CN1245257C - Mesoporous molecular sieve multiphase catalyst containing niobium for oxidative synthesis of glutaraldehyde by cyclopentene and preparation method thereof - Google Patents
Mesoporous molecular sieve multiphase catalyst containing niobium for oxidative synthesis of glutaraldehyde by cyclopentene and preparation method thereof Download PDFInfo
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- CN1245257C CN1245257C CN 200410015894 CN200410015894A CN1245257C CN 1245257 C CN1245257 C CN 1245257C CN 200410015894 CN200410015894 CN 200410015894 CN 200410015894 A CN200410015894 A CN 200410015894A CN 1245257 C CN1245257 C CN 1245257C
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- glutaraldehyde
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- molecular sieve
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Abstract
The present invention relates to a catalyst for oxidizing cyclopentene to synthesize glutaraldehyde and a preparing method thereof. The catalyst is a mesoporous molecular sieve (Nb/MCM-41) containing niobic acid, in which the weight content of niobium is 0.7 to 28% of that of the mesoporous molecular sieve (Nb/MCM-41). The niobic acid can be added by using a traditional immersion method or an in-situ synthesis method. The catalyst directly uses ethanol as solvent rather than expensive tertiary butyl alcohol. Under the action of aqueous hydrogen peroxide solution in a 30 to 70% concentration, glutaraldehyde can be directly obtained in a yield of 50%. The method has the advantages of simple technological process, effective production cost reduction, product competitiveness improvement and excellent industrial application prospects.
Description
Technical field
The invention belongs to chemical technology field, is a kind of Catalysts and its preparation method that is used for the cyclopentene heterogeneous catalytic oxidation synthesis of glutaraldehyde.
Background technology
Glutaraldehyde (Glutaraldehyde, OHC (CH
2)
3CHO) be unusual important chemical product; its two aldehyde radicals are very active; can carry out multiple differential responses; especially have crosslinked, as to solidify protein effect, so it is widely used as the crosslinking agent of fixative, protein and poly-hydroxylic species that disinfectant, leather retanning agent, optics and electron microscope histotomy use and little micella curing agent etc.Along with the variation of expanding economy and environment, infective virus such as AIDS (HIVs), hepatitis B, venereal disease, tuberculosis have caused people's common concern.China's hepatitis b virus carrier surpasses 100,000,000 at present, and the HIVs carrier also has the situation of quick growth, and regularly disinfecting of field of medical and sanitary facilities, public place and domestic environment becomes the mode that the public generally adopts.As the non-toxic quick-acting disinfection sanitizer that the Ministry of Public Health is recommended, glutaraldehyde has special effect to killing hepatitis type B virus, thereby glutaraldehyde has boundless market prospects in this regard.Recently, the appearance of novel SARS virus (SARS) has proposed challenge to traditional environment disinfected mode, because traditional Peracetic acid and chlorine-containing disinfectant can not be ignored the influence of environment.And glutaraldehyde is recommended as the environment disinfectant because its environmental friendliness and preferable biodegradability are subjected to favoring widely by The World Health Organization (WHO).China is leather big producing country, and what traditional industry adopted easily brings the serious pollution problem of chrome waste water with 50% potassium bichromate solution as tanning agent, if replace half of present chrome tanning consumption with glutaraldehyde, promptly year needs 6000 tons of 25% glutaraldehyde water solutions; In addition, aspect oil exploitation, glutaraldehyde is as the oil-field flooding bactericide, and the glutaraldehyde water solution of year demand 25% is more than 10000 tons.Everything shows that glutaraldehyde has unusual wide application prospect in China, and according to estimates, domestic pure glutaraldehyde aggregate demand will reach 20000 tons/year at present.And the domestic used glutaraldehyde overwhelming majority at present is by import, has only minority the unit productions of methacrylaldehyde method, 2000 tons/year of total productive capacity less thaies such as Wuhan Organic Chemical Plant.On the other hand, according to the prediction of China Petrochemical Industry calendar year 2001, the ethene annual production of China is near 5,000,000 tons, the carbon 5 (C of institute's by-product
5) surpassing 650,000 tons, cyclopentadiene wherein reaches 180,000 tons.And, Shanghai City will be set up the petrochemical industry base of domestic maximum at Hangzhou Wan, and the output of carbon 5 also will be largely increased, and this just provides sufficient raw material for the development glutaraldehyde, therefore, the output of glutaraldehyde will can not be subjected to the restriction of raw material sources and can be greatly improved.From above background material as can be known, the research of the novel inexpensive process route of glutaraldehyde is not only had huge commercial Application and economic worth, but also can make full use of the byproduct cyclopentadiene of producing in the petrochemical industry, to comprehensive utilization of C
5Raw material, the utilization rate that improves oil plays a driving role.
