CN111617785A - Supported ruthenium-based phosphide catalyst and preparation method thereof - Google Patents
Supported ruthenium-based phosphide catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN111617785A CN111617785A CN202010655245.3A CN202010655245A CN111617785A CN 111617785 A CN111617785 A CN 111617785A CN 202010655245 A CN202010655245 A CN 202010655245A CN 111617785 A CN111617785 A CN 111617785A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- phosphoric acid
- ruthenium
- molecular sieve
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 27
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 74
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 37
- 238000005470 impregnation Methods 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 21
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 21
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 21
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 229910001868 water Inorganic materials 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 24
- 238000011068 loading method Methods 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910026161 MgAl2O4 Inorganic materials 0.000 claims description 11
- 229910052596 spinel Inorganic materials 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 5
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 38
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000001294 propane Substances 0.000 abstract description 18
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 abstract description 7
- 239000012018 catalyst precursor Substances 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 150000003303 ruthenium Chemical class 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 230000009849 deactivation Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/394—
-
- B01J35/40—
-
- B01J35/50—
-
- 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
-
- 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
Abstract
The invention discloses a load type ruthenium phosphide catalyst and a preparation method thereof, wherein the adopted preparation method is SiO2、Al2O3When the oxide is used as a carrier, phosphoric acid and a ruthenium source are respectively immobilized on the carrier by a strong electrostatic adsorption-impregnation method, and PO is obtained by roastingx‑RuOya/ZT catalyst precursor, reducing the catalyst precursor with a reducing atmosphere, RuO under thermal driveyAnd POxSolid-solid reaction is carried out to form Ru-P bond, and the Ru-P/ZT catalyst is obtained. The active component Ru-P of the catalyst has the nano-particle size of 2-6 nm. The strong electrostatic adsorption between the phosphorus source and the ruthenium salt and the carrier leads phosphide nano-particles to be separatedThe powder is uniform, the size is small, and the reaction condition in the preparation process is mild, simple and green. The ruthenium-based phosphide catalyst shows excellent selectivity and stability in the propane dehydrogenation reaction.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a supported ruthenium-based phosphide catalyst and a preparation method thereof.
Background
As a supporting scientific technology in the petroleum industry, the chemical industry, the energy industry and many other industries, the catalytic technology plays a key role in solving the important problems of energy, environment and the like existing in the current development, wherein the development of a novel high-efficiency catalyst is the core power of the progress of the catalytic technology. The transition metal phosphide has a special crystal structure and noble metal-like properties, and shows good catalytic performance in catalytic hydrodesulfurization, hydrodenitrogenation and electrochemical hydrogen production reactions, so that the transition metal phosphide catalyst is developed rapidly in recent years, and the application field is expanded continuously.
The metal Ru belongs to rare platinum group metal elements, has lower price compared with platinum, and is a metal catalyst with wide application prospect. However, the most thermodynamically stable structure of Ru is a hexagonal close-packed structure, and most transition metals (Pt, Cu, Ir, Pd, Au, etc.) are face-centered cubic structures, and it is known from phase diagrams that achieving bulk alloying of Ru with metal elements of different lattice structures is very challenging even above the melting point, so that modification of the geometric structure and electronic structure of Ru atoms by introducing a second metal is greatly limited, and application thereof in catalytic reactions is hindered. In the transition metal phosphide, phosphorus atoms can form an alloy-like structure by bonding with metal Ru atoms, so that the electronic structure and surface properties of the Ru atoms can be modified to a greater extent, and the catalytic performance is changed. The traditional preparation method of transition metal phosphide comprises a high-temperature phosphating method of elemental metal and red phosphorus and PH3Gas reduction method, J.Catal.,2006,237(1), 118-130 at pH3Processing metallic nickel at 250 ℃ as a phosphorus source to prepare nickel phosphide Ni2P catalyst, which has harsh reaction conditions and involves a large amount of highly toxic PH3The gas escapes. Therefore, in recent years, a precursor and trioctylphosphine solvothermal method, a metal phosphate temperature programmed reduction method, and the like have been developed. The document J.Am.chem.Soc.,2017,139,15,5494-5502 reports rhodium R acetylacetonateh(acac)3Takes n-trioctylphosphine TOP as a phosphorus source and oleylamine as a solvent as a metal source to successfully synthesize Rh through a hydrothermal reaction2P nanocubes. The process reactants are highly flammable and corrosive, require oxygen-free operation, are difficult and dangerous to operate. The document Angew. chem. int. Ed.,2014,53, 14433->650 ℃) and reducing metal phosphate in hydrogen atmosphere to prepare molybdenum phosphide MoP, and the phosphide obtained by the method has large particle size and irregular appearance, and most of the phosphide particles are agglomerated particles.
