[go: up one dir, main page]

WO2021128867A1 - 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 - Google Patents

一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 Download PDF

Info

Publication number
WO2021128867A1
WO2021128867A1 PCT/CN2020/108566 CN2020108566W WO2021128867A1 WO 2021128867 A1 WO2021128867 A1 WO 2021128867A1 CN 2020108566 W CN2020108566 W CN 2020108566W WO 2021128867 A1 WO2021128867 A1 WO 2021128867A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
propane
dehydrogenation
carrier
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2020/108566
Other languages
English (en)
French (fr)
Inventor
卓润生
张辰
张平
杨光友
刘新生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rezel Catalysts Co Ltd
Original Assignee
Rezel Catalysts Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rezel Catalysts Co Ltd filed Critical Rezel Catalysts Co Ltd
Priority to EP20905470.9A priority Critical patent/EP4023332B1/en
Priority to US17/042,132 priority patent/US20230096172A1/en
Publication of WO2021128867A1 publication Critical patent/WO2021128867A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • C07C5/3337—Catalytic processes with metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
    • C07C2523/63—Platinum group metals with rare earths or actinides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the field of industrial catalyst preparation, in particular to a catalyst used for propane dehydrogenation to propylene, and a preparation method and application thereof.
  • Propylene is one of the important raw materials for the production of industrial products such as acrolein, polypropylene, acetone, polyacrylonitrile and propylene oxide.
  • the traditional propylene production process is fluidized catalytic cracking and steam cracking of naphtha and light diesel. With the rapid consumption of fossil energy, traditional propylene production methods can no longer 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-to-olefins (FTO).
  • PDH propane dehydrogenation
  • MTO methanol-to-olefins
  • FTO Fischer-Tropsch synthesis-to-olefins
  • the PDH process exclusively produces propylene rather than mixed olefins, and the equipment is easy to be large.
  • the PDH process includes the direct PDH process without adding an oxidant: Catofin (Lummus, CrO x -based catalyst), Oleflex (UOP, Pt-based catalyst) and O 2 oxidized PDH process: Star (Thyssen Krupp, calcium, zinc aluminum Salt-loaded Pt). Since the propylene selectivity of direct PDH is higher than that of oxidized PDH, direct PDH has been mainly commercialized. Direct PDH is a highly endothermic reaction limited by thermodynamics. Propane CH bond activation is the rate-determining step that determines the catalytic performance of PDH. However, the CH bond of propane is highly stable, so a higher reaction temperature (550-700°C) is required to achieve the cleavage of the CH bond.
  • CC bonds are more advantageous than CH bonds to break at high temperatures, and the product propylene is more difficult to desorb than propane, so side reactions such as cracking, deep dehydrogenation, or polymerization are prone to occur, resulting in low selectivity and coking.
  • Pt-based catalysts Compared with CrO x -based catalysts, Pt-based catalysts have the advantages of environmental protection and high stability. However, the supported Pt catalysts without promoters and unmodified supports are not selective to propylene, and are prone to form heavy carbon deposits to cover the active sites, leading to rapid catalyst deactivation. Therefore, additives need to be added to increase the selectivity of propylene.
  • Pt-Sn such as:
  • Patent CN108722468B discloses a propane dehydrogenation catalyst with spherical smectite mesoporous composite material as the carrier, Pt as the active component, Sn and Na as the auxiliary agent, with the help of a novel carrier with a trimodal distribution and a suitable Pt/Sn ratio , The catalyst shows good catalytic performance and stability.
  • Patent CN109529911A discloses a propane dehydrogenation catalyst with SBA-16 mesoporous silica as the carrier and Pt and Sn as the active components.
  • SBA-16 is based on cetyltrimethylammonium bromide and triblock polymer Prepared as a template.
  • the catalyst has uniform structure and pore structure, high catalytic performance and stability for propane dehydrogenation.
  • the Pt-Sn catalyst is still prone to deactivation because: 1) the active component Pt particles are sintered and covered by carbon deposits; 2) Sn is partially reduced in the propane dehydrogenation reducing atmosphere to form a Pt-Sn alloy to poison Pt; 3 ) The specific surface area, pore volume and pore diameter change under the conditions of Al 2 O 3 reaction; 4) Pt-Sn loading cannot completely eliminate the inherent acid sites of Al 2 O 3 , and there are still serious deep dehydrogenation, cracking and coking.
  • Y-modified ZrO 2 supports can significantly increase the activity of the alkane steam reforming catalysts Pt/YSZ (Fuel, 2010, 89, 2244-2251) and Pt (Rh, Pd)/YSZ catalysts Component dispersion and anti-sintering ability.
  • Y-modified Al 2 O 3 in Pd/Ce-Zr-Y/Al 2 O 3 can also increase the interaction between Pd and the carrier, and inhibit other components from causing Pd poisoning.
  • the rare earth element La can also play a similar role (Fuel.Process.Technol., 2013, 111, 94-104).
  • the present invention provides a catalyst for the dehydrogenation of propane to propylene, and a preparation method and application thereof.
  • the aim is to modify and improve the Pt-Sn-based catalyst to improve the catalytic performance and stability of the catalyst.
  • a catalyst for the dehydrogenation of propane to propylene comprising a carrier, an active component supported on the carrier, a first auxiliary agent, a second auxiliary agent, and a third auxiliary agent;
  • the carrier is alumina ball; the active component is precious metal Pt; the first additive rare earth metal element is Y, La, Ce, Pr or Nd; the second additive is Sn; the third additive
  • the auxiliary alkali metal elements are Li, Na, K, preferably K.
  • the carrier mass fraction is 80% to 99.6%, preferably 96.2% to 98.7%.
