CN-121972185-A - Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof

CN121972185ACN 121972185 ACN121972185 ACN 121972185ACN-121972185-A

Abstract

The invention discloses a catalyst for preparing propylene by propane dehydrogenation, which comprises a carrier, an active component, a first auxiliary agent and a second auxiliary agent. The invention also discloses a preparation method of the catalyst for preparing propylene by dehydrogenating propane, which comprises the following steps of S1, dissolving a first auxiliary agent and a second auxiliary agent in an alcohol solution with the concentration of 75% -95% to obtain a mixed metal alcohol solution, S2, preprocessing a carrier, vacuum-drying the carrier at 40-110 ℃ for 3-20h to obtain a preprocessed carrier, S3, dipping the preprocessed carrier in the mixed metal alcohol solution obtained in the step S1, sealing, carrying out ultrasound, drying and roasting to obtain a catalyst precursor loaded with the first auxiliary agent and the second auxiliary agent, S4, dipping the catalyst precursor in the alcohol solution of platinum, sealing, carrying out ultrasound, and then drying and roasting to obtain the catalyst. The catalyst of the invention can improve the dehydrogenation yield of propane to 38 percent.

Inventors

JIAO LIRONG
Hu Fangpeng
YANG LIUQIAN
MA JIANJI
SHI JINGJING

Assignees

金川集团股份有限公司
兰州金川科技园有限公司

Dates

Publication Date: 20260505
Application Date: 20251230

Claims (10)

1. The catalyst for preparing propylene by dehydrogenating propane is characterized by comprising a carrier, an active component, a first auxiliary agent and a second auxiliary agent; wherein the active component is noble metal salt, and the load of the active component accounts for 0.05-0.8% of the mass of the carrier; the mass ratio of the first auxiliary agent to the second auxiliary agent is 1 (0.5-10); the second auxiliary agent is one or more of rare earth metal salt, alkali metal salt and alkaline earth metal salt.
2. The catalyst for preparing propylene by dehydrogenating propane according to claim 1, wherein the first auxiliary agent is copper salt, wherein the copper salt is any one of copper chloride, copper nitrate and copper sulfate; The alkali metal salt is any one of potassium nitrate, potassium chloride, sodium chloride and lithium aluminum oxide; the alkaline earth metal salt is any one of magnesium nitrate, magnesium chloride and calcium chloride; The rare earth metal salt is any one of lanthanum nitrate and cerium nitrate; The noble metal salt is a platinum salt.
3. The catalyst for the dehydrogenation of propane to propylene according to claim 2, wherein the platinum salt is platinum nitrate or chloroplatinic acid or ammonia chloroplatinate.
4. The catalyst for producing propylene by dehydrogenating propane according to claim 1, wherein the second auxiliary agent is a rare earth metal salt and an alkali metal salt in a mass ratio of (1-1.5): 2-1.
5. The catalyst for producing propylene by dehydrogenating propane according to claim 1, wherein the second auxiliary agent is a rare earth metal salt and an alkaline earth metal salt in a mass ratio of (1-1.5): 1.
6. The catalyst for producing propylene by dehydrogenating propane according to claim 1, wherein the second auxiliary agent is an alkali metal salt and an alkaline earth metal salt in a mass ratio of (2-1): 1.
7. The catalyst for producing propylene by dehydrogenating propane according to claim 1, wherein the second auxiliary agent is a rare earth metal salt, an alkali metal salt and an alkaline earth metal salt in a mass ratio of (1-1.5): (2-1): 1.
8. The catalyst for the dehydrogenation of propane to propylene according to claim 1, wherein the carrier is Al 2 O 3 or zirconia or silica or molecular sieve.
9. A method for preparing a catalyst for producing propylene by dehydrogenating propane as claimed in any one of claims 1 to 8, comprising the steps of: S1, preprocessing a carrier, and vacuum drying the carrier at 40-110 ℃ for 3-20 hours to obtain a preprocessed carrier; s2, dissolving the first auxiliary agent and the second auxiliary agent in an alcohol solution with the concentration of 75% -95% to obtain a mixed metal alcohol solution; S3, dipping the pretreated carrier in the mixed metal alcohol solution obtained in the step S2, sealing, performing ultrasonic treatment, and drying and roasting to obtain a catalyst precursor loaded with a first auxiliary agent and a second auxiliary agent; S4, soaking the catalyst precursor in an alcohol solution of platinum, sealing, performing ultrasonic treatment, and drying and baking to obtain the catalyst; in the steps S3 and S4, the ultrasonic time is 3-40min, the roasting temperature is 380-750 ℃ and the roasting time is 2-8h; Wherein, the platinum alcohol solution is obtained by dissolving 0.05 to 0.8 percent of platinum salt in the alcohol solution; wherein the alcohol solution is any one of methanol, ethanol and propylene glycol; wherein the alcohol solution has the same volume as the carrier.
10. Use of the catalyst of claims 1-8 and the catalyst obtained by the process of claim 9 in the dehydrogenation of propane.