In summary, the common preparation method of the transition metal-based phosphide at present has harsh conditions, extremely toxic substances such as phosphine and the like are used or accompanied in the preparation process, and the size of the active component of the catalyst is difficult to control. The invention aims to provide a ruthenium-based phosphide catalyst with high catalytic activity prepared under an environment-friendly condition.
Disclosure of Invention
The invention aims to provide a kind of supported ruthenium-based phosphide catalyst, and also aims to provide a preparation method of the catalyst. The catalyst is suitable for propane dehydrogenation.
The supported ruthenium-based phosphide catalyst provided by the invention is expressed as Ru-P/ZT, wherein ZT represents a carrier, and ZT is SiO2、Al2O3、MgAl2O4Any one of a ZSM-5 molecular sieve, an SBA-15 molecular sieve, an SUZ-4 molecular sieve and an SAPO-34 molecular sieve; Ru-P is an active component, wherein the molar ratio of P/Ru is within the range of 0.1-75, the active component particles are between 2-6nm, and the Ru loading is between 0.3-10%; the catalyst forms Ru-P bonds, and continuous sites of Ru atoms are separated by P atoms. The Ru loading is the mass percentage of metal Ru in the carrier.
The preparation method of the supported ruthenium-based phosphide catalyst provided by the invention is characterized in that phosphoric acid and a ruthenium source are respectively immobilized on a carrier by a strong electrostatic adsorption-impregnation method, the phosphoric acid is firstly supported, and the phosphoric acid is roasted into an oxide form; loading ruthenium source, adjusting pH of the solution according to the property of the carrier, ensuring metal ions to be uniformly dispersed to the surface of the carrier by using strong electrostatic adsorption, and roasting again to obtain uniformly dispersed POx-RuOya/ZT catalyst precursor; finally obtaining the ruthenium-based phosphide catalyst with smaller size and uniform dispersion through reduction in a reducing atmosphere.
The specific preparation steps of the supported ruthenium-based phosphide catalyst are as follows:
A. mixing a phosphoric acid solution with the mass concentration of 40-90% with deionized water to prepare a phosphoric acid impregnation solution, dropwise adding the phosphoric acid impregnation solution onto the carrier, stirring the carrier while dropwise adding to ensure uniform loading until the carrier is saturated in water absorption; drying in an oven at 80-130 deg.C for 4-24h, and calcining at 200-600 deg.C for 2-5 h to obtain a phosphorus oxide-loaded carrier represented as POxZT, x represents the atomic ratio O/P in the phosphorus oxide, and x is in the range of 2.5 to 3.5.
The content of phosphoric acid in the phosphoric acid impregnation liquid is determined according to the Ru/P ratio set by the target catalyst, the mass concentration of the phosphoric acid impregnation liquid is within the range of 3-50%, and the volume of the phosphoric acid impregnation liquid is required to enable the carrier ZT to be adsorbed and saturated; this volume can be determined by the water absorption of the carrier. The method for testing the adsorption rate comprises the following steps: weighing 5g of carrier in a 50ml beaker, measuring 20ml of distilled water, slowly pouring the carrier into deionized water, standing at room temperature and normal pressure for 12h, and filtering off excessive water. The water absorption a of the carrier is then: a ═ 20-V)/5, where V is the filtered water volume (mL).
The carrier is SiO2、Al2O3、MgAl2O4One of ZSM-5 molecular sieve, SBA-15 molecular sieve, SUZ-4 molecular sieve and SAPO-34 molecular sieve.
