CN1175934C - Molecular sieve catalyst containing pores in tungsten media utilized for synthesizing glutaraldehyde and its preparation method - Google Patents
Molecular sieve catalyst containing pores in tungsten media utilized for synthesizing glutaraldehyde and its preparation method Download PDFInfo
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- CN1175934C CN1175934C CNB031153070A CN03115307A CN1175934C CN 1175934 C CN1175934 C CN 1175934C CN B031153070 A CNB031153070 A CN B031153070A CN 03115307 A CN03115307 A CN 03115307A CN 1175934 C CN1175934 C CN 1175934C
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Abstract
The present invention relates to a novel heterogeneous tungstenic catalyst used for selectively oxidizing cyclopentene to prepare glutaraldehyde by an aqueous hydrogen peroxide solution used as an oxidizing agent and a preparing method thereof, which belongs to the technical field of chemical industry. The tungstenic catalyst is prepared by introducing a tungsten oxide component during the process of synthesizing an SBA-15 type all-silicon mesoporous molecular sieve in an in-situ mode. The catalyst has the characteristics of high dispersion of active components and ultra-high loading capacity of tungsten oxide. The obtained heterogeneous catalyst can be applied to a catalytic selective oxidation reaction of the cyclopentene, so the selectivity of the glutaraldehyde is greatly improved, and the numeric value of the heterogeneous catalyst is far higher than the level of reported homogeneous catalysis or other heterogeneous tungstic acid carrying catalysts. The heterogeneous catalyst has the advantage of significant industrial application value.
Description
Technical field
The invention belongs to chemical technology field, is a kind of tungsten-contained mesic porous molecular sieve catalyst and manufacture method thereof that is used for the cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde.
Background technology
Glutaraldehyde is unusual important chemical product, is widely used the linking agent of making fixing agent, protein and poly-hydroxylic species that disinfectant, leather retanning agent, optics and electron microscope tissue slice use and little micella solidifying agent etc.According to estimates, domestic pure glutaraldehyde aggregate demand will reach 20000 tons/year at present.The domestic used glutaraldehyde overwhelming majority at present is by import, has only minority the unit productions of propenal method, 500 tons/year of overall throughput less thaies such as Wuhan Organic Chemical Plant.The present industrial propenal two-step approach synthesis of glutaraldehyde (spy opens clear 59-108734) that all adopts, because this method exists the raw material sources costliness, the operational condition harshness, shortcoming such as facility investment is big and seriously polluted, so scientists is devoted to the glutaraldehyde synthetic route of development of new always.Produce glutaraldehyde by cyclopentenes oxidation open loop and be considered to a up-and-coming route, because its main raw material cyclopentenes comes from the by product of refining of petroleum, the source is abundant, and is cheap.Since the eighties in last century, existing patent report comprises ring acetyl acetone (or molybdenum carbonyl)-methyl dimethylphosphite system (spy opens clear 62-29546), acetylacetone copper/B
2O
3-tributyl phosphate system (spy opens clear 62-19548), tungstic oxide/B
2O
3-butylacetate system (Chem.Lett., 1988,877), phospho-molybdic acid/arsenus acid-tributyl phosphate system (spy opens clear 57-07434), phosphorus molybdenum tungsten mixing heteropolyacid-phosphide tri-n-butyl system (Chem.Lett., 1982,1951).These catalyzer are all very sensitive to water, need in anhydrous system, to operate, and the yield of glutaraldehyde not high (being lower than 50%).And owing to relate to anhydrous hydrogen peroxide, operation is extremely dangerous, does not have industrial value substantially.The homogeneous phase tungstic acid catalyst of reports such as Jiang Anren has obtained the result (ZL 89 1 09401.6) of cyclopentenes transformation efficiency 100% and glutaraldehyde yield＞70%, but because catalyzer and product separation are relatively more difficult, industrialization at present remains in certain difficulty.SBA-15 (J.Am.Chem.Soc., 1998 (120), 6024) is a kind of novel mesoporous SiO
2Material has than bigger aperture of general mesopore molecular sieve and thicker hole wall, shows better stability, makes it have application potential in heterogeneous fields such as heterogeneous catalyst, fractionation by adsorption and Materials science.
Summary of the invention
The objective of the invention is to propose a kind of catalytic activity height, good to the glutaraldehyde selectivity, be convenient to tungsten-contained mesic porous molecular sieve catalyst that is used for the cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde of production control and preparation method thereof again.