Be in the technology of feedstock production glutaraldehyde with the cyclopentene, existing patent report has ring acetyl acetone (or molybdenum carbonyl) monomethyl dimethylphosphite system (spy opens clear 62-29546), acetylacetone copper/B
2O
3-tributyl phosphate system (spy opens clear 62-19548), tungstic acid/B2O
3-butyl acetate system (Chem.Lett., 1988,877), phosphomolybdic acid/arsenious acid-tributyl phosphate system (spy opens clear 57-07434), phosphorus molybdenum tungsten mixing heteropoly acid one phosphide tributyl system (Chem.Lett., 1982,1951).These catalyst are all very sensitive to water, need in anhydrous system, to operate, and the yield of glutaraldehyde not high (being lower than 50%).Industrial general employing methacrylaldehyde two-step method synthesis of glutaraldehyde (spy opens clear 59-108734) exists shortcomings such as seriously polluted, raw material sources costliness now.The wolframic acid of our report or the glutaraldehyde yield that the niobic acid homogeneous catalyst has obtained cyclopentene conversion ratio 100% and>50%, but because catalyst separates the comparison difficulty with product, industrialization at present remains in certain difficulty.
Summary of the invention
The objective of the invention is to propose a kind of catalytic activity height, catalytic performance good be used for the Catalysts and its preparation method that cyclopentene heterogeneous catalytic oxidation prepares glutaraldehyde.
The present invention proposes is used for the catalyst that cyclopentene heterogeneous catalytic oxidation prepares glutaraldehyde, is with the mesoporous molecular sieve catalyst that contain niobic acid of mesopore molecular sieve MCM-41 as carrier, and wherein, niobium (Nb) is 0.7 with the weight ratio of MCM-41: 100-28: 100.This catalyst has improved the decentralization of niobic acid greatly, has improved the catalytic activity of Niobic Acid agent.It is different from the common niobic acid silica heterogeneous catalyst that contains, so the present invention is referred to as to contain the niobic acid mesoporous molecular sieve catalyst, is designated as Nb/MCM41.
The catalyst that the present invention proposes, niobium pentaoxide or columbium pentachloride can be adopted in the niobium source of its niobic acid.
The concrete preparation process that contains the niobic acid mesoporous molecular sieve catalyst proposed by the invention is: take by weighing niobic acid (as Nb
2O
5NH
2O) and oxalic acid put into a container, the consumption of niobic acid is pressed Nb
2O
5With the weight ratio of oxalic acid be 1: 1-1: 100 the metering.With deionized water dissolving, add the mesoporous molecular sieve MCM-41 of corresponding part by weight then, be warming up to 50~100 ℃, evaporating solvent is to doing, oven dry again, then in Muffle furnace with 300~1000 ℃ of calcinations 2~48 hours, promptly get the catalyst finished product, be designated as Nb/MCM-41.