B. Dissolving soluble Ru salt in deionized water, fully dissolving by ultrasonic, and adjusting the pH value to 4-12 by using an alkaline solution or an acidic solution; the Ru salt solution was added dropwise to the POxIn ZT, dropwise adding under stirring until the carrier is saturated with water, drying in an oven at 80-130 deg.C for 4-24h, and calcining at 200-600 deg.C for 2-5 h to obtain precursor loaded with phosphorus oxide and ruthenium oxide, represented as POx-RuOyZT, y represents the atomic ratio of O/Ru in the ruthenium oxide, and y is 1.5-4.0;
the dosage of the deionized water is calculated according to the water absorption of the carrier based on the water absorption saturation of the carrier; the Ru salt is Ru(NH3)6·Cl3、K2Ru(NO)Cl5、K2RuCl6、Ru(NH3)5H2O·Cl3The amount of the Ru salt is determined according to the load of the metal Ru being 0.3-10%; the alkaline solution is one of ammonia water, sodium hydroxide or sodium carbonate; the acid solution is hydrochloric acid or nitric acid. Wherein the molar concentration of the sodium hydroxide and the sodium carbonate is 1-3 mol/L; wherein the mass concentration of the hydrochloric acid and the nitric acid is 10 to 30 percent.
C. To POx-RuOythe/ZT is reduced for 1 to 10 hours in a reducing atmosphere at the temperature of 400-750 ℃, wherein the gas flow rate is 20 to 100mL/min, and the temperature rising rate of the atmosphere furnace is 2 to 20 ℃/min; the ruthenium-based phosphide catalyst was obtained and was designated as Ru-P/ZT.
The reducing atmosphere is 5-40% H2/N2、5-40％CO/N2One kind of (1).
Characterization of the catalyst obtained:
FIG. 1 shows Ru-P/SiO prepared in example 12As shown in the electron microscope photograph (a) and the statistical result (b) of the particle size of the catalyst, the metal phosphide particles in the obtained supported catalyst are well dispersed on the surface of the carrier, the particle size is uniform, the particle size is small, and the average particle size is 2.8 nm.
FIG. 2 shows Ru-P/SiO prepared in example 12The extended X-ray absorption fine structure of the catalyst can be obtained by fitting, and the coordination number ratio of Ru-P bond to Ru-Ru bond is CNRu-P/CNRu-RuAt 1.0, the formation of ruthenium-based phosphide catalyst was confirmed.
FIG. 3 shows Ru-P/SiO films prepared in example 22The electron microscope photograph (a) and the particle size statistical result (b) of the catalyst show that the ruthenium phosphide particles in the obtained supported catalyst are uniformly dispersed on the surface of the carrier, the particle size distribution range is narrow, the particle size is small, and the average particle size is 2.8 nm.
FIG. 4 shows a single metal Ru catalyst (curve 1) and Ru-P/SiO prepared in example 22CO in situ IR spectrum of catalyst (curve 2), Ru-P/SiO, compared to monometallic Ru2CO bridge adsorption Peak in catalyst (1998 cm)-1) And linear adsorption peak (2025 cm)-1) Disappeared and is at 2150cm-1-2050cm-1There appears relatively weak Ru+-CO line adsorption peak, indicating that Ru consecutive sites are separated.
FIG. 5 shows Ru-P/Al prepared in example 32O3From the electron micrograph (a) and the particle size statistical result (b) of the catalyst, it can be seen that the ruthenium phosphide particles in the supported catalyst prepared in example 3 were well dispersed on the surface of the support, and the particles were uniform and small in size, and had an average particle size of 3.1 nm.
FIG. 6 shows Ru-P/Al prepared in example 32O3The extended X-ray absorption fine structure of the catalyst can be fitted to obtain a Ru-Ru bond length of
Has a Ru-P bond length of
Ratio of coordination number of Ru-P bond to Ru-Ru bond CNRu-P/CNRu-Ru0.15, indicating that a ruthenium-based phosphide catalyst was formed.
