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CN-118079896-B - Tungsten bismuth composite oxide catalyst, preparation and application

CN118079896BCN 118079896 BCN118079896 BCN 118079896BCN-118079896-B

Abstract

The invention provides a tungsten bismuth composite oxide catalyst for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, and a preparation method for preparing glutaraldehyde by using the catalyst. The catalyst has good stability, can still keep higher mechanical strength and chemical stability in the long-time reaction process, and has the advantages of simple preparation method, low raw material cost, easy expansion of preparation scale and the like. The catalyst of the invention is used in the reaction for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, has the advantages of high conversion rate of 1, 2-cyclopentane epoxide, good glutaraldehyde selectivity, high yield, good catalyst stability, easy separation and the like, and has remarkable industrial application value.

Inventors

  • DAI WEN
  • LI GUOSONG
  • LV YING

Assignees

  • 中国科学院大连化学物理研究所

Dates

Publication Date
20260512
Application Date
20221128

Claims (16)

  1. 1. The preparation method of the tungsten-bismuth composite oxide catalyst is characterized by comprising the following steps of: (1) Uniformly mixing a precursor of Al 2 O 3 , an aqueous solution of SiO 2 and a precursor of MgO and a dilute nitric acid solution containing bismuth nitrate, wherein the mass concentration of the bismuth nitrate is 10% -50%, and stirring and curing the mixture at 0-80 ℃ for 2-24 h to obtain a uniform colloid solution; (2) Dropwise adding the prepared sodium tungstate aqueous solution into the colloid solution obtained in the step (1), continuously stirring and aging for 5-24 h at 20-80 ℃, and spray drying the obtained solid solution suspension at 200-300 ℃ to obtain a catalyst precursor; The catalyst precursor is heated or baked at constant temperature, the temperature is 300-750 ℃, and the baking time is 2-20 h.
  2. 2. The method of claim 1, wherein the catalyst precursor is calcined at a temperature ranging from 400 ℃ to 650 ℃ for a period of 2 to 8 h.
  3. 3. The preparation method according to claim 1, wherein the precursor of SiO 2 is one or more selected from silica sol, 60-400 mesh column chromatography silica gel and thin layer chromatography silica gel, the precursor of MgO is one or more selected from magnesium nitrate, magnesium chloride, magnesium hydroxide and magnesium oxide, and the precursor of Al 2 O 3 is one or more selected from aluminum hydroxide, aluminum nitrate and aluminum trichloride.
  4. 4. The method according to claim 3, wherein the precursor of SiO 2 is one or more selected from silica sol, 200-300 mesh column chromatography silica gel, and thin layer chromatography silica gel.
  5. 5. The preparation method of the tungsten-bismuth composite oxide catalyst according to claim 1, wherein the adding amount of nitric acid in the step (1) is based on the pH range of the colloidal solution obtained in the step (1) being 0.1-3, the mass concentration of bismuth nitrate in the dilute nitric acid solution containing bismuth nitrate in the step (1) being 10-50%, and the adding amount of deionized water in a system being 5-45% of the mass fraction of the solid content in the solid solution suspension obtained in the step (2).
  6. 6. The preparation method according to claim 5, wherein the deionized water is added in an amount which satisfies the solid content of the solid solution suspension obtained in the step (2) by a mass fraction of 10% -30%.
  7. 7. The method according to claim 1, wherein the tungsten-bismuth composite oxide catalyst is a silica-based composition containing silica, magnesia, alumina, bismuth oxide and tungsten oxide, and contains 42 to 80 mol% of silicon, 4 to 30 mol% of magnesium, 5.5 to 28 mol% of aluminum, 6 to 30 mol% of bismuth, and 4.5 to 35 mol% of tungsten, based on the total molar amount of silicon, magnesium, aluminum, bismuth and tungsten.
  8. 8. The preparation method of the solid solution suspension according to claim 1, wherein the spray drying temperature of the solid solution suspension is 200-300 ℃, the roasting atmosphere of the catalyst precursor is one or more than two of oxygen, air, nitrogen or argon, the heating mode can be programmed heating or constant temperature, the temperature is 300-750 ℃, and the roasting time is 2-20 h.
  9. 9. The preparation method according to claim 8, wherein the spray drying temperature of the solid solution suspension is 250-300 ℃, the catalyst precursor is calcined in an air atmosphere, the temperature is increased by programming or constant temperature, the temperature is 400-650 ℃, and the calcination time is 2-8 h.
  10. 10. A tungsten bismuth composite oxide catalyst prepared by the preparation method of any one of claims 1 to 8.
  11. 11. Use of the tungsten bismuth composite oxide catalyst as claimed in claim 10 in the preparation of glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide.
  12. 12. The use according to claim 11, wherein the tungsten bismuth composite oxide catalyst is used for preparing glutaraldehyde by catalytic oxidation of 1, 2-epoxycyclopentane, and comprises the steps of mixing the tungsten bismuth composite oxide catalyst with a reaction solvent, adding 1, 2-epoxycyclopentane, adding hydrogen peroxide solution, and preparing glutaraldehyde by catalytic oxidation reaction.
  13. 13. The use according to claim 11 or 12, wherein the tungsten bismuth composite oxide catalyst is added in an amount of 1-10% by mass of 1, 2-cyclopentane epoxide, the molar ratio of hydrogen peroxide to 1, 2-cyclopentane epoxide is 1-1.5, and the volume/mass ratio of the solvent to 1, 2-cyclopentane epoxide is 1.5-8:1 (mL: g).
  14. 14. The method according to claim 13, wherein the tungsten bismuth composite oxide catalyst is added in an amount of 1-5% by mass of 1, 2-epoxycyclopentane, the molar ratio of hydrogen peroxide to 1, 2-epoxycyclopentane is 1.1-1.3, and the volume/mass ratio of the solvent to 1, 2-epoxycyclopentane is 2-4:1 (mL: g).
  15. 15. The use according to claim 12, wherein the reaction temperature is 25 ℃ to 80 ℃, the reaction time is 2 to 12 hours, and the reaction solvent is one or more of isopropanol, tertiary amyl alcohol, tertiary butanol, ethylene glycol monomethyl ether and ethylene glycol.
  16. 16. The use according to claim 15, wherein the reaction temperature is 25 ℃ to 50 ℃ and the reaction time is 2 to 6 hours.

