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CN-122006734-A - Calcium catalyst, preparation method and application thereof, and olefin oxidation method

CN122006734ACN 122006734 ACN122006734 ACN 122006734ACN-122006734-A

Abstract

The invention relates to a calcium catalyst, a preparation method and application thereof and an olefin oxidation method, wherein the general formula of an active component of the catalyst is Ca e /(MoBi a Fe b X c Y d )O j , wherein X is at least one of IB group metal element, IIB group metal element, VIIB group metal element and VIII group metal element, Y is at least one of lanthanide series metal elements, a is 0.2-0.5, b is 0.1-0.5, c is 0.5-1.5, d is 0.1-0.5, e is 0.001-0.005, and j is the total number of oxygen atoms required by the valence of each element in the catalyst. The calcium catalyst has higher reactivity, can effectively improve the conversion rate of reactants, the selectivity and the yield of target products, and is particularly suitable for being applied to oxidation reaction, especially olefin oxidation.

Inventors

  • SONG WEILIN
  • YANG BIN
  • XU WENJIE

Assignees

  • 中石化（上海）石油化工研究院有限公司
  • 中国石油化工股份有限公司

Dates

Publication Date
20260512
Application Date
20250321
Priority Date
20241111

Claims (10)

  1. 1.A calcium catalyst is characterized in that the general formula of an active component of the catalyst is Ca e /(MoBi a Fe b X c Y d )O j ; Wherein X is at least one of group IB metal element, group IIB metal element, group VIIB metal element and group VIII metal element, Y is at least one of lanthanide series metal element; the value of a is 0.2-0.5, the value of b is 0.1-0.5, the value of c is 0.5-1.5, the value of d is 0.1-0.5, the value of e is 0.001-0.005, and j is the total number of oxygen atoms required for meeting the valence of each element in the catalyst.
  2. 2. The catalyst according to claim 1, wherein, in formula Ca e /(MoBi a Fe b X c Y d )O j , X is selected from at least one of Cu, zn, mn, co, ni, preferably at least one of Cu, co and Ni, more preferably Co and Ni, and the molar ratio of Co to Ni is 0.5-5, preferably 1-2; And/or Y is selected from at least one of Ce, la, nd, pr, preferably at least one of Ce, la and Nd, more preferably Ce and La, and the molar ratio of Ce to La is 0.5-5, preferably 1-2; And/or A is 0.3-0.4, and/or b is 0.15-0.3, and/or c is 0.7-1.2, and/or d is 0.15-0.3, and/or e is 0.002-0.003.
  3. 3. A method for preparing the calcium-based catalyst according to claim 1 or 2, characterized in that the method comprises: (1) Concentrating, drying and roasting slurry containing a Mo source, a Bi source, a Fe source, an X source and a Y source to obtain a precursor 1; (2) Crushing the precursor 1, mixing the crushed precursor with a binder and water, forming, drying and roasting to obtain a precursor 2; (3) The solution containing Ca source is immersed on the precursor 2, dried and baked to obtain the calcium catalyst.
  4. 4. The preparation method according to claim 3, wherein, In the step (1), the step of (a), The drying conditions include a temperature of 50-100deg.C, and/or The roasting condition includes that the temperature is 400-650℃ and/or In the step (2), the step of (C), The precursor 1 is broken into particles smaller than 100 μm, and/or The drying conditions include a temperature of 100-150deg.C, and/or The roasting condition includes that the temperature is 500-600℃ and/or The binder is organic binder, preferably one or more selected from hydroxypropyl cellulose, sesbania powder, polyvinyl alcohol and xanthan gum, and/or The mass ratio of the binder to the precursor 1 is 1-10:100, and/or The mass ratio of water to the precursor 1 is 5-20:100.
  5. 5. The process according to claim 3 or 4, wherein in the step (3), The impregnation being by means of equal volume impregnation, and/or The drying conditions include a temperature of 80-100deg.C, and/or The roasting condition includes that the temperature is 300-450℃ and/or The Ca source-containing solution is a calcium-containing alcoholic solution, preferably the Ca source-containing solution has a concentration of 1-10 wt.%, preferably the alcohol is a C1-C5 liquid alcohol, more preferably ethanol.
  6. 6. A calcium-based catalyst prepared by the method of any one of claims 3-5.
  7. 7. Use of the calcium-based catalyst according to any one of claims 1-2, 6 in an oxidation reaction, preferably in the oxidation of olefins, more preferably the olefins are C3-C5 alpha-olefins.
  8. 8. A process for oxidizing an olefin, which comprises contacting an olefin-containing raw gas with an oxidizing agent in the presence of the calcium-based catalyst according to any one of claims 1 to 2 and 6.
  9. 9. The method of claim 8, wherein, The olefin is a C3-C5 alpha-olefin, preferably propylene, and/or The olefin-containing feed gas further comprises a diluent gas selected from inert gases and/or steam, and/or The oxidizing agent is selected from one or more of oxidizing gases, preferably oxygen and/or air.
  10. 10. The method according to claim 8 or 9, wherein, The conditions of the contact reaction include: At a temperature of 300-450 ℃, preferably 310-350 ℃, and/or Pressure of 0.01-0.08MPa, and/or The volume-mass space velocity of the feed gas containing olefin is 1500-3000 mL/g.h, and/or The volume ratio of olefin, diluent gas and oxidant is 1:0.5-5:6-8.