FIG. 7 shows Ru-P/SiO in example 12Catalyst (Curve 1) and Ru-P/SiO in example 22Catalyst (curve 2) propylene selectivity as a function of propane conversion in the propane dehydrogenation reaction at 550 ℃. As can be seen from the graph, the Ru-P/SiO prepared in example 1 increased with propane conversion from 5% to 25%2Propylene selectivity of the catalyst is always maintained>93% Ru-P/SiO prepared in example 22Propylene selectivity of the catalyst is always maintained>83％。
FIG. 8 shows Ru-P/SiO in example 12Catalyst (Curve 1), Ru-P/SiO in example 22Catalyst (curve 2) propane conversion at 550 ℃ over time in the propane dehydrogenation reaction. As can be seen from the figure, the catalyst has better stability, and the Ru-P/SiO prepared in example 12The deactivation constant of the catalyst is only 0.107h within 2h of reaction time-1Ru-P/SiO prepared in example 22The deactivation constant of the catalyst is 0.115h within 2h of reaction time-1。
The invention has the beneficial effects that: by using a strong electrostatic adsorption-impregnation method with SiO2、Al2O3Taking phosphoric acid as a phosphorus source, taking the hydroxyl functional groups on the surface of the carrier to generate strong adsorption with the phosphoric acid, and roasting to take PO as the phosphorus sourcexImmobilizing the species to a carrier; then, the Ru source is immobilized on the surface of the carrier by using a similar method to obtain POx-RuOya/ZT catalyst precursor. Reducing the catalyst precursor under a reducing atmosphere, RuO under thermal driveyAnd POxSolid-solid reaction occurs to generate Ru-P bond. According to the method, the phosphide nanoparticles are uniformly dispersed and have small size under the strong electrostatic adsorption action of the precursor and the carrier, and the regulation and control of the Ru-based phosphide structure and the catalytic performance are realized by adjusting the molar ratio of phosphorus to ruthenium. The reaction conditions in the preparation process are mild, simple and green. The ruthenium-based phosphide catalyst prepared by the method has excellent selectivity and stability in propane dehydrogenation reaction.
Description of the drawings:
FIG. 1 shows Ru-P/SiO films prepared in example 12Electron micrograph (a) and particle size statistics (b) of the catalyst.
FIG. 2 shows Ru-P/SiO in example 12Extended X-ray absorption fine structure results of the catalyst.
FIG. 3 shows Ru-P/SiO films prepared in example 22Electron micrograph (a) and particle size statistics (b) of the catalyst.
FIG. 4 shows a single metal Ru catalyst (Curve 1) and Ru-P/SiO prepared in example 22CO in situ IR spectrum of catalyst (curve 2).
FIG. 5 shows Ru-P/Al prepared in example 32O3Electron micrograph (a) and particle size statistics (b) of the catalyst.
FIG. 6 shows Ru-P/Al in example 32O3Extended X-ray absorption fine structure results of the catalyst.
FIG. 7 shows Ru-P/SiO powders in example 12Catalyst (Curve 1), Ru-P/SiO in example 22(Curve 2) catalyst propylene selection in propane dehydrogenationPerformance as a function of propane conversion.
FIG. 8 shows Ru-P/SiO films, respectively, in example 12Catalyst (Curve 1), Ru-P/SiO in example 22Catalyst (curve 2) propane conversion over time in the propane dehydrogenation reaction.
The specific implementation mode is as follows:
example 1
The target catalyst has 2% of Ru loading and 50 of P/Ru molar ratio.
A. Uniformly mixing 3.3ml of phosphoric acid with the mass concentration of 85% with 2.5ml of deionized water to obtain 48.3% phosphoric acid impregnation liquid, and dropwise adding the impregnation liquid to 5g of SiO with the particle size of 35-60 meshes2On the upper part, SiO is stirred while dropwise adding2To ensure uniform loading until SiO2Absorbing water to saturate, drying in a drying oven at 125 ℃ for 12h, and roasting at 250 ℃ for 3h to obtain POx/SiO2。
B. 0.3126g Ru (NH)3)6·Cl3Dissolving in 5.8ml deionized water, ultrasonic dissolving, adjusting pH to-11 with 25% ammonia water to obtain Ru (NH)3)6·Cl3Dropwise adding the solution into the PO obtained in the step Ax/SiO2In the preparation, the mixture is added dropwise to PO while stirringx/SiO2Absorbing water to saturate, drying in a 125 ℃ oven for 12h, roasting at 300 ℃ for 3h to obtain POx-RuOy/SiO2。
C. To POx-RuOy/SiO2At 600 ℃ 5% H2/N2Reducing for 3h in the atmosphere, wherein the gas flow rate is 40mL/min, the temperature rise rate of the atmosphere furnace is 2 ℃/min, and obtaining Ru-P/SiO2Catalyst with 2% Ru loading and a P/Ru molar ratio of 50.