Description

Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof Technical Field The invention relates to the technical field of catalysts, in particular to a catalyst for preparing propylene by propane dehydrogenation, a preparation method and application thereof. Background With the massive extraction and utilization of shale gas, propane becomes an inexpensive chemical raw material. The conversion of propane into a propylene product with high added value is significant to the economic development, so that the utilization rate of the propane raw material can be improved, the huge demand of the market on the propylene product can be met, and the research and application of new technology of economic, environment-friendly and efficient propylene development are greatly promoted. In the prior art, the platinum-based propane dehydrogenation catalyst commonly used in the propane dehydrogenation process often has the problems of easy sintering, carbon deposition and the like of the platinum base, so that the catalyst is deactivated rapidly and is irreversible in sintering, and the existing platinum-based propane dehydrogenation catalyst has great room for improvement. Disclosure of Invention Aiming at the technical problems, the invention provides a catalyst for preparing propylene by dehydrogenating propane, and a preparation method and application thereof. In order to achieve the above purpose, the technical scheme of the invention is as follows: the catalyst for preparing propylene by dehydrogenating propane includes carrier, active component, first assistant and second assistant; wherein the active component is noble metal salt, and the load of the active component accounts for 0.05-0.8% of the mass of the carrier; the mass ratio of the first auxiliary agent to the second auxiliary agent is 1 (0.5-10); the second auxiliary agent is one or more of rare earth metal salt, alkali metal salt and alkaline earth metal salt. Wherein the first auxiliary agent is copper salt, and the copper salt is any one of copper chloride, copper nitrate and copper sulfate; The alkali metal salt is any one of potassium nitrate, potassium chloride, sodium chloride and lithium aluminum oxide; the alkaline earth metal salt is any one of magnesium nitrate, magnesium chloride and calcium chloride; The rare earth metal salt is any one of lanthanum nitrate and cerium nitrate; The noble metal salt is a platinum salt. Wherein the platinum salt is platinum nitrate or chloroplatinic acid or ammonia chloroplatinate. Wherein the second auxiliary agent is rare earth metal salt and alkali metal salt with the mass ratio of (1-1.5) to (2-1). Wherein the second auxiliary agent is rare earth metal salt and alkaline earth metal salt with the mass ratio of (1-1.5) being 1. Wherein the second auxiliary agent is alkali metal salt and alkaline earth metal salt with the mass ratio of (2-1) being 1. Wherein the second auxiliary agent is rare earth metal salt, alkali metal salt and alkaline earth metal salt with the mass ratio of (1-1.5) to (2-1) of 1. Wherein the carrier is Al 2O3 or zirconia or silica or molecular sieve. The invention also provides a preparation method of the catalyst for preparing propylene by dehydrogenating propane, which comprises the following steps: S1, preprocessing a carrier, and vacuum drying the carrier at 40-110 ℃ for 3-20 hours to obtain a preprocessed carrier; s2, dissolving the first auxiliary agent and the second auxiliary agent in an alcohol solution with the concentration of 75% -95% to obtain a mixed metal alcohol solution; S3, dipping the pretreated carrier in the mixed metal alcohol solution obtained in the step S2, sealing, performing ultrasonic treatment, and drying and roasting to obtain a catalyst precursor loaded with a first auxiliary agent and a second auxiliary agent; S4, soaking the catalyst precursor in an alcohol solution of platinum, sealing, performing ultrasonic treatment, and drying and baking to obtain the catalyst; in the steps S3 and S4, the ultrasonic time is 3-40min, the roasting temperature is 380-750 ℃ and the roasting time is 2-8h; Wherein, the platinum alcohol solution is obtained by dissolving 0.05 to 0.8 percent of platinum salt in the alcohol solution. Wherein the alcohol solution is any one of methanol, ethanol and propylene glycol. Wherein the alcohol solution has the same volume as the carrier. The invention also provides application of the catalyst in propane dehydrogenation. The beneficial effects of the invention are as follows: 1. The catalyst of the invention can effectively control the size and the surface area of the active component of the catalyst under the synergistic effect of the first auxiliary agent and the second auxiliary agent, enhance the dispersibility of the active component, solve the problems of easy sintering of the platinum base of the active component and carbon deposition caused by the acidity of the catalyst carrier in th