Description

Calcium catalyst, preparation method and application thereof, and olefin oxidation method Technical Field The invention relates to a calcium catalyst, a preparation method and application thereof, and an olefin oxidation method. Background Acrolein is also called allylaldehyde, is mainly used for preparing bactericide glutaraldehyde, animal feed additive methionine, producing pesticide imidacloprid, antitumor agent 2, 3-dibromoacrolein and the like, can produce acrylic acid through oxidation, can further synthesize acrylic ester through reduction, can produce propanol through reduction, and is an important intermediate for synthesizing glycerol, allyl thiourea, allyl isothioate, perfume and medicine. The catalytic oxidation of propylene is one of the main ways to synthesize acrolein, and at present, 80% of acrolein yield in the world adopts the process route, and the catalyst component is mainly a Mo and Bi composite oxide system. The improvement of the catalyst is mainly carried out in terms of the activity and stability of the catalyst, such as adding transition metal into the active component to improve the activity and increase the yield of target products, adding rare earth elements to improve the oxidation-reduction capability, adding elements such as Fe, co, ni and the like to inhibit the sublimation of Mo, stabilizing the active component of the catalyst, prolonging the service life of the catalyst and the like. In addition, because of the severe exothermic phenomenon in the reaction, it is very important to control the reaction temperature of the catalyst bed, and the excessive hot spot temperature not only enables the reaction to proceed in the deep oxidation direction, reduces the yield of acrolein, but also shortens the service life of the catalyst and affects the stable operation of the device. US6268529 proposes a propylene oxidation catalyst with a propylene conversion of 98.1% but with an acrolein yield of only 65.3% and an acrylic acid yield of 20.8%. CN1564709 improves catalyst performance by adding organic carboxylic acid to overcome catalyst non-uniformity caused by layering between metal salts during the co-precipitation process of catalyst preparation. The method is used for propylene oxidation reaction, the propylene conversion rate is 98.12% at the highest, and the acrolein selectivity is 82.53% at the highest. The acid-base property of the surface of the catalyst influences the adsorption and desorption of reactants and products, thereby influencing the oxidation reaction degree of the reaction, so that the acid-base property of the surface of the catalyst is regulated, the oxidation reaction depth can be controlled, and the yield of acrolein is improved. Alkaline earth metals and alkali metals are commonly used to regulate the selective oxidation of propylene to improve selectivity and yield (e.g., CN1169619C, CN 1183088C), but the reaction gas for the selective oxidation of propylene to acrolein contains a large amount of water, the alkali metals are unstable in water gas, and the alkaline earth metals tend to be covered by other components due to the formation of precipitates. Disclosure of Invention Aiming at the defects of the prior art, one of the technical problems to be solved by the invention is to provide a novel calcium catalyst which has higher reactivity, can effectively improve the conversion rate of reactants, the selectivity and the yield of target products, is particularly suitable for being applied to oxidation reaction, and is particularly suitable for being applied to olefin oxidation. In order to achieve the above object, the first aspect of the present invention provides a calcium-based catalyst, wherein the active component of the catalyst has a general formula of Ca e/(MoBiaFebXcYd)Oj, wherein X is at least one of a group IB metal element, a group IIB metal element, a group VIIB metal element, and a group VIII metal element, Y is at least one of a lanthanide series metal element, a has a value of 0.2 to 0.5, b has a value of 0.1 to 0.5, c has a value of 0.5 to 1.5, d has a value of 0.1 to 0.5, and e has a value of 0.001 to 0.005, j is the total number of oxygen atoms required to satisfy the valence of each element in the catalyst. The second aspect of the present invention provides a method for preparing the calcium-based catalyst of the present invention, comprising: (1) Concentrating, drying and roasting slurry containing a Mo source, a Bi source, a Fe source, an X source and a Y source to obtain a precursor 1; (2) Crushing the precursor 1, mixing the crushed precursor with a binder and water, forming, drying and roasting to obtain a precursor 2; (3) The solution containing Ca source is immersed on the precursor 2, dried and baked to obtain the calcium catalyst. The third aspect of the invention provides the calcium-based catalyst prepared by the method. In a fourth aspect, the present invention provides the use of the calcium-based catalyst according to th