Example 2
The target catalyst has 1 percent of Ru load and 15 mole ratio of P/Ru
A. Uniformly mixing 1.1ml of phosphoric acid with the mass concentration of 40% and 4.7ml of deionized water to obtain a phosphoric acid impregnation solution with the mass concentration of 7.6%, and dropwise adding the phosphoric acid impregnation solution to 5g of SiO with the particle size of 35-60 meshes2On the upper part, SiO is stirred while dropwise adding2To ensure uniform loading until SiO2Absorbing water to saturate, drying in a drying oven at 125 ℃ for 12h, and finally roasting at 250 ℃ for 3h to obtain a carrier POx/SiO2。
B. 0.1563g Ru (NH)3)6·Cl3Dissolving in 5.5ml deionized water, ultrasonic dissolving, adjusting pH to-11 with 3mol/L sodium bicarbonate solution, and obtaining PO by the above stepsx/SiO2Dropping Ru (NH) dropwise3)6·Cl3The solution was added dropwise to PO with stirringx/SiO2Absorbing water to saturate, drying in a drying oven at 125 ℃ for 12h, and finally roasting at 300 ℃ for 3h to obtain POx-RuOy/SiO2。
C. To POx-RuOy/SiO2At 700 ℃ 10% CO/N2Reducing for 4h in the atmosphere, wherein the gas flow rate is 40mL/min, and the temperature rise rate of the atmosphere furnace is 5 ℃/min; obtaining Ru-P/SiO2Catalyst with a Ru loading of 1% and a P/Ru molar ratio of 15.
Example 3
The target catalyst has a Ru loading of 10% and a P/Ru molar ratio of 1.
A. 0.73ml of phosphoric acid with the mass concentration of 40 percent and 5.27ml of deionized water are uniformly mixed to obtain a phosphoric acid impregnation liquid with the mass concentration of 4.9 percent, and the phosphoric acid impregnation liquid is dropwise added to 5g of Al2O3Adding Al on the powder while stirring2O3To ensure uniform loading until Al2O3Absorbing water to saturate, drying in a drying oven at 80 ℃ for 24h, and finally roasting at 350 ℃ for 4 hours to obtain a carrier POx/Al2O3。
B. 1.9356g K will be mixed2RuCl6Dissolving in 5.8ml deionized water, ultrasonic dissolving, adjusting pH to-5 with 15% dilute hydrochloric acid, and getting PO by the above stepsx/Al2O3Dropwise adding K2RuCl6The solution was added dropwise to PO with stirringx/Al2O3Absorbing water to saturate, drying in a drying oven at 80 ℃ for 24h, and finally roasting at 500 ℃ for 4h to obtain POx-RuOy/Al2O3。
C. To POx-RuOy/Al2O3At 600 ℃ 5% H2/N2Reducing for 4h in atmosphere, wherein the gas flow rate is 60mL/min, the temperature rise rate of the atmosphere furnace is 10 ℃/min, and obtaining Ru-P/Al2O3The catalyst has Ru loading of 10% and P/Ru molar ratio of 1.
Example 4
The target catalyst has 5% of Ru loading and 10 of P/Ru molar ratio.
A. Uniformly mixing 3.5ml of phosphoric acid with the mass concentration of 40% and 2.5ml of deionized water to obtain a phosphoric acid impregnation liquid with the mass concentration of 23.3%, and dropwise adding the phosphoric acid impregnation liquid to 5g of Al2O3Adding Al on the powder while stirring2O3To ensure uniform loading until Al2O3Absorbing water to saturate, drying in a drying oven at 80 ℃ for 24h, and finally roasting at 350 ℃ for 4h to obtain a carrier POx/Al2O3。
B. 0.7673g Ru (NH)3)5H2O·Cl3Dissolving in 5.9ml deionized water, ultrasonic dissolving, adjusting pH to-10 with 25% ammonia water, and obtaining PO by the above stepsx/Al2O3Dropping Ru (NH) dropwise3)5H2O·Cl3The solution was added dropwise to PO with stirringx/Al2O3Absorbing water to saturate, drying in a drying oven at 80 ℃ for 24h, and finally roasting at 300 ℃ for 3h to obtain POx-RuOy/Al2O3。
C. To POx-RuOy/Al2O3At 700 ℃ 5% CO/N2Reducing for 5h in atmosphere, wherein the gas flow rate is 40mL/min, the temperature rise rate of the atmosphere furnace is 5 ℃/min, and Ru-P/Al is obtained2O3Catalyst, wherein the Ru loading is 5% and the P/Ru molar ratio is 10.
Example 5
The target catalyst has 4% Ru loading and 25P/Ru molar ratio.
