Patent Application
20230096172
The invention relates to the field of industrial catalyst preparation, in particular to a catalyst for propane dehydrogenation to propylene and a preparation method and application thereof.
Propylene is one of the important raw materials for the production of acrolein, polypropylene, acetone, polyacrylonitrile and propylene oxide. The traditional propylene production process is fluid catalytic cracking and steam cracking of naphtha and light diesel oil. With the rapid consumption of fossil energy, the traditional propylene production method cannot meet the increasing demand for propylene. Therefore, new propylene production processes have been developed, such as propane dehydrogenation (PDH), methanol to olefins (MTO) and Fischer-Tropsch synthesis (FTO). Among them, PDH process is specialized in producing propylene rather than mixed olefins. The plant is easy to be expanded to large-scale, with fewer reaction by-products, easy separation of reactants and products, and low cost. In addition, the rapid development of fracturing technology makes it possible to exploit and utilize shale gas in large scale. Propane is the main component of shale gas, which will significantly reduce the price of propane and give more prominence to the advantages of PDH process.
Up to now, PDH process includes direct PDH process without oxidant: Catofin (Lummus, CrOx based catalyst), Oleflex (UOP, Pt based catalyst) and oxidized PDH process with O2: Star (Thyssen Krupp, Pt supported on calcium and zinc aluminates). Since the propylene selectivity of direct PDH is higher than that of oxidized PDH, direct PDH has been mainly industrialized. Direct PDH is a highly endothermic reaction with thermodynamic limitation and the activation of propane C—H bond is the decisive step which determines the catalytic performance of PDH. The C—H bond of propane is very stable, so a higher reaction temperature (550-700° C.) is needed to achieve C—H bond fracture. However, at high temperature C—C bond breaking is more favorable than C—H bond breaking, and propylene is more difficult to desorb than propane, so it is prone to cracking, deep dehydrogenation or polymerization reactions, resulting in low selectivity and coking.
Compared with CrOx-based catalysts, Pt based catalysts have the advantages of environmental protection and high stability. However, the supported Pt catalyst without promoter and unmodified support has no selectivity for propylene, which is easy to form heavy carbon deposition to cover the active sites, resulting in rapid deactivation of the catalyst. Therefore, it is necessary to add additives to improve propylene selectivity. At present, the research is mainly made on Pt—Sn based catalysts.
For example, patent CN108722468b discloses a propane dehydrogenation catalyst with spherical montmorillonite mesoporous composite as support, Pt as active component, Sn and Na as promoters. With the help of novel support with three peak por size distribution and appropriate Pt/Sn ratio, the catalyst shows good catalytic performance and stability.
Patent CN109529911A discloses a propane dehydrogenation catalyst with SBA-16 mesoporous silicon as support and Pt and Sn as active components. SBA-16 is prepared with cetyltrimethylammonium bromide and triblock polymer as template. The catalyst has uniform framework structure and pore distribution, high catalytic performance and stability for propane dehydrogenation.
However, Pt—Sn catalyst is still easy to be deactivated because of the following reasons: 1) the active component Pt particles are sintered and covered by carbon deposition; 2) partial reduction of Sn in propane dehydrogenation atmosphere results in Pt—Sn alloy which poisons Pt; 3) the specific surface area, pore volume and pore diameter change of Al2O3 occurs under the reaction condition; 4) Pt—Sn loading cannot completely eliminate the inherent acid sites of Al2O3 which cause serious deep dehydrogenation, cracking and coking. Therefore, it is necessary to further improve the Pt—Sn catalyst by introducing other components, enhancing the interaction between Pt and support and promoter, inhibiting Pt sintering and Sn segregating resulting in irreversible poisoning of Pt, and reducing the acidity of Al2O3.
The introduction of low acidic oxides into the carrier can reduce the acidity of the carrier, improve the “Pt-carrier” interaction, and limit the segregation and reduction of
Sn. Generally, the addition of alkali metal elements (Li, Na, K) can reduce the acidity of the carrier, and causes part of its activity loss. Rare earth metal elements are potential excellent promoters: for example, Y-modified ZrO2 support can significantly improve the dispersion and anti-sintering ability of Pt/YSZ (fuel, 2010, 89, 2244-2251) and Pt (Rh, Pd)/YSZ catalysts. Y modified Al2O3 can also improve the interactions between Pd and carrier in Pd/Ce—Zr—Y/Al2O3 catalyst, and inhibit other components in the catalyst causing Pd poisoning. La can also play a similar role as reported in Fuel. Process. Technol., 2013, 111, 94-104.