  • the mass fraction of the active component Pt is 0.1% to 5%, preferably 0.2% to 0.5%;
  • the mass fraction of the second auxiliary agent Sn is 0.1% to 5%, preferably 0.1% to 0.3%;
  • the mass fraction of the third auxiliary agent K is 0.1% to 5%, preferably 0.5% to 1%.
  • the catalyst includes a carrier and an active component supported on the carrier and a first auxiliary agent, a second auxiliary agent and a third auxiliary agent;
  • the carrier is alumina balls, the active component is Pt, the first auxiliary is rare earth elements, the second auxiliary is Sn, and the third auxiliary is K;
  • the carrier mass fraction is 96.2%-98.7%
  • the Pt mass fraction is 0.2%-0.5%
  • the rare-earth metal element Y, La, Ce, Pr or Nd is 0.5%-2%
  • Sn The mass fraction is 0.1% to 0.3%
  • the mass fraction of K is 0.5% to 1%.
  • a method for preparing a catalyst for the dehydrogenation of propane to propylene includes the following steps:
  • the alumina ball carrier is immersed in the immersion solution A, dried and roasted after the immersion is completed;
  • step 1) the Pt precursor is chloroplatinic acid, and the Sn precursor is SnCl 2 ;
  • the competitive adsorbent in step 1) is inorganic and organic acids: concentrated hydrochloric acid, concentrated nitric acid, oxalic acid, citric acid, preferably concentrated hydrochloric acid;
  • step 1) the amount of the competitive adsorbent in step 1) is 7-9% of the impregnating solution A;
  • the rare earth metal precursor in step 3) is a soluble salt, preferably YCl 3 , LaCl 3 , Ce(NO 3 ) 3 , Pr(NO 3 ) 3 and Nd(NO 3 ) 3 ;
  • the K precursor in step 3) is a soluble potassium salt, preferably KNO 3 ;
  • step 2) and step 4 the impregnated alumina balls are vacuum dried at 80-120°C for 6-10 hours, and calcined at 550-650°C for 3-5 hours, to obtain a propane dehydrogenation to olefin catalyst.
  • the reaction conditions for the dehydrogenation of propane to propylene are: the reaction is carried out in a quartz tube fixed bed reactor, the reaction temperature is 550°C to 650°C, and the total mass is empty. The speed is 1h -1 ⁇ 5h -1 , and the ratio of hydrogen/propane flow rate is 1/4-1/1.
  • the Pt-Sn-based catalyst is modified and improved by using the rare earth metal elements Y, La, Ce, Pr, and Nd as the first auxiliary agent to reduce the acidity of the carrier, inhibit Pt sintering and Sn precipitation, and the alloying of Sn to Pt. Improve the catalytic performance and stability of the catalyst.
  • the present invention has the following advantages and beneficial effects:
  • a catalyst for the dehydrogenation of propane to propylene of the present invention uses rare earth metal elements Y, La, Ce, Pr, and Nd as the first auxiliary agent to modify and improve the Pt-Sn-based catalyst.
  • the catalytic performance and stability performance are high;
  • the preparation method of a catalyst for the dehydrogenation of propane to propylene of the present invention reduces the acidity of the carrier, suppresses Pt sintering and Sn precipitation, and Sn alloys Pt, and improves the catalytic performance and stability of the catalyst.
  • catalyst 1 Pt-Sn-KY/Al 2 O 3 was prepared , and the catalytic performance of propane dehydrogenation to propylene was tested.
  • Preparation 1) Prepare a H 2 PtCl 6 ⁇ 6H 2 O solution with a mass concentration of 0.02 g/g and a SnCl 2 ⁇ 2H 2 O solution with a mass concentration of 0.04 g/g. Take 4.075g and 0.729g of H 2 PtCl 6 ⁇ 6H 2 O solution and SnCl 2 ⁇ 2H 2 O solution respectively, then add concentrated hydrochloric acid and deionized water to make the volume of Pt-Sn impregnation solution equal to 10g Al 2 O 3 carrier total water absorption The mass of concentrated hydrochloric acid is 8.3% of the mass of the dipping solution. After stirring, 10g Al 2 O 3 ball carrier is dipped. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and baking at 600°C for 4 hours;
  • step 2) Prepare a KNO 3 solution with a mass concentration of 0.07 g/g and a YCl 3 solution with a mass concentration of 0.312 g/g. Take 3.023g and 0.722g of KNO 3 solution and YCl 3 solution respectively, and add deionized water to make the volume of KY impregnation solution equal to the total water absorption of 10g Al 2 O 3 carrier. After being evenly stirred, the Al 2 O 3 spherical support calcined in step 1) is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and calcination at 600°C for 4 hours to obtain a Pt-Sn-KY/Al 2 O 3 propane dehydrogenation catalyst.
  • catalyst 2 Pt-Sn-K-La/Al 2 O 3 was prepared , and the catalytic performance of the dehydrogenation of propane to propylene was tested.
  • Preparation 1) Prepare a H 2 PtCl 6 ⁇ 6H 2 O solution with a mass concentration of 0.02 g/g and a SnCl 2 ⁇ 2H 2 O solution with a mass concentration of 0.04 g/g. Take 4.075g and 0.729g of H 2 PtCl 6 ⁇ 6H 2 O solution and SnCl 2 ⁇ 2H 2 O solution respectively, then add concentrated hydrochloric acid and deionized water to make the volume of Pt-Sn impregnation solution equal to 10g Al 2 O 3 carrier total water absorption The mass of concentrated hydrochloric acid is 8.3% of the mass of the dipping solution. After stirring, 10g Al 2 O 3 ball carrier is dipped. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and baking at 600°C for 4 hours;
  • step 2) Prepare a KNO 3 solution with a mass concentration of 0.07 g/g and a LaCl 3 solution with a mass concentration of 0.271 g/g. Take 3.023g and 0.667g of KNO 3 solution and LaCl 3 solution respectively, and add deionized water to make the volume of K-La impregnation solution equal to the total water absorption of 10g Al 2 O 3 carrier. After being evenly stirred, the Al 2 O 3 spherical support calcined in step 1) is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and calcination at 600°C for 4 hours to obtain a Pt-Sn-K-La/Al 2 O 3 propane dehydrogenation catalyst.
  • catalyst 3 Pt-Sn-K-Ce/Al 2 O 3 was prepared , and the catalytic performance of the dehydrogenation of propane to propylene was tested.