A. 3.3ml of phosphoric acid with the mass concentration of 85 percent and 6.7ml of deionized water are mixed evenly,obtaining 28.1 percent phosphoric acid impregnation liquid, dropwise adding the phosphoric acid impregnation liquid to 5g of ZSM-5 molecular sieve powder while stirring the ZSM-5 molecular sieve to ensure uniform loading until the carrier is saturated by water absorption, drying the carrier in a drying oven at the temperature of 130 ℃ for 12 hours, and finally roasting the carrier at the temperature of 500 ℃ for 2 hours to obtain the carrier POx/ZSM-5。
B. Mixing 0.7653g K2Ru(NO)Cl5Dissolving in 9.3ml deionized water, ultrasonic dissolving, adjusting pH to-6 with 20% dilute nitric acid, and obtaining PO by the above stepsxZSM-5 dropwise adding K2Ru(NO)Cl5The solution was added dropwise to PO with stirringxZSM-5 saturated with water, drying in oven at 130 deg.C for 12h, and calcining at 500 deg.C for 2 hr to obtain POx-RuOy/ZSM-5。
C. To POx-RuOyZSM-5 at 550 ℃ with 5% H2/N2Reducing for 4h in the atmosphere, wherein the gas flow rate is 60mL/min, the temperature rising rate of the atmosphere furnace is 2 ℃/min, and finally obtaining the Ru-P/ZSM-5 catalyst, wherein the Ru loading is 4%, and the P/Ru molar ratio is 25.
Example 6
The target catalyst has 2.5% of Ru loading and 20 of P/Ru molar ratio.
A. 1.65ml of phosphoric acid with the mass concentration of 85 percent and 6.35ml of deionized water are uniformly mixed to obtain a phosphoric acid impregnation liquid with the mass concentration of 17.5 percent, and the phosphoric acid impregnation liquid is dropwise added to 5g of MgAl2O4Adding MgAl on the powder while stirring2O4To ensure uniform loading until the carrier absorbs water to saturation, drying in an oven at 100 deg.C for 12h, and finally calcining at 200 deg.C for 4 hr to obtain carrier POx/MgAl2O4。
B. 0.3907g Ru (NH)3)6·Cl3Dissolving in 8.0ml deionized water, ultrasonic dissolving, adjusting pH to-10 with 25% ammonia water, and obtaining PO by the above stepsx/MgAl2O4Dropping Ru (NH) dropwise3)6·Cl3The solution was added dropwise to PO with stirringx/MgAl2O4Absorbing water to saturation, drying in an oven at 100 deg.C for 12h, and roasting at 200 deg.C for 4 hr to obtain POx-RuOy/MgAl2O4。
C. To POx-RuOy/MgAl2O4At 600 ℃ 40% H2/N2Reducing for 3h in atmosphere, wherein the gas flow rate is 30mL/min, the temperature rise rate of the atmosphere furnace is 5 ℃/min, and obtaining Ru-P/MgAl2O4The catalyst of (1), wherein the Ru loading is 2.5% and the P/Ru molar ratio is 20.
Application example 1:
the performance of the propane dehydrogenation reaction of the catalyst of example 1-2 was evaluated by using a fixed-bed microreactor as the evaluation device, and the operation procedure was as follows:
0.2g of the Ru-P/SiO powder of example 1 were weighed out separately2And 0.3g of example 2Ru-P/SiO2Adding quartz sand into a catalyst sample, mixing to 1g, uniformly mixing, and filling into a quartz tube with the outer diameter of 9mm, wherein the relative pressure of a reaction system is 5 psi. Before the reaction starts, the catalyst is first prereduced at a gas flow rate of 100ml/min 5% H2/N2Reducing for 30min at 600 ℃ in the atmosphere. Keeping the reaction temperature at 550 ℃, introducing reaction gas, namely the mixture of propane, hydrogen and balance gas nitrogen, with the total gas flow rate of 100ml/min and the concentration of 5 percent C3H8/N2And 5% of H2/N2Flow rates were all 50ml/min, C3H8、H2、N2The contents are respectively 2.5%, 2.5% and 95%. The concentration of the reactants and products was analyzed by on-line gas chromatography (Agilent 6890) using a hydrogen flame ionization detector and capillary column model Restek Rt-aluminum BOND/Na2SO4(inner diameter 0.32mm, length 30m, film thickness 0.5 μm). The results of the catalyst's propane conversion, propylene selectivity and deactivation constant at 550 ℃ are shown in table 1:
TABLE 1
| Catalyst sample | Example 1 | Example 2 | Comparative example |
| Propane conversion (%) | 25.0 | 25.0 | 19.0 |
| Propylene selectivity (%) | 93.0 | 83.5 | 59.2 |
| Deactivation constant | 0.107 | 0.115 | 1.0 |
The comparative sample is Pt/SiO reported in the document J.Am.chem.Soc.2018,140,11674-116792The performance of the catalyst in propane dehydrogenation reaction at 550 ℃, and the Pt catalyst is a commonly used propane dehydrogenation catalyst. Compared with a comparative example, the Ru-P catalyst prepared by the invention has more excellent activity and selectivity, and the deactivation constant is far lower than that of the comparative example.