To sum up, although Pt—Sn based catalysts are the main catalysts for propane dehydrogenation to propylene, and Sn can improve the propylene selectivity and propylene yield of the catalysts, the support acidity is still strong, the instability of Pt particles and the alloying of Sn to Pt are still easy to lead to the deactivation of Pt—Sn catalysts. Therefore, the problem needs to be resolved.
In order to solve the above technical problems, the invention provides a catalyst for propane dehydrogenation to propylene, a preparation method and application thereof. The purpose of this invention is to modify and improve the Pt—Sn based catalyst, and improve its catalytic performance and stability.
The invention is realized by the following technical scheme:
A catalyst for propane dehydrogenation to propylene comprises a carrier, an active component supported on the carrier, a first promoter, a second promoter and a third promoter;
The carrier is alumina ball; the active component is noble metal Pt; the rare earth metal elements of the first auxiliary agent are Y, La, Ce, Pr or Nd; the second auxiliary agent is Sn; the alkali metal elements of the third auxiliary agent are Li, Na and K, preferably K.
As for the content of each component in the catalyst, the mass fraction of the carrier is 80%˜99.6%, preferably 96.2%˜98.7%, taking the total mass of the catalyst as the standard;
The mass fraction of the active component Pt is 0.1%˜5%, preferably 0.2%˜0.5%;
The content of rare earth metal elements Y, La, Ce, Pr or Nd in the first additive is 0.1%˜5%, preferably 0.5%˜2%;
The mass fraction of Sn in the second additive is 0.1%˜5%, preferably 0.1%˜0.3%;
The mass fraction of the third additive K is 0.1%˜5%, preferably 0.5%˜1%.
In a preferred scheme of the invention, the catalyst comprises a carrier, an active component supported on the carrier, a first promoter, a second promoter and a third promoter;
The carrier is alumina ball, the active component Pt, the first auxiliary agent is rare earth element, the second auxiliary agent Sn and the third auxiliary agent K;
Taking the total mass of the catalyst as the standard, the mass fraction of support is 96.2%˜98.7%, the mass fraction of Pt is 0.2%˜0.5%, the mass fraction of rare earth elements Y, La, Ce, Pr or Nd is 0.5%˜2%, the mass fraction of Sn is 0.1%˜0.3%, and the mass fraction of K is 0.5%˜1%
A preparation method of a catalyst for propane dehydrogenation to propylene comprises the following steps:
1) Pt precursor, Sn precursor and competitive adsorption agent were dissolved in water to form impregnation solution A;
2) The alumina ball carrier is impregnated in the impregnation solution A, and then dried and calcined;
3) The rare earth metal precursor and K precursor are dissolved in water to form impregnation solution B;
4) The catalyst for propane dehydrogenation was prepared by impregnating the carrier in impregnation solution B, drying and calcining after impregnation.
Furthermore, in step 1), Pt precursor is chloroplatinic acid and Sn precursor is SnCl2;
Furthermore, the competitive adsorption agent in step 1) is one of the following inorganic and organic acid: concentrated hydrochloric acid, concentrated nitric acid, oxalic acid and citric acid, and concentrated hydrochloric acid is preferred;
Furthermore, the amount of competitive adsorption agent in step 1) is 7-9% of impregnation solution A;
Furthermore, the rare earth metal precursors in step 3) are soluble salts, preferably YCl3, LaCl3, Ce (NO3)3, PR (NO3)3 and Nd (NO3)3;
Furthermore, the K precursor in step 3) is soluble potassium salt, and KNO3 is preferred;
Furthermore, the impregnated alumina balls are dried in vacuum at 80-120° C. for 6-10 h and calcined at 550-650° C. for 3-5h to obtain the catalyst for propane dehydrogenation to olefins.
The application of the catalyst in propane dehydrogenation to propylene of this invention: specifically, the reaction conditions of propane dehydrogenation to propylene testing are as follows: the reaction is carried out in a quartz tube fixed bed reactor, the reaction temperature is 550° C.˜650° C., the total space velocity is 1 h−1˜5 h−1, and the hydrogen/propane flow ratio is 1/4-1/1.