  • Preparation 1) Prepare a H 2 PtCl 6 ⁇ 6H 2 O solution with a mass concentration of 0.02 g/g and a SnCl 2 ⁇ 2H 2 O solution with a mass concentration of 0.04 g/g. Take 4.075g and 0.729g of H 2 PtCl 6 ⁇ 6H 2 O solution and SnCl 2 ⁇ 2H 2 O solution respectively, then add concentrated hydrochloric acid and deionized water to make the volume of Pt-Sn impregnation solution equal to 10g Al 2 O 3 carrier total water absorption The mass of concentrated hydrochloric acid is 8.3% of the mass of the impregnating solution. After stirring, 10g Al 2 O 3 ball carrier is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and baking at 600°C for 4 hours;
  • step 2) Prepare a KNO 3 solution with a mass concentration of 0.07 g/g and a Ce(NO 3 ) 3 ⁇ 6H 2 O solution with a mass concentration of 0.2 g/g. Take 3.023g and 1.585g of KNO 3 solution and Ce(NO 3 ) 3 ⁇ 6H 2 O solution respectively, and add deionized water to make the volume of K-Ce impregnation solution equal to the total water absorption of 10g Al 2 O 3 carrier. After being evenly stirred, the Al 2 O 3 spherical support calcined in step 1) is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and calcination at 600°C for 4 hours to obtain a Pt-Sn-K-Ce/Al 2 O 3 propane dehydrogenation catalyst.
  • catalyst 4 Pt-Sn-K-Pr/Al 2 O 3 was prepared , and the catalytic performance of the dehydrogenation of propane to propylene was tested.
  • Preparation 1) Prepare a H 2 PtCl 6 ⁇ 6H 2 O solution with a mass concentration of 0.02 g/g and a SnCl 2 ⁇ 2H 2 O solution with a mass concentration of 0.04 g/g. Take 4.075g and 0.729g of H 2 PtCl 6 ⁇ 6H 2 O solution and SnCl 2 ⁇ 2H 2 O solution respectively, then add concentrated hydrochloric acid and deionized water to make the volume of Pt-Sn impregnation solution equal to 10g Al 2 O 3 carrier total water absorption The mass of concentrated hydrochloric acid is 8.3% of the mass of the dipping solution. After stirring, 10g Al 2 O 3 ball carrier is dipped. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and baking at 600°C for 4 hours;
  • step 2) Prepare a KNO 3 solution with a mass concentration of 0.07 g/g and a Pr(NO 3 ) 3 ⁇ 6H 2 O solution with a mass concentration of 0.2 g/g. Take 3.023g and 1.579g of KNO 3 solution and Pr(NO 3 ) 3 ⁇ 6H 2 O solution respectively, and add deionized water to make the volume of K-Pr impregnation solution equal to the total water absorption of 10g Al 2 O 3 carrier. After being evenly stirred, the Al 2 O 3 spherical support calcined in step 1) is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and calcination at 600°C for 4 hours to obtain a Pt-Sn-K-Pr/Al 2 O 3 propane dehydrogenation catalyst.
  • catalyst 5 Pt-Sn-K-Nd/Al 2 O 3 was prepared , and its catalytic performance for propane dehydrogenation to propylene was tested.
  • Preparation 1) Prepare a H 2 PtCl 6 ⁇ 6H 2 O solution with a mass concentration of 0.02 g/g and a SnCl 2 ⁇ 2H 2 O solution with a mass concentration of 0.04 g/g. Take 4.075g and 0.729g of H 2 PtCl 6 ⁇ 6H 2 O solution and SnCl 2 ⁇ 2H 2 O solution respectively, then add concentrated hydrochloric acid and deionized water to make the volume of Pt-Sn impregnation solution equal to 10g Al 2 O 3 carrier total water absorption The mass of concentrated hydrochloric acid is 8.3% of the mass of the dipping solution. After stirring, 10g Al 2 O 3 ball carrier is dipped. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and baking at 600°C for 4 hours;
  • Step 2) Prepare a KNO 3 solution with a mass concentration of 0.07 g/g and a Nd(NO 3 ) 3 ⁇ 6H 2 O solution with a mass concentration of 0.2 g/g. Take 3.023 g and 1.555 g of KNO 3 solution and Nd(NO 3 ) 3 ⁇ 6H 2 O solution, respectively, and add deionized water to make the volume of the K-Pr impregnation solution equal to the total water absorption of 10 g of Al 2 O 3 carrier. After being evenly stirred, the Al 2 O 3 spherical support calcined in step 1) is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and calcination at 600°C for 4 hours to obtain a Pt-Sn-K-Nd/Al 2 O 3 propane dehydrogenation catalyst.
  • catalyst 6 Pt-Sn-K/Al 2 O 3 was prepared , and the catalytic performance of propane dehydrogenation to propylene was tested.
  • the catalyst is a blank comparative example, and the first auxiliary agent rare earth metal element is not added.
  • Preparation 1) Prepare a H 2 PtCl 6 ⁇ 6H 2 O solution with a mass concentration of 0.02 g/g and a SnCl 2 ⁇ 2H 2 O solution with a mass concentration of 0.04 g/g. Take 4.075g and 0.729g of H 2 PtCl 6 ⁇ 6H 2 O solution and SnCl 2 ⁇ 2H 2 O solution respectively, then add concentrated hydrochloric acid and deionized water to make the volume of Pt-Sn impregnation solution equal to 10g Al 2 O 3 carrier total water absorption The mass of concentrated hydrochloric acid is 8.3% of the mass of the dipping solution. After stirring, 10g Al 2 O 3 ball carrier is dipped. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and baking at 600°C for 4 hours;
  • step 2) Prepare a KNO 3 solution with a mass concentration of 0.07 g/g. Separately take 3.023 g of KNO 3 solution, and then add deionized water to make the volume of the K immersion solution equal to the total water absorption of 10 g of Al 2 O 3 carrier. After being evenly stirred, the Al 2 O 3 spherical support calcined in step 1) is impregnated. After immersing for 4 hours, vacuum drying at 100°C for 8 hours, and calcination at 600°C for 4 hours to obtain a Pt-Sn-K/Al 2 O 3 propane dehydrogenation catalyst.
  • the content detection of the active components and auxiliary agents of the catalyst 1-6 is shown in Table 1; the catalytic performance detection of the catalyst prepared in Examples 1-5 and the blank comparative example 1 is shown in Table 2.
  • Table 1 and Table 2 show that the addition of rare earth metal elements can improve the performance of the Pt-Sn-based propane dehydrogenation catalyst.
  • Y will significantly improve the Pt-Sn-based propane dehydrogenation.
  • La can only slightly promote the catalytic performance and stability of the catalyst.
  • Ce and Pr will reduce the catalytic performance and stability of Pt-Sn-based catalysts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用，所述催化剂包括载体以及负载在载体上的活性组分和助剂；其中，载体为氧化铝球，所述活性组分为铂族金属，所述助剂包括三种：稀土元素(Y、La、Ce、Pr、Nd)、锡和碱金属元素(Li、Na、K)；使用该催化剂进行丙烷脱氢制丙烯反应时，可以得到较高的丙烷转化率和丙烯选择性。

