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CN-122006769-A - Double-component catalyst, preparation method and application thereof, and method for preparing olefin by hydrogenation of carbon dioxide

CN122006769ACN 122006769 ACN122006769 ACN 122006769ACN-122006769-A

Abstract

The invention relates to the technical field of catalyst preparation, and provides a two-component catalyst, a preparation method and application thereof, and a method for preparing olefin by carbon dioxide hydrogenation. The double-component catalyst comprises a component I and a component II, wherein the component I comprises a composition with a chemical formula of Fe 100 A a B b Si c O x in terms of atomic ratio, A is selected from at least one of Mn and Mo, B is selected from at least one of alkali metals, a is 10-200, B is 1-10, C is 50-500, x is the total number of oxygen atoms required for meeting the valence of each element in the component I, the component II comprises a composition with a chemical formula of (Fe 4 N) 25 (K 2 O) d ) in terms of atomic ratio, and d is 1-10.

Inventors

  • PANG YINGCONG
  • LI JIANFENG
  • DAI YIMIN

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
20241108

Claims (10)

  1. 1. A two-component catalyst, characterized in that the catalyst comprises component I and component II; The component I comprises a composition with a chemical formula of Fe 100 A a B b Si c O x in terms of atomic ratio, wherein A is selected from one of Mn and Mo, B is selected from at least one of alkali metals, a is 10-200, B is 1-10, c is 50-500, and x is the total number of oxygen atoms required for meeting the valence of each element in the component I; the component II comprises a composition with a chemical formula of (Fe 4 N) 25 (K 2 O) d ) in terms of atomic ratio, wherein d has a value range of 1-10.
  2. 2. The catalyst according to claim 1, wherein the mass ratio of the component I to the component II is 0.2-5:1.
  3. 3. A process for preparing a catalyst according to claim 1 or 2, comprising mixing the component I and the component II to obtain the catalyst.
  4. 4. The method according to claim 3, wherein the component I is prepared by precipitating Fe ions in a Fe precursor solution to obtain Fe hydroxide, obtaining a mixture comprising Fe hydroxide, A precursor, B precursor, si precursor and water, spray-drying, and first calcining to obtain the component I; Preferably, the method comprises the steps of, The molar ratio of the Fe precursor calculated by Fe to the A precursor calculated by A to the B precursor calculated by B to the Si precursor calculated by Si is 100:10-200:1-10:50-500.
  5. 5. The method of claim 4, wherein the precipitating comprises mixing a Fe precursor solution with a precipitating agent; And/or before the mixture is spray dried, adjusting the pH value of the mixture to be 1-5; And/or the inlet temperature of the spray drying is 280-350 ℃, and the outlet temperature is 120-210 ℃; And/or, the spray-dried medium is air; and/or the roasting temperature of the first roasting is 400-700 ℃ and the roasting time is 0.5-5 h.
  6. 6. The preparation method of the component II according to any one of claims 3 to 5, wherein the preparation method comprises the steps of immersing a solution comprising a K precursor on an iron oxide, performing second roasting, and performing nitriding treatment in a mixed atmosphere comprising ammonia and hydrogen at 500-800 ℃ to obtain the component II; Preferably, the method comprises the steps of, The molar ratio of the Fe precursor to the K precursor is 100:2-20; and/or the second roasting temperature is 500-800 ℃ and the second roasting time is 1-6 h; And/or the nitriding treatment time is 3-30 hours; And/or the volume ratio of the ammonia gas to the hydrogen gas in the mixed atmosphere is 0.5-5:1.
  7. 7. The preparation method of the iron oxide according to claim 6, wherein the preparation method comprises the steps of precipitating Fe ions in the Fe precursor solution to obtain Fe hydroxide, washing, drying and third roasting the Fe hydroxide to obtain the iron oxide; preferably, the third roasting temperature is 550-800 ℃ and the roasting time is 1-6 h.
  8. 8. Use of a two-component catalyst according to claim 1 or 2 or a two-component catalyst prepared according to any one of claims 3 to 7 in a reaction for the hydrogenation of carbon dioxide to olefins.
  9. 9. A method for preparing olefin by hydrogenation of carbon dioxide, which is characterized by comprising the steps of contacting and reacting a raw material comprising CO 2 and H 2 with the two-component catalyst according to claim 1 or 2 or the two-component catalyst prepared by the preparation method according to any one of claims 3-7 to generate olefin; Preferably, the method comprises the steps of, The reaction temperature is 320-400 ℃; And/or the reaction pressure is 2-8 MPa; And/or the standard volume space velocity of the catalyst load is 2000-9000 h -1 ; and/or the molar ratio of CO 2 to H 2 is 0.2-1:1.
  10. 10. The method of claim 9, wherein the catalyst is treated with CH 4 prior to use; Preferably, the method comprises the steps of, The temperature of the treatment by adopting CH 4 is 400-500 ℃; And/or the pressure of the treatment by adopting CH 4 is 0.5-5 MPa; And/or the treatment time by adopting CH 4 is 3-10 hours; And/or the actual volume space velocity of the catalyst load treated by CH 4 is 300-1200 h -1 .