The tungsten-contained mesic porous molecular sieve catalyst that is used for the cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde that the present invention proposes is to introduce WO in the building-up process original position of mesoporous molecular sieve SBA-15
3Active ingredient and preparing is designated as W-SBA-15, wherein SiO
2And WO
3The molar ratio scope be generally 5.8～73.4.
Above-mentioned tungsten-contained mesic porous molecular sieve catalyst adopts the in-situ synthetic method preparation.Its concrete steps are: P123 (is EO with the template triblock polymer
20PO
70EO
20Be called for short P123) be dissolved in the aqueous hydrochloric acid, stir, add tetraethoxy then, continue to stir, make the tetraethoxy partial hydrolysis, splash into the aqueous solution in tungstenic source, continue to stir 20-30 hour, make it become glue, the colloid that obtains is moved in the autoclave, and crystallization is 24～108 hours under 80～200 ℃ of temperature; Take out, filter, washing, template is removed in roasting, and granulation promptly gets the catalyzer finished product.
Among the above-mentioned preparation method, the consumption of template P123 is 1～5% of a tetraethoxy weight, is preferably 1～3%; The consumption of said hydrolyzed agent hydrochloric acid is 1-5 a times of tetraethoxy weight, is preferably 1-3 doubly; Add water consumption in the hydrochloric acid and be tetraethoxy weight 5-20 doubly, be preferably 8-16 doubly.
Among the above-mentioned preparation method, the tungsten source can be a kind of of phospho-wolframic acid, sodium wolframate, ammonium tungstate, and the tungsten source is a sodium wolframate preferably.According to consumption, it is mixed with dilute aqueous soln uses.The joining day of the sodium wolframate aqueous solution is generally teos hydrolysis and began the back 1～12 hour, and the reasonable time is 3～6 hours.The one-tenth glue temperature of system is 10～100 ℃, and becoming the glue temperature preferably is 30～80 ℃.Become the glue process need to stir (induction stirring or mechanical stirring); Crystallization temperature is generally 80～200 ℃, and crystallization temperature is 90～140 ℃ preferably, and crystallization time was generally 24～108 hours, and the time is 50～90 hours preferably.Bake out temperature to solids is generally 80～120 ℃, and bake out temperature is 90～100 ℃ preferably.After the oven dry, need further to remove residual moisture and template.The removal method adopts temperature-programmed calcination.The atmosphere of roasting is generally air, oxygen, nitrogen or argon gas, is preferably air or oxygen.Maturing temperature is generally 300～1200 ℃, and reasonable temperature range is 400～1000 ℃.Catalyzer after the roasting can wear on demand that the particle and the activated back of all size is standby, and reasonable size range is 20～60 orders, and the better scope of activation temperature is 300～800 ℃.
The electron micrograph of typical W-SBA-15 catalyzer is seen Fig. 1 and Fig. 2.
Can test with the following method the activity of such catalysts that the present invention proposes:
Cyclopentenes catalytic oxidation among the present invention is to carry out in the round-bottomed flask of sealing, adopts induction stirring.Reaction conditions is that 30～45 ℃ of oil baths add in the 140mL t-butanol solvent and contain 0.5～0.8mol H
2O
250% or 30% aqueous hydrogen peroxide solution, add 2.3g catalyzer and 0.2～0.4mol cyclopentenes then, stirring reaction 12～60h.Reacted cyclopentenes transformation efficiency and glutaraldehyde selectivity adopt gas chromatographic analysis to measure, and identify each component with chromatograph-mas spectrometer.
The present invention is owing to adopted original position synthetic method that tungsten is introduced framework of molecular sieve, improved the dispersive ability of molecular sieve greatly to wolframic acid, improved the effect of tungsten source and framework of molecular sieve, this catalyzer demonstrates excellent catalytic performance in the reaction of cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde, its to the selectivity of glutaraldehyde far above all catalyzer of having revealed.The SBA-15 mesoporous molecular sieve catalyst of this novel tungstenic has represented the application prospect that good cyclopentenes catalyzed oxidation prepares glutaraldehyde.
The advantage of catalyzer provided by the invention is specific as follows:
1. this catalyzer has well kept mesoporous molecular sieve SBA-15 distinctive ring shape pattern and mesoporous characteristic when introducing the tungsten source.