Description

一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 技术领域
本发明涉及工业催化剂制备领域，具体涉及一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用。
背景技术
丙烯是生产丙烯醛、聚丙烯、丙酮、聚丙烯腈和环氧丙烷等工业产品的重要原料之一。传统的丙烯生产工艺是石脑油和轻柴油的流化催化裂化和蒸汽裂解。随着化石能源的快速消耗，传统丙烯生产方法已不能满足日益增长的丙烯需求。因此，已经发展出新的丙烯生产工艺，如丙烷脱氢(PDH)、甲醇制烯烃(MTO)和费托合成制烯烃(FTO).其中，PDH工艺专产丙烯而非混合烯烃，装置容易大型化，反应副产物较少，反应物和产物易分离、成本较低。此外，目前迅速发展的压裂技术，使大量开采和利用页岩气成为可能。而丙烷是页岩气的主要成分，会使丙烷价格显著降低，愈发凸显PDH工艺的优势。
迄今为止，PDH工艺包括不添加氧化剂的直接PDH工艺：Catofin(Lummus，CrO x基催化剂)、Oleflex(UOP，Pt基催化剂)和添加O 2的氧化PDH工艺：Star(Thyssen Krupp,钙、锌铝酸盐负载的Pt).鉴于直接PDH的丙烯选择性高于氧化PDH，因此已实现工业化的主要以直接PDH为主。直接PDH是热力学限制的高吸热反应，丙烷C-H键活化是决定PDH催化性能决速步骤。但是丙烷的C-H键高度稳定，因此需要较高的反应温度(550-700℃)来实现C-H键断裂。然而，高温下C-C键比C-H键断裂更有利，产物丙烯比丙烷更难脱附，因此容易发生裂化、深度脱氢或聚合反应等副反应，导致低选择性和结焦。
与CrO x基催化剂相比，Pt基催化剂具有环保、高稳定性等优点。但是无助剂、载体未修饰的负载型Pt催化剂对丙烯无选择性，容易形成重质积碳覆盖活性位点导致催化剂快速失活。因此，需要添加助剂以提高丙烯选择性，目前主要以Pt-Sn为基础展开研究，例如：
专利CN108722468B公开了一种以球形蒙脱石介孔复合材料为载体，Pt为活性组分、Sn和Na为助剂的丙烷脱氢催化剂，借助具有三峰分布的新颖载体和适宜的Pt/Sn比例，该催化剂表现出较好的催化性能和稳定性。
专利CN109529911A公开了一种以SBA-16介孔硅为载体，Pt、Sn为活性组分的丙烷脱氢催化剂，SBA-16是以十六烷基三甲基溴化铵和三嵌段聚合物为模板剂制备的。该催化剂具有结构、孔结构均一，较高丙烷脱氢催化性能和稳定性。
但是Pt-Sn催化剂依然易于失活，原因在于：1)活性组分Pt颗粒烧结及被积炭所覆盖；2)Sn在丙烷脱氢还原气氛中部分还原形成Pt-Sn合金使Pt中毒；3)Al 2O 3反应条件下比表 面积、孔体积和孔径改变；4)Pt-Sn负载无法完全消除Al 2O 3固有酸位点，依然存在严重的深度脱氢、裂化和结焦。因此，需要进一步改进Pt-Sn催化剂：负载其他组分，增强Pt与载体和助剂相互作用，抑制Pt烧结和Sn析出导致Pt不可逆中毒，降低Al 2O 3酸性。
通过向载体引入低酸性氧化物有助于降低载体酸性，提高“Pt-载体”相互作用，限制Sn析出和还原。通常加入碱金属元素(Li、Na、K)仅能降低载体酸性，且会损失部分活性。稀土金属元素是潜在优良助剂：例如Y改性的ZrO 2载体能够明显提高烷烃蒸汽重整催化剂Pt/YSZ(Fuel,2010,89,2244-2251)和Pt(Rh、Pd)/YSZ催化剂活性组分分散性和抗烧结能力。Y改性的Al 2O 3在Pd/Ce–Zr–Y/Al 2O 3也能提高Pd与载体相互作用，抑制其它组分造成Pd中毒。稀土元素La亦能起到类似作用(Fuel.Process.Technol.,2013,111,94-104).
综上所述，目前丙烷脱氢制丙烯催化剂尽管以Pt-Sn基催化剂为主，且Sn能提高催化剂丙烯选择性和丙烯产率，但是载体酸性依然较强，Pt颗粒不稳定和Sn对Pt的合金化等问题依然容易导致Pt-Sn催化剂失活。因此，需要进一步解决该问题。
发明内容
为了解决以上技术问题，本发明提供一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用。旨在对Pt-Sn基催化剂进行修饰和改进，提高催化剂催化性能和稳定性。
本发明通过下述技术方案实现：
一种用于丙烷脱氢制丙烯的催化剂，该催化剂包括载体以及负载在载体上的活性组分和第一助剂、第二助剂以及第三助剂；
所述载体为氧化铝球；所述活性组分为贵金属Pt；所述第一助剂稀土金属元素为Y、La、Ce、Pr或Nd；所述第二助剂为Sn；所述第三助剂碱金属元素为Li、Na、K，优选K.
关于该催化剂中各组分含量，以所述催化剂总质量为标准，所述载体质量分数为80％～99.6％，优选为96.2％～98.7％.
所述活性组分Pt质量分数为0.1％～5％，优选为0.2％～0.5％；
所述第一助剂稀土金属元素Y、La、Ce、Pr或Nd，质量分数为0.1％～5％，优选为0.5％～2％；
所述第二助剂Sn质量分数为0.1％～5％，优选为0.1％～0.3％；
所述第三助剂K质量分数为0.1％～5％，优选为0.5％～1％.
在本发明的一个优选方案中，该催化剂包括载体以及负载在载体上的活性组分和第一助剂、第二助剂以及第三助剂；
所述载体为氧化铝球，活性组分Pt，第一助剂为稀土元素，第二助剂Sn，第三助剂K；
以所述催化剂总质量为标准，载体质量分数为96.2％～98.7％，Pt质量分数0.2％～0.5％，稀土金属元素Y、La、Ce、Pr或Nd质量分数为0.5％～2％，Sn质量分数为0.1％～0.3％，K质 量分数为0.5％～1％.
一种用于丙烷脱氢制丙烯的催化剂的制备方法，包括以下步骤：
1)将Pt前驱体、Sn前躯体和竞争吸附剂溶于水中形成浸渍液A；
2)将氧化铝球载体浸渍在浸渍液A中，浸渍完成后经干燥、焙烧；
3)将稀土金属前驱体、K前驱体溶于水中形成浸渍液B；
4)将2)中焙烧后载体浸渍在浸渍液B中，浸渍完成后经干燥、焙烧得到丙烷脱氢催化剂。
进一步的，步骤1)中Pt前驱体为氯铂酸、Sn前驱体为SnCl 2；
进一步的，步骤1)中所述竞争吸附剂为无机及有机酸：浓盐酸、浓硝酸、草酸、柠檬酸，优选浓盐酸；
进一步的，步骤1)中所述竞争吸附剂用量为浸渍液A的7-9％；
进一步的，步骤3)中稀土金属前驱体为可溶性盐，优选为YCl 3、LaCl 3、Ce(NO 3) 3、Pr(NO 3) 3和Nd(NO 3) 3；
进一步的，步骤3)中K前驱体为可溶性钾盐，优选KNO 3；
进一步的，步骤2)和步骤4)中将浸渍后的氧化铝球在80-120℃真空干燥6-10h，在550-650℃焙烧3-5h，即得到丙烷脱氢制烯烃催化剂。
本发明催化剂在丙烷脱氢制丙烯中的应用：具体的，所述丙烷脱氢制丙烯的反应条件为：反应在石英管固定床反应器中进行，反应温度550℃～650℃，总质量空速为1h -1～5h -1，氢气/丙烷流量比例1/4-1/1.
