting according to method for preparing.The initial compounds of tungsten can be wolframic acid, ammonium tungstate or sodium tungstate, preferably ammonium tungstate.Solution temperature is 50～100 ℃, better is 70～90 ℃.Cosolvent can be oxalic acid, ammoniacal liquor or hydrogen peroxide, preferably oxalic acid.The cosolvent addition is 0.1～2.0 times of tungsten source, and ratio is 0.2～1.0 times preferably.Stirring into the glue temperature is 20～100 ℃, and temperature is 50～80 ℃ preferably.Ageing time is 2～24 hours, is preferably 6～18 hours.Baking temperature is 70～150 ℃, is preferably 90～120 ℃, and the time is 1～5 hour, is preferably 2～3 hours.Sintering temperature is 200～450 ℃, is preferably 300～400 ℃.Roasting time is 1～5 hour, is preferably 2～3 hours.
Key of the present invention is to adopt tungsten modification HMS mesoporous molecular sieve as carrier, and the load tungsten oxide is as active component.The inventor found through experiments, and this catalyst is being used for the reaction of oxidizing-synthesizing glutaric dialdehyde with cyclopentene, when particularly adopting hydrogen peroxide to be oxidant, has very desirable reactivity and selectivity.Compared with prior art, the performance that the invention has the advantages that catalyst is more good, is presented as that the required reaction time is shorter, and the yield of glutaraldehyde is between 70～80%, and have long service life, repeated use still can keep good reaction activity more than 5 times.
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:
One, the preparation of carrier:
[embodiment 1]
At room temperature, respectively 2.5g wolframic acid, 15ml aqueous hydrogen peroxide solution (concentration 30%) and 1.4g oxalic acid are added in the 35ml deionized water, stir dissolving fully after 30 minutes.
The 5.1g lauryl amine is added in the solution that is made into by 0.5g hydrochloric acid, 55ml deionized water and 34ml ethanol, after the stirring and dissolving, the solution that adds the above-mentioned Tungstenic compound of 17ml simultaneously, and by the solution that 23ml tetraethyl orthosilicate and 20ml ethanol are made into, continue to stir 30 minutes.Aging 18 hours then, filter, successively use ethanol and water washing.Under 120 ℃ of temperature dry 2 hours, in 450 ℃ of roasting temperatures 4 hours, get 100～120 order powder after grinding screening, obtain tungsten modification HMS mesoporous molecular sieve as carrier.The carrier specific area is 700～1200m
2/ g, average pore size is 3～6nm.
[embodiment 2～5]
Change the raw material proportioning, all the other are with embodiment 1.
Two, load active component
[embodiment 6]
Respectively 1.1g ammonium tungstate and 0.6g oxalic acid are added the 12ml temperature and be in 85 ℃ the deionized water, continuous stirring added the carrier that 3g is made by embodiment 1 after 20 minutes.Be cooled to room temperature, left standstill aging 16 hours, in 120 ℃ of dryings 2 hours, roasting was 2 hours in 250～300 ℃ of air, obtains catalyst prod.
[embodiment 7～18]
Change the raw material consumption, and the carrier that adopts different embodiment to obtain, all the other are with embodiment 6.
WO in the mol ratio of silicon and tungsten and the catalyst in its carrier of the catalyst that embodiment 6～18 makes
3Contain scale 1.
Table 1.
| Carrier embodiment | Si in the carrier: W (mol ratio) | WO in the catalyst 3Content (wt%) | |
| Embodiment 6 | Embodiment 1 | 30∶1 | 10 |
| Embodiment 7 | Embodiment 1 | 30∶1 | 5 |
| Embodiment 8 | Embodiment 1 | 30∶1 | 8 |
| Embodiment 9 | Embodiment 1 | 30∶1 | 15 |
| Embodiment 10 | Embodiment 2 | 20∶1 | 5 |
| Embodiment 11 | Embodiment 2 | 20∶1 | 10 |
| Embodiment 12 | Embodiment 2 | 20∶1 | 15 |
| Embodiment 13 | Embodiment 3 | 40∶1 | 5 |
| Embodiment 14 | Embodiment 3 | 40∶1 | 10 |
| Embodiment 15 | Embodiment 3 | 40∶1 | 15 |
| Embodiment 16 | Embodiment 4 | 45∶1 | 5 |
| Embodiment 17 | Embodiment 4 | 45∶1 | 10 |
| Embodiment 18 | Embodiment 5 | 50∶1 | 15 |
The catalyst that the foregoing description 6～18 obtains carries out activity rating with following condition:
In being three mouthfuls of round-bottomed flasks of 250ml, volume carries out the reaction of cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde.Adopt 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.Stirring reaction 14 hours.Adopt gas-chromatography internal standard method analytical reactions liquid to form, thus the conversion ratio of ring amylene and glutaraldehyde yield.