Description

Tungsten bismuth composite oxide catalyst, preparation and application Technical Field The invention relates to the field of solid-liquid heterogeneous catalytic reaction, in particular to a high-efficiency catalyst for preparing glutaraldehyde by catalytic oxidation of 1, 2-cyclopentane epoxide, and a preparation method for producing glutaraldehyde by using the catalyst. Background Glutaraldehyde (GA for short), colorless or pale yellow oily liquid with pungent smell, is easily dissolved in water and ethanol, is dissolved in benzene, is nonflammable and nonvolatile, and is unstable in air. Can be oxidized by air at normal temperature, and is easy to undergo condensation, polymerization and other reactions. It is an important saturated straight-chain aliphatic dialdehyde, is an important fine chemical product and intermediate, and has the functions of crosslinking and solidifying protein. Is a high-efficiency low-toxicity sterilizing disinfectant, an excellent leather tanning agent, a color kinescope film hardening agent and an organic synthetic agent, and is widely applied to the fields of biomedical engineering, cell immunology, biochemistry, leather chemistry, histochemistry, microorganism industry, environmental protection and the like. The existing glutaraldehyde preparation methods mainly comprise a pyridine method, a pyran method, a pentanediol oxidation method, a glutaric acid reduction method, a cyclopentene oxidation method and the like. The earliest method for industrial production is a pyridine method, wherein pyridine is reduced to dihydropyridine, hydroxylamine is used for treatment to obtain glutaric oxime, and finally sodium nitrite and hydrochloric acid are used for converting the glutaric oxime to glutaraldehyde, so that the conversion rate of the method reaches 90%, and the yield is less than 50%. The method has the defects of high raw material consumption, high cost, high pollution, poor product quality and the like, and is eliminated. The pyran method is to synthesize 2-ethoxy-3, 4-dihydropyran by taking acrolein and vinyl diethyl ether as raw materials in a cyclic manner, and then to hydrolyze and open the ring to glutaraldehyde, and has the defects of high raw material cost, long process route and low product yield (for example, patent CN 102066302A). The pentanediol oxidation method has the disadvantages of low control of oxidation depth, low yield, high raw material shortage cost and the like of oxidation reaction although the reaction route is short, so that industrialization is difficult to realize. The glutaric acid method uses the by-product glutaric acid in the adipic acid production process as raw material, palladium as catalyst and tertiary first as auxiliary agent to reduce the glutaric acid into glutaraldehyde, the yield is 55-88%. Compared with the existing pyran method, the cost of the method can be reduced by 20%, but the method has the problem of short service life of the catalyst at present. The cyclopentene oxidation method is a method which is studied more nowadays and is also a synthetic route with the most development prospect at present. The route for synthesizing glutaraldehyde by catalytic oxidation of cyclopentene mainly comprises an ozone oxidation method, an oxide oxidation method, a cyclopentyl vicinal diol oxidation method, an air oxidation method, a hydrogen peroxide oxidation method and the like, wherein the oxidant is hydrogen peroxide, and has the advantages of low cost, sufficient raw material supply, clean process, short route, mild condition and the like, and has wide development prospect. The process of oxidizing cyclopentene under hydrogen peroxide to synthesize glutaraldehyde is that cyclopentene first reacts to produce 1, 2-epoxycyclopentane, and then the 1, 2-epoxycyclopentane is converted into beta-hydroxycyclopentyl hydroperoxide intermediate product, and beta-hydroxycyclopentyl hydroperoxide is rearranged to glutaraldehyde. The catalysts currently used for this reaction are typically molybdenum-based compounds, tungsten-based compounds, heteropolyacids, complex metal oxides, tungsten-based molecular sieve catalysts which support the active components onto mesoporous molecular sieves, and the like. In view of the ease of catalyst separation, current research on tungsten-based supported catalysts and tungsten-based molecular sieve catalysts is receiving extensive attention from the scholars. Chinese patent CN1425498 provides a tungsten-containing catalyst loaded by TiO2 microsphere as a carrier through closed crystallization, and the glutaraldehyde yield is up to 69.4 and 60.3 percent at the minimum. Chinese patent CN1680032a discloses a synthesis method of tungsten-based molecular sieve catalyst for preparing glutaraldehyde by selectively catalyzing and oxidizing cyclopentene with hydrogen peroxide as oxidant, which is prepared by introducing active tungsten source in situ into synthesized all-silicon mesoporous molecular sieve skeleton. The y