The invention uses rare earth metal elements Y, La, Ce, Pr and Nd as the first promoter to modify and improve the Pt—Sn based catalyst, so as to reduce the support acidity, inhibit Pt sintering and Sn segregation, and Sn alloying of Pt, and improve the catalytic performance and stability of the catalyst.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. The catalyst for propane dehydrogenation to propylene is modified and improved by using rare earth metal elements Y, La, Ce, Pr and Nd as the first promoter, which has high catalytic performance and stability;
2. The preparation method of the catalyst for propane dehydrogenation to propylene reduces the acidity of the support, inhibits Pt sintering and Sn segregation, and Sn alloying of Pt, and improves the catalytic performance and stability of the catalyst.
In order to make the purpose, the technical scheme and the advantages of the invention clearer, the present invention is further described in detail in combination with the embodiment. The schematic implementation and description of the invention are only used to explain the invention, not as the limitation of the invention.
In this embodiment, Catalyst 1, Pt—Sn—K—Y/Al2O3 is prepared, and its catalytic performance for propane dehydrogenation to propylene is tested.
Preparation: 1) prepare 0.02 g/g H2PtCl6.6H2O aqueous solution and 0.04 g/g SnCl2.2H2O aqueous solution.
Take 4.075 g and 0.729 g H2PtCl6.6H2O solution and SnCl2.2H2O solution respectively and put into a glass beaker, then add concentrated hydrochloric acid and deionized water, so that the volume of Pt—Sn impregnation solution is equal to the total volume of water absorbed by 10 g Al2O3 carrier, and the mass of concentrated hydrochloric acid is 8.3% of the mass of impregnation solution. After stirring evenly, impregnate 10 g alumina ball carrier with the solution. After soaking for 4 h, vacuum drying at 100° C. for 8 h and then calcine at 600° C. for 4 h;
2) Prepare KNO3 aqueous solution with mass concentration of 0.07 g/g and YCl3 aqueous solution with mass concentration of 0.312 g/g respectively.
Take 3.023 g and 0.722 g KNO3 solution and YCl3 solution and put into a glass beaker and then add deionized water to make the volume of K—Y impregnation solution equal to the total volume of water absorption capacity of 10 g Al2O3 carrier. After stirring evenly, the alumina ball carrier calcined in step 1) is impregnated with the K—Y impregnation solution. The final Pt—Sn—K—Y/Al2O3 catalyst for propane dehydrogenation is then obtained by impregnation for 4 h, vacuum drying at 100° C. for 8 h and calcination at 600° C. for 4h.
Catalyst evaluation: a quartz tube fixed bed reactor was filled with 3 g Catalyst 1, the total mass space velocity of hydrogen and propane was controlled at 3 h−1, the hydrogen/propane flow ratio was 1/4, the reaction pressure was atmospheric pressure, the bed temperature was 610° C., and the reaction products were analyzed by using Shimadzu GC-2014C gas chromatography.
In this embodiment, Catalyst 2, Pt—Sn—K—La/Al2O3 is prepared, and its catalytic performance for propane dehydrogenation to propylene is tested.
Preparation: 1) prepare 0.02 g/g H2PtCl6.6H2O aqueous solution and 0.04 g/g SnCl2.2H2O aqueous solution.
Take 4.075 g and 0.729 g H2PtCl6.6H2O solution and SnCl2.2H2O solution respectively and put into a glass beaker, then add concentrated hydrochloric acid and deionized water, so that the volume of Pt—Sn impregnation solution is equal to the total volume of water adsorbed by 10 g Al2O3 carrier, and the mass of concentrated hydrochloric acid is 8.3% of the mass of impregnation solution. After stirring evenly, impregnate 10 g alumina ball carrier with this solution. Then soaking for 4 h, vacuum drying at 100° C. for 8 h and calcining at 600° C. for 4 h;
2) Prepare KNO3 aqueous solution with mass concentration of 0.07 g/g and LaCl3 aqueous solution with mass concentration of 0.271 g/g respectively.
Take 3.023 g and 0.667 g KNO3 solution and LaCl3 solution respectively and put into a glass beaker, and then add deionized water to make the volume of K—La impregnation solution equal to the total volume of water absorption capacity of 10 g Al2O3 carrier. After stirring evenly, the alumina ball carrier calcined in step 1) is impregnated with this solution. The final Pt—Sn—K—La/Al2O3 catalyst for propane dehydrogenation is obtained by impregnation for 4 h, vacuum drying at 100° C. for 8 h and calcination at 600° C. for 4 h.
Catalyst evaluation: a quartz tube fixed bed reactor was filled with 3 g Catalyst 2, the total mass space velocity of hydrogen and propane was controlled to be 3 h−1, the hydrogen/propane flow ratio was 1/4, the reaction pressure was atmospheric pressure, the bed temperature was 610° C., and the reaction products were analyzed by using Shimadzu GC-2014C gas chromatography.