本发明通过采用稀土金属元素Y、La、Ce、Pr、Nd为第一助剂对Pt-Sn基催化剂进行修饰和改进，降低载体酸性、抑制Pt烧结和Sn析出及Sn对Pt的合金化、提高催化剂催化性能和稳定性。
本发明与现有技术相比，具有如下的优点和有益效果：
1、本发明一种用于丙烷脱氢制丙烯的催化剂通过采用稀土金属元素Y、La、Ce、Pr、Nd为第一助剂对Pt-Sn基催化剂进行修饰和改进，催化性能和稳定性能高；
2、本发明一种用于丙烷脱氢制丙烯的催化剂的制备方法降低载体酸性、抑制Pt烧结和Sn析出及Sn对Pt的合金化、提高催化剂催化性能和稳定性。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，下面结合实施例，对本发明作进一步的详细说明，本发明的示意性实施方式及其说明仅用于解释本发明，并不作为对本发明的限定。
实施例1
本实施例制备催化剂1，Pt-Sn-K-Y/Al 2O 3，并对其丙烷脱氢制丙烯的催化性能进行测试。
制备：1)配置质量浓度为0.02g/g的H 2PtCl 6·6H 2O溶液，质量浓度0.04g/g的SnCl 2·2H 2O溶液。分别取H 2PtCl 6·6H 2O溶液和SnCl 2·2H 2O溶液4.075g和0.729g,再加入浓盐酸和去离子水，使Pt-Sn浸渍液体积等于10g Al 2O 3载体总吸水量，且浓盐酸质量为浸渍液质量的8.3％.搅拌均匀后浸渍10g Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h；
2)配置质量浓度为0.07g/g的KNO 3溶液，质量浓度为0.312g/g的YCl 3溶液。分别取KNO 3溶液和YCl 3溶液3.023g和0.722g，再加入去离子水，使K-Y浸渍液体积等于10g Al 2O 3载体总吸水量。搅拌均匀后浸渍步骤1)中焙烧后的Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h得到Pt-Sn-K-Y/Al 2O 3丙烷脱氢催化剂。
评价：在石英管固定床反应器中装填3g催化剂1，控制氢气和丙烷总质量空速为3h -1，氢气/丙烷流量比1/4，反应压力为常压，床层温度610℃，反应产物用岛津GC-2014C气相色谱进行分析。
实施例2
本实施例制备催化剂2，Pt-Sn-K-La/Al 2O 3，并对其丙烷脱氢制丙烯的催化性能进行测试。
制备：1)配置质量浓度为0.02g/g的H 2PtCl 6·6H 2O溶液，质量浓度0.04g/g的SnCl 2·2H 2O溶液。分别取H 2PtCl 6·6H 2O溶液和SnCl 2·2H 2O溶液4.075g和0.729g,再加入浓盐酸和去离子水，使Pt-Sn浸渍液体积等于10g Al 2O 3载体总吸水量，且浓盐酸质量为浸渍液质量的8.3％.搅拌均匀后浸渍10g Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h；
2)配置质量浓度为0.07g/g的KNO 3溶液，质量浓度为0.271g/g的LaCl 3溶液。分别取KNO 3溶液和LaCl 3溶液3.023g和0.667g，再加入去离子水，使K-La浸渍液体积等于10g Al 2O 3载体总吸水量。搅拌均匀后浸渍步骤1)中焙烧后的Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h得到Pt-Sn-K-La/Al 2O 3丙烷脱氢催化剂。
评价：在石英管固定床反应器中装填3g催化剂2，控制氢气和丙烷总质量空速为3h -1，氢气/丙烷流量比1/4，反应压力为常压，床层温度610℃，反应产物用岛津GC-2014C气相色谱进行分析。
实施例3
本实施例制备催化剂3，Pt-Sn-K-Ce/Al 2O 3，并对其丙烷脱氢制丙烯的催化性能进行测试。
制备：1)配置质量浓度为0.02g/g的H 2PtCl 6·6H 2O溶液，质量浓度0.04g/g的SnCl 2·2H 2O溶液。分别取H 2PtCl 6·6H 2O溶液和SnCl 2·2H 2O溶液4.075g和0.729g,再加入浓盐酸和去离子水，使Pt-Sn浸渍液体积等于10g Al 2O 3载体总吸水量，且浓盐酸质量为浸渍液质量的8.3％. 搅拌均匀后浸渍10g Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h；
2)配置质量浓度为0.07g/g的KNO 3溶液，质量浓度为0.2g/g的Ce(NO 3) 3·6H 2O溶液。分别取KNO 3溶液和Ce(NO 3) 3·6H 2O溶液3.023g和1.585g，再加入去离子水，使K-Ce浸渍液体积等于10g Al 2O 3载体总吸水量。搅拌均匀后浸渍步骤1)中焙烧后的Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h得到Pt-Sn-K-Ce/Al 2O 3丙烷脱氢催化剂。
评价：在石英管固定床反应器中装填3g催化剂3，控制氢气和丙烷总质量空速为3h -1，氢气/丙烷流量比1/4，反应压力为常压，床层温度610℃，反应产物用岛津GC-2014C气相色谱进行分析。
实施例4
本实施例制备催化剂4，Pt-Sn-K-Pr/Al 2O 3，并对其丙烷脱氢制丙烯的催化性能进行测试。
制备：1)配置质量浓度为0.02g/g的H 2PtCl 6·6H 2O溶液，质量浓度0.04g/g的SnCl 2·2H 2O溶液。分别取H 2PtCl 6·6H 2O溶液和SnCl 2·2H 2O溶液4.075g和0.729g,再加入浓盐酸和去离子水，使Pt-Sn浸渍液体积等于10g Al 2O 3载体总吸水量，且浓盐酸质量为浸渍液质量的8.3％.搅拌均匀后浸渍10g Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h；
2)配置质量浓度为0.07g/g的KNO 3溶液，质量浓度为0.2g/g的Pr(NO 3) 3·6H 2O溶液。分别取KNO 3溶液和Pr(NO 3) 3·6H 2O溶液3.023g和1.579g，再加入去离子水，使K-Pr浸渍液体积等于10g Al 2O 3载体总吸水量。搅拌均匀后浸渍步骤1)中焙烧后的Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h得到Pt-Sn-K-Pr/Al 2O 3丙烷脱氢催化剂。
评价：在石英管固定床反应器中装填3g催化剂4，控制氢气和丙烷总质量空速为3h -1，氢气/丙烷流量比1/4，反应压力为常压，床层温度610℃，反应产物用岛津GC-2014C气相色谱进行分析。
实施例5
本实施例制备催化剂5，Pt-Sn-K-Nd/Al 2O 3,并对其丙烷脱氢制丙烯催化性能进行测试。