These catalyzer tungsten species be uniformly dispersed and dispersion amount big.
3. catalyst activity height reaches more than 94% the transformation efficiency of cyclopentenes, and the selectivity of glutaraldehyde is reached more than 84%, and the glutaraldehyde yield reaches 80%, shows excellent catalytic performance.
4. this catalyzer is insensitive to reaction parameter, broad between the operational zone, and elasticity is big, is convenient to production control.
5. the tungsten on this catalyzer combines with carrier firmly, after tens of experiment circulations, does not find that also it comes off from carrier surface.
6. this Preparation of Catalyst is simple, and intensity is big, and is wear-resistant, and can reuse, and regeneration back catalytic performance is good.
Description of drawings
Fig. 1 is the stereoscan photograph of W-SBA-15 catalyzer.
Fig. 2 is the transmission electron microscope photo of W-SBA-15 catalyzer.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:40 ℃ oil bath, induction stirring adds the concentrated hydrochloric acid of 60mL and contains in the 312mL deionized water of 0.3g template P123 (molecular weight is 5800), stirs 4 hours.Add the 25.6g tetraethoxy, stirred 1 hour, add the 10mL aqueous solution that contains the 0.495g phospho-wolframic acid, continue to stir 24 hours.The colloid that obtains changed in the 1000mL autoclave seal, take out after 72 hours 100 ℃ of following crystallization; Filter, washing, 100 ℃ were dried by the fire 24 hours.Roasting is more than 6 hours in 700 ℃ of oxygen atmosphere, granulation, and 40～60 orders that sieve, 800 ℃ of activation obtained the 1# catalyzer after 3 hours.
Embodiment 2:35 ℃ oil bath, mechanical stirring adds the concentrated hydrochloric acid of 90mL and contains in the 468mL deionized water of 0.5g template P123 (molecular weight is 5800), stirs 6 hours.Add the 25.6g tetraethoxy, stirred 2 hours, add the 10mL aqueous solution that contains the 1.05g ammonium tungstate, continue to stir 36 hours.The colloid that obtains changed in the 1000mL autoclave seal, take out after 48 hours 100 ℃ of following crystallization; Surplus with embodiment 1, obtain the 2# catalyzer.
Embodiment 3:50 ℃ oil bath, induction stirring adds the concentrated hydrochloric acid of 45mL and contains in the 208mL deionized water of 0.4g template P123 (molecular weight is 5800), stirs 3 hours.Add the 25.6g tetraethoxy, stirred 1.5 hours, add the 10mL aqueous solution that contains the 2.15g sodium wolframate, continue to stir 48 hours.The colloid that obtains changed in the 500mL autoclave seal, take out after 96 hours 100 ℃ of following crystallization; Surplus with embodiment 1, obtain the 3# catalyzer.
Embodiment 4:30 ℃ oil bath, mechanical stirring adds the concentrated hydrochloric acid of 60mL and contains in the 624mL deionized water of 1.0g template P123 (molecular weight is 5800), stirs 5 hours.Add the 25.6g tetraethoxy, stirred 3 hours, add the 10mL aqueous solution that contains the 3.25g sodium wolframate, continue to stir 32 hours.The colloid that obtains changed in the 1000mL autoclave seal, take out after 108 hours 100 ℃ of following crystallization; Surplus with embodiment 1, obtain the 4# catalyzer.
Embodiment 5:60 ℃ oil bath, induction stirring adds the concentrated hydrochloric acid of 100mL and contains in the 780mL deionized water of 0.8g template P123 (molecular weight is 5800), stirs 3 hours.Add the 25.6g tetraethoxy, stirred 2 hours, add the 10mL aqueous solution that contains the 4.35g sodium wolframate, continue to stir 48 hours.The colloid that obtains changed in the 2000mL autoclave seal, take out after 96 hours 130 ℃ of following crystallization; Surplus with embodiment 1, obtain the 5# catalyzer.
5 catalyzer of embodiment 1～embodiment 5 are carried out active testing, and gained the results are shown in subordinate list 1.