Embodiment 6～18 activity of such catalysts evaluation results see Table 2.
Table 2.
| Cyclopentene conversion ratio (%) | Glutaraldehyde yield (%) | |
| Embodiment 6 | 97.0 | 76.8 |
| Embodiment 7 | 99.0 | 76.1 |
| Embodiment 8 | 95.4 | 71.8 |
| Embodiment 9 | 91.5 | 73.7 |
| Embodiment 10 | 96.0 | 76.8 |
| Embodiment 11 | 100 | 81.4 |
| Embodiment 12 | 99.3 | 77.6 |
| Embodiment 13 | 98.1 | 78.6 |
| Embodiment 14 | 100 | 79.5 |
| Embodiment 15 | 96.8 | 76.8 |
| Embodiment 16 | 98.6 | 76.9 |
| Embodiment 17 | 94.9 | 74.7 |
| Embodiment 18 | 95.4 | 72.6 |
Claims (4)
1. one kind is used for the catalyst that the cyclopentene catalytic oxidation prepares glutaraldehyde, it is characterized in that this catalyst is a carrier with tungsten modification HMS mesoporous molecular sieve, and the mol ratio of silicon and tungsten is (10～80) in the carrier: 1, and specific area is 700～1200m
2/ g, average pore size is 3～6nm, load active component WO
3, WO in the catalyst
3Content be 2～20wt%.
2. catalyst according to claim 1 is characterized in that the mol ratio of silicon and tungsten in the described catalyst carrier is (20～50): 1.
3. catalyst according to claim 1, the content that it is characterized in that WO3 in the described catalyst is 5～15wt%.
4. catalyst according to claim 1, the granularity that it is characterized in that described catalyst is 100～120 orders.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA200610029427XA CN101112690A (en) | 2006-07-27 | 2006-07-27 | Catalyzer for preparing glutaraldehyde by the catalytic oxidation of cyclopentene |
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|---|---|---|---|
| CNA200610029427XA CN101112690A (en) | 2006-07-27 | 2006-07-27 | Catalyzer for preparing glutaraldehyde by the catalytic oxidation of cyclopentene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383965A (en) * | 2014-11-19 | 2015-03-04 | 河南工业大学 | Metal-organic framework immobilized tungsten oxide catalyst for synthesizing glutaraldehyde and production method of metal-organic framework immobilized tungsten oxide catalyst |
| CN109939671A (en) * | 2019-04-12 | 2019-06-28 | 浙江工业大学 | A kind of method for preventing W loss in WO3-H2O2 catalytic oxidation system |
| CN116003236A (en) * | 2023-02-14 | 2023-04-25 | 山东京博石油化工有限公司 | Production method of glutaraldehyde |
-
2006
- 2006-07-27 CN CNA200610029427XA patent/CN101112690A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383965A (en) * | 2014-11-19 | 2015-03-04 | 河南工业大学 | Metal-organic framework immobilized tungsten oxide catalyst for synthesizing glutaraldehyde and production method of metal-organic framework immobilized tungsten oxide catalyst |
| CN104383965B (en) * | 2014-11-19 | 2016-05-25 | 河南工业大学 | The immobilized tungsten oxide catalyst of a kind of metal-organic framework for the synthesis of glutaraldehyde and production method thereof |
| CN109939671A (en) * | 2019-04-12 | 2019-06-28 | 浙江工业大学 | A kind of method for preventing W loss in WO3-H2O2 catalytic oxidation system |
| CN116003236A (en) * | 2023-02-14 | 2023-04-25 | 山东京博石油化工有限公司 | Production method of glutaraldehyde |
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