制备：1)配置质量浓度为0.02g/g的H 2PtCl 6·6H 2O溶液，质量浓度0.04g/g的SnCl 2·2H 2O溶液。分别取H 2PtCl 6·6H 2O溶液和SnCl 2·2H 2O溶液4.075g和0.729g,再加入浓盐酸和去离子水，使Pt-Sn浸渍液体积等于10g Al 2O 3载体总吸水量，且浓盐酸质量为浸渍液质量的8.3％.搅拌均匀后浸渍10g Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h；
2)配置质量浓度为0.07g/g的KNO 3溶液，质量浓度为0.2g/g的Nd(NO 3) 3·6H 2O溶液。分别取KNO 3溶液和Nd(NO 3) 3·6H 2O溶液3.023g和1.555g，再加入去离子水，使K-Pr浸渍液体积等于10g Al 2O 3载体总吸水量。搅拌均匀后浸渍步骤1)中焙烧后的Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h得到Pt-Sn-K-Nd/Al 2O 3丙烷脱氢催化剂。
评价：在石英管固定床反应器中装填3g催化剂5，控制氢气和丙烷总质量空速为3h -1，氢气/丙烷流量比1/4，反应压力为常压，床层温度610℃，反应产物用岛津GC-2014C气相色谱进行分析。
空白对比例1
本实施例制备催化剂6，Pt-Sn-K/Al 2O 3，并对其丙烷脱氢制丙烯的催化性能进行测试。该催化剂为空白对比例，未加入第一助剂稀土金属元素。
制备：1)配置质量浓度为0.02g/g的H 2PtCl 6·6H 2O溶液，质量浓度0.04g/g的SnCl 2·2H 2O溶液。分别取H 2PtCl 6·6H 2O溶液和SnCl 2·2H 2O溶液4.075g和0.729g,再加入浓盐酸和去离子水，使Pt-Sn浸渍液体积等于10g Al 2O 3载体总吸水量，且浓盐酸质量为浸渍液质量的8.3％.搅拌均匀后浸渍10g Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h；
2)配置质量浓度为0.07g/g的KNO 3溶液。分别取KNO 3溶液3.023g，再加入去离子水，使K浸渍液体积等于10g Al 2O 3载体总吸水量。搅拌均匀后浸渍步骤1)中焙烧后的Al 2O 3球载体。浸渍4h后于100℃真空干燥8h，在600℃下焙烧4h得到Pt-Sn-K/Al 2O 3丙烷脱氢催化剂。
评价：在石英管固定床反应器中装填3g催化剂6，控制氢气和丙烷总质量空速为3h -1，氢气/丙烷流量比1/4，反应压力为常压，床层温度610℃，反应产物用岛津GC-2014C气相色谱进行分析。
催化剂1-6的活性组分和助剂的含量检测如表1所示；实施例1-5及空白对比例1制备的催化剂催化性能检测如表2所示。
表1 催化剂活性组分和助剂的含量
Figure PCTCN2020108566-appb-000001
表2 催化剂催化性能
Figure PCTCN2020108566-appb-000002
Figure PCTCN2020108566-appb-000003
结合表1、表2的评价结果表明：加入稀土金属元素会实现对Pt-Sn基丙烷脱氢催化剂性能的改性，与空白对比例1相比，Y会显著提高Pt-Sn基丙烷脱氢催化剂的催化性能和稳定性，La只能起到轻微的促进作用。Ce、Pr则会降低Pt-Sn基催化剂的催化性能和稳定性。
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种用于丙烷脱氢制丙烯的催化剂，该催化剂包括：载体以及负载在载体上的活性组分和助剂，其特征在于，所述载体为氧化铝球，所述活性组分为铂族金属，所述助剂包括第一助剂稀土元素、第二助剂锡和第三助剂碱金属元素。
  2. 根据权利要求1所述的一种用于丙烷脱氢制丙烯的催化剂，其特征在于，所述活性组分为Pt，所述第一助剂稀土元素为Y、La、Ce、Pr或Nd；所述第三助剂碱金属元素为Li、Na、K中的一种。
  3. 根据权利要求1所述的一种用于丙烷脱氢制丙烯的催化剂，其特征在于，以催化剂总质量为标准，所述载体质量分数为80％～99.6％，所述活性组分Pt质量分数为0.1％～5％，所述第一助剂稀土元素质量分数为0.1％～5％，所述第二助剂Sn质量分数为0.1％～5％，所述第三助剂碱金属元素质量分数为0.1％～5％。
  4. 根据权利要求1-3中任意一项权利要求所述的一种用于丙烷脱氢制丙烯的催化剂的制备方法，其特征在于，包括以下内容：
    1)将Pt前驱体、Sn前躯体溶于水中形成混合溶液，然后加入竞争吸附剂得到浸渍液A；
    2)将氧化铝球载体浸渍在浸渍液A中，浸渍完成后经干燥、焙烧；
    3)将稀土金属前驱体、K前驱体溶于水中形成混合溶液得到浸渍液B；
    4)将步骤2)中焙烧后的载体浸渍在浸渍液B中，浸渍完成后经干燥、焙烧即得到丙烷脱氢催化剂。
  5. 根据权利要求4所述的一种用于丙烷脱氢制丙烯的催化剂的制备方法，其特征在于，所述Pt前驱体为氯铂酸；所述Sn前驱体为SnCl 2。
  6. 根据权利要求4所述的一种用于丙烷脱氢制丙烯的催化剂的制备方法，其特征在于，所述竞争吸附剂为无机酸或有机酸中的一种或多种；所述竞争吸附剂用量为浸渍液A质量的7-9％。
  7. 根据权利要求4所述的一种用于丙烷脱氢制丙烯的催化剂的制备方法，其特征在于，所述稀土金属前驱体为稀土金属元素的可溶性盐。
  8. 根据权利要求4所述的一种用于丙烷脱氢制丙烯的催化剂的制备方法，其特征在于，所述K前驱体为可溶性钾盐。
  9. 根据权利要求4所述的一种用于丙烷脱氢制丙烯的催化剂的制备方法，其特征在于，在步骤2)和步骤4)中，所述干燥采用真空干燥，干燥温度80-120℃，干燥时间6-10h；所述焙烧温度550-650℃，焙烧时间3-5h。
  10. 根据权利要求1所述的一种用于丙烷脱氢制丙烯的催化剂的应用，其特征在于，采用石英管固定床反应器进行丙烷脱氢，脱氢反应温度550℃～650℃，质量空速为1h -1～5h -1， 氢气/丙烷流量比例1/4-1/1。
PCT/CN2020/108566 2019-12-26 2020-08-12 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用 Ceased WO2021128867A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20905470.9A EP4023332B1 (en) 2019-12-26 2020-08-12 Catalyst for preparing propylene by propane dehydrogenation, preparation method therefor, and use thereof
US17/042,132 US20230096172A1 (en) 2019-12-26 2020-08-12 A catalyst for propane dehydrogenation to propylene and its preparation method and application