Subordinate list 1. contains wolframic acid mesoporous molecular sieve catalyst active testing result
| Catalyzer | Cyclopentenes transformation efficiency (wt%) | Glutaraldehyde selectivity (wt%) | Glutaraldehyde yield (wt%) |
| 1# | 80 | 80.6 | 64.5 |
| 2# | 86 | 82.5 | 70.9 |
| 3# | 94 | 83.9 | 78.9 |
| 4# | 70 | 77.6 | 54.3 |
| 5# | 65 | 72.3 | 47.0 |
Claims (9)
1, a kind of tungsten-contained mesic porous molecular sieve catalyst that is used for the cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde is characterized in that original position is introduced WO in the process of synthetic SBA-15 mesopore molecular sieve
3Prepare after the active ingredient, wherein, SiO
2With WO
3Molar ratio be 5.8-73.4.
2, a kind of Preparation of catalysts method as claimed in claim 1, it is characterized in that concrete steps are: P123 is dissolved in the aqueous hydrochloric acid with the template triblock polymer, stir, add tetraethoxy then, continue to stir, make the tetraethoxy partial hydrolysis, splash into the aqueous solution in tungstenic source, continue to stir 20-30 hour, make it become glue, the colloid that obtains is moved in the autoclave, and crystallization is 24～108 hours under 80～200 ℃ of temperature; Take out, filter, washing, template is removed in roasting, and granulation promptly gets the catalyzer finished product.
3, Preparation of catalysts method according to claim 2, the consumption that it is characterized in that the template P123 that building-up process adopts is 1～5% of a tetraethoxy weight.
4, Preparation of catalysts method according to claim 2, the consumption that it is characterized in that the hydrolytic reagent hydrochloric acid that building-up process adopts are 1～5 times of tetraethoxy weight.
5, Preparation of catalysts method according to claim 2, the consumption that it is characterized in that the water of dilute hydrochloric acid in the building-up process are 5～20 times of tetraethoxy weight.
6, Preparation of catalysts method according to claim 2 is characterized in that the tungsten source adopts a kind of of phospho-wolframic acid, sodium wolframate, ammonium tungstate.
7, Preparation of catalysts method according to claim 2, the hydrolysis time that it is characterized in that tetraethoxy is 1～12 hour.
8, Preparation of catalysts method according to claim 2 is characterized in that it is 10～100 ℃ that catalyzer becomes the glue temperature.
9, Preparation of catalysts method according to claim 2 is characterized in that it is 300～1200 ℃ that catalyzer is removed the maturing temperature of template.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100408179C (en) * | 2005-05-20 | 2008-08-06 | 中国科学院大连化学物理研究所 | Transition metal catalyst for gas phase synthesis of N-alkylaniline by aniline and alcohol |
| CN100363103C (en) * | 2005-07-14 | 2008-01-23 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| CN100363104C (en) * | 2005-07-14 | 2008-01-23 | 北京化工大学 | Porous molecular sieve catalyst for assembling tungsten carbide and its preparation |
| CN100445254C (en) * | 2005-08-09 | 2008-12-24 | 中国石化上海石油化工股份有限公司 | Method of synthesizing glutaraldehyde by oxidation of cyclo amylene |
| CN101172240B (en) * | 2006-11-02 | 2010-09-01 | 中国石油化工股份有限公司 | Method for preparing propylene by butylene disproportionation |
| CN101172241B (en) * | 2006-11-02 | 2010-07-21 | 中国石油化工股份有限公司 | Method for butylene disproportionation for generating propylene |
| CN101190867B (en) * | 2006-11-21 | 2010-10-06 | 中国石油化工股份有限公司 | Method for preparing propylene by olefin dismutation reaction |
| CN109499604A (en) * | 2017-11-29 | 2019-03-22 | 江南大学 | The mesoporous WO of one-step synthesis method3The method of/SBA-15 |
| CN108295889A (en) * | 2018-02-09 | 2018-07-20 | 青岛科技大学 | A kind of oxidation of cyclopentene synthesizing glutaric acid mesoporous silicon oxide supported tungsten oxide catalysts 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 |
| CN114426468B (en) * | 2020-10-16 | 2024-05-28 | 中国石油化工股份有限公司 | Method for preparing glutaraldehyde by taking cyclopentene as raw material |
| CN113813986B (en) * | 2021-11-02 | 2024-04-02 | 烟台东化新材料有限公司 | Tungsten-based molecular sieve catalyst, preparation method thereof and method for preparing glutaraldehyde by catalytic oxidation of cyclopentene |
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