In this embodiment, Catalyst 3, Pt—Sn—K—Ce/Al2O3 is prepared, and its catalytic performance for propane dehydrogenation to propylene is tested.
Preparation: 1) prepare 0.02 g/g H2PtCl6.6H2O aqueous solution and 0.04 g/g SnCl2.2H2O aqueous solution. Take 4.075 g and 0.729 g H2PtCl6.6H2O solution and SnCl2.2H2O solution respectively and put into a glass beaker, then add concentrated hydrochloric acid and deionized water, so that the volume of Pt—Sn impregnation solution is equal to the total volume of water absorbed by 10 g Al2O3 carrier, and the mass of concentrated hydrochloric acid is 8.3% of the mass of impregnation solution. After stirring evenly, impregnate 10 g alumina ball carrier with this solution. Then soaking for 4 h, vacuum drying at 100° C. for 8 h and calcining at 600° C. for 4 h;
2) Prepare KNO3 aqueous solution with mass concentration of 0.07 g/g and Ce(NO3)3.6H2O aqueous solution with mass concentration of 0.2 g/g respectively.
Take 3.023 g and 1.585 g KNO3 solution and Ce(NO3)3.6H2O solution respectively and put into a glass beaker, and then add deionized water to make the volume of K—Ce impregnation solution equal to the total volume of water absorption capacity of 10 g Al2O3 carrier. After stirring evenly, the alumina ball carrier calcined in step 1) is impregnated with this solution. The final Pt—Sn—K—Ce/Al2O3 catalyst for propane dehydrogenation was obtained by impregnation for 4 h, vacuum drying at 100° C. for 8 h and calcination at 600° C. for 4 h.
Catalyst evaluation: a quartz tube fixed bed reactor was filled with 3 g Catalyst 3, the total mass space velocity of hydrogen and propane was controlled to be 3 h−1, the hydrogen/propane flow ratio was 1/4, the reaction pressure was atmospheric pressure, the bed temperature was 610° C., and the reaction products were analyzed by using Shimadzu GC-2014C gas chromatography.
In this embodiment, Catalyst 4, Pt—Sn—K—Pr/Al2O3 is prepared, and its catalytic performance for propane dehydrogenation to propylene is tested.
Preparation: 1) prepare 0.02 g/g H2PtCl6.6H2O aqueous solution and 0.04 g/g SnCl2.2H2O aqueous solution.
Take 4.075 g and 0.729 g H2PtCl6.6H2O solution and SnCl2.2H2O solution respectively and put into a glass beaker, then add concentrated hydrochloric acid and deionized water, so that the volume of Pt—Sn impregnation solution is equal to the total volume of water absorbed by 10 g Al2O3 carrier, and the mass of concentrated hydrochloric acid is 8.3% of the mass of impregnation solution. After stirring evenly, impregnate 10 g alumina ball carrier with this solution. Then soaking for 4 h, vacuum drying at 100° C. for 8 h and calcining at 600° C. for 4 h;
2) Prepare KNO3 aqueous solution with mass concentration of 0.07 g/g and Pr(NO3)3.6H2O aqueous solution with mass concentration of 0.2 g/g respectively.
Take the KNO3 solution and Pr(NO3)3.6H2O solution 3.023 g and 1.579 g respectively, then add deionized water to make the volume of K—Pr impregnation solution equal to the total volume of water absorption capacity of 10 g Al2O3 carrier. After stirring evenly, the alumina ball carrier calcined in step 1) is impregnated with this solution. The final Pt—Sn—K—Pr/Al2O3 catalyst for propane dehydrogenation was obtained by impregnation for 4h, vacuum drying at 100° C. for 8h and calcination at 600° C. for 4h.
Catalyst evaluation: a quartz tube fixed bed reactor was filled with 3 g Catalyst 4, the total mass space velocity of hydrogen and propane was controlled to be 3 h−1, the hydrogen/propane flow ratio was 1/4, the reaction pressure was atmospheric pressure, the bed temperature was 610° C., and the reaction products were analyzed by using Shimadzu GC-2014C gas chromatography.
In this embodiment, Catalyst 4, Pt—Sn—K—Nd/Al2O3 is prepared, and its catalytic performance for propane dehydrogenation to propylene is tested.
Preparation: 1) prepare 0.02 g/g H2PtCl6.6H2O aqueous solution and 0.04 g/g SnCl2.2H2O aqueous solution.