Among the above-mentioned preparation method, niobic acid can adopt active niobic acid (Nb
2O
5NH
2O).Concrete preparation process is: take by weighing a certain amount of niobium pentaoxide (Nb
2O
5), add K
2S
2O
7In crucible, mix, as far as possible with K
2S
2O
7Cover Nb
2O
5, in Muffle furnace,, make fusion with 300~800 ℃ of heating 1~10 hour.After the fused solution cooling, behind oxalic acid solution dipping (oxalic acid: Nb=50~5: 1 mol ratios), suction filtration, washing, filtrate adds capacity ammoniacal liquor, and solution produces white precipitate, and standing over night is dried the white precipitate that suction filtration goes out under infrared lamp, promptly obtain active niobic acid (Nb
2O
5NH
2O).During the Nb/MCM41 Preparation of Catalyst, the temperature of oven dry is generally 50~120 ℃, and bake out temperature is 80~100 ℃ preferably.After the oven dry, need further to remove residual moisture and template agent.The removal method adopts temperature-programmed calcination.The atmosphere of roasting is generally air, oxygen, nitrogen or argon gas, is preferably air or oxygen.Sintering temperature is generally 300~1000 ℃, and reasonable temperature is 500~800 ℃.Catalyst after the roasting can be worn into the particle of all size on demand, and reasonable granularity is 20~60 orders.
Activity of such catalysts provided by the invention can be tested with the following method
Cyclopentene catalytic oxidation among the present invention is to carry out in the round-bottomed flask of sealing, adopts electromagnetic agitation.Reaction condition is 15~55 ℃ of oil baths, an amount of Nb/MCM-41, H
2O
2(50%w/w) 20 mMs, 8~20 milliliters of ethanol, cyclopentene 10 mMs, the reaction time was generally 4~36 hours.After reaction finished, reactant liquor was removed catalyst through centrifugation, got the upper strata centrifugal clear liquid and carried out gas chromatographic analysis to measure cyclopentene conversion ratio and glutaraldehyde selectivity, and product adopts chromatograph-mass spectrometer to identify.
Mesopore molecular sieve MCM-41 used among the present invention developed (BeekJC by U.S. Mobil company in 1992, VartulJC, KothWJ, et al.A new family of mesoporous mdecular sieve prepared with liquidcrystal templates.J Am Chem Soc, 1992,114 (27): 10834-10843).
The concrete advantage of catalyst provided by the invention
1, this catalyst has kept distinctive pattern of mesopore molecular sieve MCM-41 and mesoporous characteristic when introducing niobic acid.
2, catalyst activity height reaches more than 90% the conversion ratio of cyclopentene, and the selectivity of glutaraldehyde is reached more than 50%, shows excellent catalytic performance.
3, this catalyst is insensitive to response parameter, broad between the operating space, and elasticity is big, is convenient to production control.
4, this Preparation of Catalyst is simple, and can reuse, and regeneration back catalytic performance is good.
5, cheap, the gentle and free of contamination H of this catalyst utilization
2O
2As catalyst, ethanol cheap and easy to get is directly prepared glutaraldehyde as reaction dissolvent through one-step oxidation process, and cost greatly reduces, and has very big competitive advantage.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1: take by weighing contain 0.02 the gram Nb
2O
5Nb
2O
5NH
2O and 2 gram oxalic acid are put into 100 ml beakers, with 80 ml deionized water 50 ℃ of dissolvings, add 2 gram MCM-41 then, be warming up to 90 ℃, evaporating solvent is to doing, and is placed on infrared lamp under dry fully back then and dries by the fire 12 hours in 120 ℃ baking oven, in the oxygen atmosphere 300 ℃ of roastings 2 hours, granulation, 40~60 orders that sieve obtain the 1# catalyst.
Embodiment 2: take by weighing contain 0.1 the gram Nb
2O
5Nb
2O
5NH
2O and 5 gram oxalic acid are put into 100 ml beakers, with 80 ml deionized water 80 ℃ of dissolvings, add 2 gram MCM-41 then, be warming up to 90 ℃, evaporating solvent is to doing, and is placed on infrared lamp under dry fully back then and dries by the fire 24 hours in 140 ℃ baking oven, in the oxygen atmosphere in 800 ℃ of roastings 12 hours, granulation, 40~60 orders that sieve obtain the 2# catalyst.