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201911370195.8A CN111085199A (zh) 2019-12-26 2019-12-26 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用
CN201911370195.8 2019-12-26

Publications (1)

Publication Number Publication Date
WO2021128867A1 true WO2021128867A1 (zh) 2021-07-01

Family

ID=70396810

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/108566 Ceased WO2021128867A1 (zh) 2019-12-26 2020-08-12 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用

Country Status (5)

Country Link
US (1) US20230096172A1 (zh)
EP (1) EP4023332B1 (zh)
CN (1) CN111085199A (zh)
SA (1) SA521422673B1 (zh)
WO (1) WO2021128867A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114602445A (zh) * 2022-03-21 2022-06-10 福州大学 一种以碳包覆氧化铝核壳结构为载体的铂系催化剂及其制备方法和应用
CN115779894A (zh) * 2022-12-27 2023-03-14 黄河三角洲京博化工研究院有限公司 以双金属氧化物为载体的Pt系催化剂及制备方法和应用
CN116273137A (zh) * 2023-03-20 2023-06-23 湘潭大学 丙烷直接脱氢制丙烯的方法及其催化剂与制备方法
CN116393165A (zh) * 2023-03-31 2023-07-07 福州大学 以Beta分子筛为载体的丙烷脱氢催化剂及制备方法
CN116510727A (zh) * 2023-04-04 2023-08-01 福州大学 一种用于丙烷脱氢制丙烯Pt基单原子催化剂及其制备方法
CN117899861A (zh) * 2024-01-08 2024-04-19 中国科学院生态环境研究中心 一种丙烷氧化脱氢单原子体系催化剂、其制备方法和制丙烯方法

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111085199A (zh) * 2019-12-26 2020-05-01 四川润和催化新材料股份有限公司 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用
CN113877577B (zh) * 2020-07-02 2024-01-30 中国石油化工股份有限公司 催化剂及其制备方法和提高烷烃转化率的方法
CN111790384B (zh) * 2020-07-31 2021-09-28 福州大学 用于丙烷脱氢制丙烯的Pt基多组分催化剂及其制备方法
CN112812751A (zh) * 2020-10-14 2021-05-18 中国科学院大连化学物理研究所 一种丙烷脱氢制丙烯工艺用储热材料及其制备方法
CN114425322B (zh) * 2020-10-15 2024-03-26 中国石油化工股份有限公司 一种负载型丙烷脱氢催化剂及其制备方法
CN114618575B (zh) * 2020-12-08 2023-08-15 中国科学院大连化学物理研究所 丙烷脱氢制丙烯的复合型催化剂、其制备方法及应用
CN113578321B (zh) * 2021-07-29 2023-04-07 陕西师范大学 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的金属氧化物改性铂基催化剂及方法
CN113578345B (zh) * 2021-07-29 2023-04-07 陕西师范大学 二氧化碳氧化丙烷临氢脱氢制丙烯和合成气的铂基复合催化剂及方法
CN113751080B (zh) * 2021-08-26 2023-12-22 润和催化剂股份有限公司 一种改性氧化铝载体及其制备方法和应用
CN113694923A (zh) * 2021-09-29 2021-11-26 淄博市翔力致高新材料有限责任公司 一种低碳烷烃脱氢催化剂及其制备方法及应用
CN116408074B (zh) * 2021-12-31 2025-07-11 中国石油天然气股份有限公司 一种低Pt载量丙烷脱氢催化剂及其应用
CN115138361A (zh) * 2022-07-04 2022-10-04 黄河三角洲京博化工研究院有限公司 一种有序介孔低碳烷烃脱氢催化剂、制备方法及应用
CN116393125B (zh) * 2023-04-16 2024-10-18 北京化工大学 一种丙烷脱氢催化剂及其制备方法和应用
CN116803498B (zh) * 2023-06-13 2024-02-13 北京海望氢能科技有限公司 一种脱氢催化剂、制备方法及其在二苯胺脱氢制备咔唑中的应用
CN117181221B (zh) * 2023-09-20 2026-01-06 北京交通大学 一种对丙烷脱氢具有高稳定性的双原子催化剂及制备方法
CN120054483A (zh) * 2023-11-30 2025-05-30 中国石油化工股份有限公司 一种用于丙烷脱氢制丙烯的催化剂及其制备和应用
WO2025156479A1 (zh) * 2024-01-25 2025-07-31 上海润和盛建设备科技有限公司 一种移动床丙烷脱氢转化的工艺方法和反应系统
CN118577266A (zh) * 2024-05-20 2024-09-03 北京化工大学 一种高分散锡掺杂的γ-Al2O3的制备方法及应用

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4762960A (en) * 1987-02-25 1988-08-09 Uop Inc. Dehydrogenation catalyst composition and paraffin dehydrogenation
US6756515B2 (en) * 2001-06-22 2004-06-29 Uop Llc Dehydrogenation process using layered catalyst composition
WO2007033934A2 (de) * 2005-09-20 2007-03-29 Basf Se Verfahren zur ermittlung der tortuosität, katalysatorträger, katalysator und verfahren zur dehydrierung von kohlenwasserstoffen
CN102775262A (zh) * 2011-05-13 2012-11-14 中国石油天然气股份有限公司 一种低碳烷烃脱氢制备烯烃的方法
CN103394349A (zh) * 2013-07-26 2013-11-20 中国石油大学(华东) 一种用于低碳烷烃脱氢的催化剂及其制备方法
CN104072325A (zh) * 2014-07-10 2014-10-01 南京沃来德能源科技有限公司 一种提高低碳烷烃脱氢反应性能的方法
CN104084198A (zh) * 2014-07-15 2014-10-08 华陆工程科技有限责任公司 一种丙烷脱氢制丙烯的铂氧化铝系列催化剂及制备方法
CN104084218A (zh) * 2014-07-10 2014-10-08 南京沃来德能源科技有限公司 一种低碳烷烃脱氢催化剂的再生方法
CN104148069A (zh) * 2014-08-18 2014-11-19 华陆工程科技有限责任公司 一种丙烷脱氢制丙烯的四元铂基催化剂及制备方法和应用
WO2018108443A1 (en) * 2016-12-13 2018-06-21 SMH Co., Ltd. Catalyst system and process utilizing the catalyst system
CN108295846A (zh) * 2018-02-11 2018-07-20 四川润和催化新材料股份有限公司 一种烷烃脱氢催化剂及其制备方法
CN108722468A (zh) 2017-04-20 2018-11-02 中国石油化工股份有限公司 一种丙烷脱氢催化剂及其制备方法和丙烷脱氢制丙烯的方法
CN109126788A (zh) * 2018-08-01 2019-01-04 西安凯立新材料股份有限公司 一种烷烃脱氢的铂氧化铝复合催化剂
CN109529911A (zh) 2018-12-14 2019-03-29 中国石油大学(北京) 一种丙烷无氧脱氢用铂锡基介孔催化剂及其制备和应用
CN110237849A (zh) * 2019-07-03 2019-09-17 福州大学 一种用于丙烷脱氢制丙烯的铂基催化剂及其制备方法
CN111085199A (zh) * 2019-12-26 2020-05-01 四川润和催化新材料股份有限公司 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2453366C1 (ru) * 2010-11-29 2012-06-20 Учреждение Российской академии наук Институт катализа им. Г.К. Борескова Сибирского отделения РАН Катализатор и способ получения синтез-газа
CN108786897B (zh) * 2017-05-05 2019-09-27 中国石油化工股份有限公司 负载型催化剂及其制备方法和应用和丙烷脱氢制丙烯的方法