Take 4.075 g and 0.729 g H2PtCl6.6H2O solution and SnCl2.2H2O solution respectively and put into a glass beaker, then add concentrated hydrochloric acid and deionized water, so that the volume of Pt—Sn impregnation solution is equal to the total volume of water absorbed by 10 g Al2O3 carrier, and the mass of concentrated hydrochloric acid is 8.3% of the mass of impregnation solution. After stirring evenly, impregnate 10 g alumina ball carrier with this solution. Then soaking for 4 h, vacuum drying at 100° C. for 8 h and calcining at 600° C. for 4 h;
2) Prepare KNO3 aqueous solution with mass concentration of 0.07 g/g and Nd(NO3)3.6H2O aqueous solution with mass concentration of 0.2 g/g.
Take 3.023 g and 1.555 g of KNO3 solution and Nd(NO3)3.6H2O solution and put into a glass beaker, and then add deionized water to make the volume of K—Pr impregnation solution equal to the total volume of water absorption capacity of 10 g Al2O3 carrier. After stirring evenly, the alumina ball carrier calcined in step 1) is impregnated with this solution. The final Pt—Sn—K—Nd/Al2O3 catalyst for propane dehydrogenation was obtained by impregnation for 4 h, vacuum drying at 100° C. for 8 h and calcination at 600° C. for 4 h.
Catalyst evaluation: a quartz tube fixed bed reactor was filled with 3 g Catalyst 5, the total mass space velocity of hydrogen and propane was controlled to be 3 h−1, the hydrogen/propane flow ratio was 1/4, the reaction pressure was atmospheric pressure, the bed temperature was 610° C., and the reaction products were analyzed by using Shimadzu GC-2014C gas chromatography.
In this comparative embodiment, Catalyst 6, Pt—Sn—K/Al2O3 is prepared, and its catalytic performance for propane dehydrogenation to propylene is tested. The catalyst does not contain any rare earth elements as the first promoter.
Preparation: 1) prepare 0.02 g/g H2PtCl6.6H2O aqueous solution and 0.04 g/g SnCl2.2H2O aqueous solution.
Take 4.075 g and 0.729 g H2PtCl6.6H2O solution and SnCl2.2H2O solution respectively and put into a glass beaker, then add concentrated hydrochloric acid and deionized water, so that the volume of Pt—Sn impregnation solution is equal to the total volume of water adsorbed by 10 g Al2O3 carrier, and the mass of concentrated hydrochloric acid is 8.3% of the mass of impregnation solution. After stirring evenly, impregnate 10 g alumina ball carrier with this solution. Then soaking for 4 h, vacuum drying at 100° C. for 8 h and calcining at 600° C. for 4 h;
2) Prepare KNO3 aqueous solution with mass concentration of 0.07 g/g.
Take 3.023 g KNO3 solution and put into a glass beaker, and then add deionized water to make the volume of K impregnation solution equal to the total volume of water absorption capacity of 10 g Al2O3 carrier. After stirring thoroughly, the alumina ball carrier calcined in step 1) is impregnated with this solution. The final Pt—Sn—K/Al2O3 catalyst for propane dehydrogenation was obtained by impregnation for 4 h, vacuum drying at 100° C. for 8 h and calcination at 600° C. for 4 h.
Catalyst evaluation: a quartz tube fixed bed reactor was filled with 3 g Catalyst 6, the total mass space velocity of hydrogen and propane was controlled to be 3 h−1, the hydrogen/propane flow ratio was 1/4, the reaction pressure was atmospheric pressure, the bed temperature was 610° C., and the reaction products were analyzed by using Shimadzu GC-2014C gas chromatography.
The content of active components and promoters of Catalysts 1-6 is shown in Table 1; The testing results of catalytic performance of the catalysts prepared by examples 1-5 and comparative example 1 are given in Table 2.
Combined with the evaluation results in Tables 1 and 2, it is shown that the performance of Pt—Sn based propane dehydrogenation catalyst can be modified by adding rare earth metal elements. Compared with comparative example 1, Y can significantly improve the catalytic performance and stability of Pt—Sn based propane dehydrogenation catalyst, while La can only play a slightly improving role. Ce and Pr decrease the catalytic performance and stability of Pt—Sn based catalysts.
The above-mentioned specific implementation examples further describe the purpose, technical scheme and beneficial effect of the invention. It should be understood that the above-mentioned is only the specific implementation examples of the invention, and is not used to limit the protection scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201911370195.8 | Dec 2019 | CN | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2020/108566 | 8/12/2020 | WO |