Embodiment 3: take by weighing be equivalent to 0.4 the gram Nb
2O
5NbCl
5Put into 100 ml beakers with 20 milliliters of ethanol, add 2 gram MCM-41 then, normal temperature flooded 24 hours down, be warming up to 90 ℃, evaporating solvent is to doing, and is placed on infrared lamp under dry fully back then and dries by the fire 48 hours in 100 ℃ baking oven, in the oxygen atmosphere 1000 ℃ of roastings 24 hours, granulation, 40~60 orders that sieve obtain the 3# catalyst.
Embodiment 4: take by weighing contain 0.8 the gram Nb
2O
5Nb
2O
5NH
2O and 0.8 gram oxalic acid are put into 100 ml beakers, with 80 ml deionized water 100 ℃ of dissolvings, add 2 gram MCM-41 then, be warming up to 90 ℃, evaporating solvent is to doing, and is placed on infrared lamp under dry fully back then and dries by the fire 12 hours in 140 ℃ baking oven, in the oxygen atmosphere 600 ℃ of roastings 2 hours, granulation, 40~60 orders that sieve obtain the 4# catalyst.
The comparative example: take by weighing contain 0.2 the gram Nb
2O
5Nb
2O
5NH
2O and 5 gram oxalic acid are put into 100 ml beakers, with 80 ml deionized water 80 ℃ of dissolvings, add 2 gram common commercial silica then, be warming up to 90 ℃, evaporating solvent is to doing, and is placed on infrared lamp under dry fully back then and dries by the fire 12 hours in 120 ℃ baking oven, in the oxygen atmosphere 700 ℃ of roastings more than 12 hours, granulation, 40~60 orders that sieve obtain support type Nb
2O
5/ SiO
2, be designated as the 5# catalyst.
5 catalyst of embodiment 1~embodiment 4 and comparative example are carried out active testing, and the condition and the reaction result that are adopted are listed in table 1.
Table 1 contains niobic acid mesoporous molecular sieve catalyst reaction condition and active result
Catalyst | Temperature (℃) | Cyclopentene conversion ratio (mol%) | Glutaraldehyde selectivity (mol%) | Glutaraldehyde yield (mol%) |
1# | 35 | 84.4 | 50.1 | 42.3 |
2# | 35 | 85.8 | 57.4 | 49.3 |
3# | 35 | 83.9 | 58.5 | 49.2 |
4# | 35 | 81.5 | 61.0 | 49.7 |
5# | 35 | 40.3 | 34.5 | 13.9 |
Claims (3)
1, the heterogeneous catalyst used of a kind of oxidizing-synthesizing glutaric dialdehyde with cyclopentene is characterized in that with mesopore molecular sieve MCM-41 be carrier, wherein contains the niobic acid with catalytic activity, and the weight ratio of niobium and MCM-41 is 3.5: 100--28: 100.
2, a kind of preparation method of heterogeneous catalyst as claimed in claim 1 is characterized in that concrete steps are as follows: niobic acid and oxalic acid are put into a container, and the consumption of niobic acid is pressed Nb
2O
5Or NbCl
5With the weight ratio of oxalic acid be 1: 1--1: 100; With deionized water dissolving, be 3.5 by niobium and MCM-41 then: 100--28: 100 part by weight adds mesopore molecular sieve MCM-41, is warming up to 50~100 ℃, evaporating solvent is to doing, oven dry with 300~1000 ℃ of calcinations 2~48 hours, promptly gets the catalyst finished product then.
3, a kind of preparation method of glutaraldehyde is a raw material with the cyclopentene, and under organic solvent, catalyst and the hydrogen peroxide effect as oxidant, stirring reaction makes the glutaraldehyde reactant liquor, it is characterized in that using heterogeneous catalyst as claimed in claim 1.
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