Description

Double-component catalyst, preparation method and application thereof, and method for preparing olefin by hydrogenation of carbon dioxide Technical Field The invention relates to the technical field of catalyst preparation, in particular to a two-component catalyst, a preparation method and application thereof, and a method for preparing olefin by hydrogenation of carbon dioxide. Background CO 2 is a major greenhouse gas, and its dramatic increase in emissions results in a series of environmental and climate problems such as global temperature rise. Thus, capture and utilization of CO 2 has attracted considerable attention in both academia and industry, which is desirable to help address environmental and energy issues. Wherein its conversion to chemicals is a very promising way of utilization. Combining green hydrogen with CO 2 not only consumes CO 2, but also converts it into valuable carbonaceous chemicals, reducing the dependence on fossil energy. Numerous processes for converting CO 2 to various carbonaceous chemicals have been disclosed in the prior art. For example, patent CN110947384a discloses a method for converting CO 2 to methanol by hydrogenation, and patent CN111790436B discloses a technology for converting CO 2 to aromatic hydrocarbons. Because of the stability of the molecules of CO 2 and the difficulty in carbon chain growth, the prior art for preparing organic hydrocarbons, particularly olefins, by hydrogenating CO 2 generally prepares lower olefins as the main product, and reports about preparing C 4 + olefins by hydrogenating CO 2 are relatively few. To improve the efficient utilization of CO 2, there is no surprise in developing techniques for the hydroconversion thereof to olefins, particularly C 4 + linear alpha olefins. Disclosure of Invention The invention aims to provide a two-component catalyst, a preparation method and application thereof and a method for preparing olefin by hydrogenating carbon dioxide, so as to solve the technical problem that CO 2 is difficult to prepare C 4 + olefin by hydrogenating in the prior art. In order to achieve the above purpose, the invention adopts the following technical scheme: In a first aspect, the present invention provides a two-component catalyst comprising component I and component II; The component I comprises a composition with a chemical formula of Fe 100AaBbSicOx in terms of atomic ratio, wherein A is selected from one of Mn and Mo, B is selected from at least one of alkali metals, a is 10-200, B is 1-10, c is 50-500, and x is the total number of oxygen atoms required for meeting the valence of each element in the component I; the component II comprises a composition with a chemical formula of (Fe 4N)25(K2O)d) in terms of atomic ratio, wherein d has a value range of 1-10. According to some embodiments of the invention, B is selected from at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs). According to some embodiments of the invention, a has a value ranging from 30 to 150. According to some embodiments of the invention, b has a value ranging from 3 to 10. According to some embodiments of the invention, the value range of c is 100-450. According to some embodiments of the invention, d has a value ranging from 3 to 7. According to some embodiments of the invention, the mass ratio of the component I to the component II is 0.2-5:1. In a second aspect, the invention provides a method for preparing the catalyst of the first aspect, which comprises mixing the component I and the component II to obtain the catalyst. According to some embodiments of the invention, the preparation method of the component I comprises the steps of precipitating Fe ions in a Fe precursor solution to obtain Fe hydroxide, obtaining a mixture comprising Fe hydroxide, an A precursor, a B precursor, a Si precursor and water, and spray-drying and first roasting to obtain the component I. According to some embodiments of the present invention, the molar ratio of the Fe precursor calculated as Fe, the a precursor calculated as a, the B precursor calculated as B, and the Si precursor calculated as Si is 100:10 to 200:1 to 10:50 to 500. According to some embodiments of the invention, the precipitating comprises mixing the Fe precursor solution with a precipitating agent. According to some embodiments of the invention, the precipitant comprises an alkaline substance, such as ammonia. According to some embodiments of the invention, the first Fe precursor comprises at least one of Fe salts, such as ferric nitrate, ferric chloride, ferric citrate, and the like. According to some embodiments of the invention, the a precursor comprises at least one of a Mn salt, a Mo salt, for example, the Mn salt may be manganese nitrate or the like, and the Mo salt may be ammonium heptamolybdate or the like. According to some embodiments of the invention, the B precursor comprises at least one of alkali metal salts, e.g., naOH, naNO 3、KOH、KNO3、RbOH、RbNO3, etc. Ac