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4762960A (en) * 1987-02-25 1988-08-09 Uop Inc. Dehydrogenation catalyst composition and paraffin dehydrogenation
US6756515B2 (en) * 2001-06-22 2004-06-29 Uop Llc Dehydrogenation process using layered catalyst composition
WO2007033934A2 (de) * 2005-09-20 2007-03-29 Basf Se Verfahren zur ermittlung der tortuosität, katalysatorträger, katalysator und verfahren zur dehydrierung von kohlenwasserstoffen
CN102775262A (zh) * 2011-05-13 2012-11-14 中国石油天然气股份有限公司 一种低碳烷烃脱氢制备烯烃的方法
CN103394349A (zh) * 2013-07-26 2013-11-20 中国石油大学(华东) 一种用于低碳烷烃脱氢的催化剂及其制备方法
CN104072325A (zh) * 2014-07-10 2014-10-01 南京沃来德能源科技有限公司 一种提高低碳烷烃脱氢反应性能的方法
CN104084218A (zh) * 2014-07-10 2014-10-08 南京沃来德能源科技有限公司 一种低碳烷烃脱氢催化剂的再生方法
CN104084198A (zh) * 2014-07-15 2014-10-08 华陆工程科技有限责任公司 一种丙烷脱氢制丙烯的铂氧化铝系列催化剂及制备方法
CN104148069A (zh) * 2014-08-18 2014-11-19 华陆工程科技有限责任公司 一种丙烷脱氢制丙烯的四元铂基催化剂及制备方法和应用
WO2018108443A1 (en) * 2016-12-13 2018-06-21 SMH Co., Ltd. Catalyst system and process utilizing the catalyst system
CN108722468A (zh) 2017-04-20 2018-11-02 中国石油化工股份有限公司 一种丙烷脱氢催化剂及其制备方法和丙烷脱氢制丙烯的方法
CN108295846A (zh) * 2018-02-11 2018-07-20 四川润和催化新材料股份有限公司 一种烷烃脱氢催化剂及其制备方法
CN109126788A (zh) * 2018-08-01 2019-01-04 西安凯立新材料股份有限公司 一种烷烃脱氢的铂氧化铝复合催化剂
CN109529911A (zh) 2018-12-14 2019-03-29 中国石油大学(北京) 一种丙烷无氧脱氢用铂锡基介孔催化剂及其制备和应用
CN110237849A (zh) * 2019-07-03 2019-09-17 福州大学 一种用于丙烷脱氢制丙烯的铂基催化剂及其制备方法
CN111085199A (zh) * 2019-12-26 2020-05-01 四川润和催化新材料股份有限公司 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114602445A (zh) * 2022-03-21 2022-06-10 福州大学 一种以碳包覆氧化铝核壳结构为载体的铂系催化剂及其制备方法和应用
CN115779894A (zh) * 2022-12-27 2023-03-14 黄河三角洲京博化工研究院有限公司 以双金属氧化物为载体的Pt系催化剂及制备方法和应用
CN116273137A (zh) * 2023-03-20 2023-06-23 湘潭大学 丙烷直接脱氢制丙烯的方法及其催化剂与制备方法
CN116393165A (zh) * 2023-03-31 2023-07-07 福州大学 以Beta分子筛为载体的丙烷脱氢催化剂及制备方法
CN116510727A (zh) * 2023-04-04 2023-08-01 福州大学 一种用于丙烷脱氢制丙烯Pt基单原子催化剂及其制备方法
CN117899861A (zh) * 2024-01-08 2024-04-19 中国科学院生态环境研究中心 一种丙烷氧化脱氢单原子体系催化剂、其制备方法和制丙烯方法

Also Published As

Publication number Publication date
EP4023332A4 (en) 2022-11-09
EP4023332C0 (en) 2023-10-11
US20230096172A1 (en) 2023-03-30
EP4023332A1 (en) 2022-07-06
EP4023332B1 (en) 2023-10-11
CN111085199A (zh) 2020-05-01
SA521422673B1 (ar) 2024-08-15

Similar Documents

Publication Publication Date Title
WO2021128867A1 (zh) 一种用于丙烷脱氢制丙烯的催化剂及其制备方法与应用
CN103212411B (zh) 低碳烷烃脱氢制取烯烃的高效催化剂及其制备方法
CN106512994B (zh) 一种抗积碳铂基丙烷脱氢制丙烯催化剂及其制备方法
CN105251486B (zh) 应用于丙烷脱氢制丙烯的负载型铂系催化剂及其制备方法
CN104148060B (zh) 一种负载于双氧化物复合载体的铂催化剂及其制备方法和应用
CN104525196B (zh) 负载于双氧化物复合载体的铂镓催化剂及其制备方法和应用
CN113019412B (zh) 一种轻质烷烃脱氢制烯烃催化剂、其制备方法及应用
CN104525194B (zh) 一种异丁烷脱氢制异丁烯用催化剂及其制备方法与应用
CN108579742B (zh) 脱氢催化剂及其制备方法
CN101164690A (zh) 一种负载型铂基三元催化剂及制法和应用
CN111790381B (zh) 一种用于低碳烷烃脱氢的金属催化剂
CN112934230B (zh) 低Pt型长链烷烃脱氢催化剂、其制备方法及应用
CN110603096A (zh) 高再生效率的直链轻烃的脱氢催化剂的制备方法
CN106268806B (zh) 一种甲醇羰基化的催化剂及其制备和应用
CN104289219B (zh) 一种低碳烷烃脱氢催化剂的制备方法
CN105797723A (zh) 一种甲醇甲醛低温深度氧化催化剂
CN101455962A (zh) 由环己酮二聚物脱氢制备邻苯基苯酚的催化剂及其制备方法
CN101337185B (zh) 催化甲苯选择氧化制苯甲醛和苯甲酸的钒氧化物和钒银氧化物
CN113019394B (zh) 氨分解制氢Ni-Pt/CeO2催化剂及其制备方法和应用
CN105214697A (zh) 一种低链烷烃脱氢制烯烃催化剂及制备方法
CN113385172B (zh) 一种乙烷临氢脱氢制乙烯的催化剂及其制备和应用
CN108654637A (zh) 一种钴基催化剂及制备方法和应用及费托合成方法
CN104368360B (zh) 一种巴豆醛气相选择性加氢合成巴豆醇的催化剂及制备方法
CN116060046A (zh) 一种低碳烷烃脱氢催化剂及其制备方法和应用
CN1465436A (zh) 一种正构烷烃异构化催化剂及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20905470

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020905470

Country of ref document: EP

Effective date: 20220329

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 521422673

Country of ref document: SA

WWE Wipo information: entry into national phase

Ref document number: 521422673

Country of ref document: SA

WWG Wipo information: grant in national office

Ref document number: 521422673

Country of ref document: SA