Claims (2)
1. A preparation method of a supported ruthenium-based phosphide catalyst comprises the following specific preparation steps:
A. mixing a phosphoric acid solution with the mass concentration of 40-90% with deionized water to prepare a phosphoric acid impregnation solution, dropwise adding the phosphoric acid impregnation solution onto the carrier, stirring the carrier while dropwise adding to ensure uniform loading until the carrier is saturated in water absorption; drying in an oven at 80-130 deg.C for 4-24h, and calcining at 200-600 deg.C for 2-5 h to obtain phosphorus-loaded materialSupport for oxides, denoted POxZT, x represents the atomic ratio O/P in the phosphorus oxide, x is in the range of 2.5-3.5;
the content of phosphoric acid in the phosphoric acid impregnation liquid is determined according to the Ru/P ratio set by the target catalyst, the mass concentration of the phosphoric acid impregnation liquid is 3-50%, and the volume of the phosphoric acid impregnation liquid is required to enable the carrier ZT to be adsorbed and saturated; the carrier is SiO2、Al2O3、MgAl2O4Any one of a ZSM-5 molecular sieve, an SBA-15 molecular sieve, an SUZ-4 molecular sieve and an SAPO-34 molecular sieve;
B. dissolving soluble Ru salt in deionized water, fully dissolving by ultrasonic, and adjusting the pH value to 4-12 by using an alkaline solution or an acidic solution; the Ru salt solution was added dropwise to the POxIn ZT, dropwise adding under stirring until the carrier is saturated with water, drying in an oven at 80-130 deg.C for 4-24h, and calcining at 200-600 deg.C for 2-5 h to obtain precursor loaded with phosphorus oxide and ruthenium oxide, represented as POx-RuOyZT, y represents the atomic ratio of O/Ru in the ruthenium oxide, and y is 1.5-4.0;
the dosage of the deionized water is calculated according to the water absorption of the carrier based on the water absorption saturation of the carrier; the Ru salt is Ru (NH)3)6·Cl3、K2Ru(NO)Cl5、K2RuCl6、Ru(NH3)5H2O·Cl3The amount of the Ru salt is determined according to the load of the metal Ru being 0.3-10%; the alkaline solution is one of ammonia water, sodium hydroxide or sodium carbonate; the acid solution is hydrochloric acid or nitric acid; wherein the molar concentration of the sodium hydroxide and the sodium carbonate is 1-3 mol/L; wherein the mass concentration of the hydrochloric acid and the nitric acid is 10-30%;
C. the PO obtained in the step Bx-RuOyThe ZT is reduced for 1 to 10 hours in a reducing atmosphere at the temperature of 400-750 ℃; wherein the gas flow rate is 20-100mL/min, and the temperature rise rate of the atmosphere furnace is 2-20 ℃/min; obtaining a ruthenium-based phosphide catalyst expressed as Ru-P/ZT; the reducing atmosphere is 5-40% of H2/N2Or 5-40% CO/N2One kind of (1).
2. The supported ruthenium-based phosphide catalyst prepared according to the process of claim 1, represented as Ru-P/ZT, wherein ZT represents a support and ZT is SiO2、Al2O3、MgAl2O4Any one of a ZSM-5 molecular sieve, an SBA-15 molecular sieve, an SUZ-4 molecular sieve and an SAPO-34 molecular sieve; Ru-P is an active component, wherein the molar ratio of P/Ru is 0.1-75, the active component particles are 2-6nm, and the Ru loading is 0.3-10%; the Ru loading is the mass percentage of metal Ru in the carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010655245.3A CN111617785B (en) | 2020-07-09 | 2020-07-09 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010655245.3A CN111617785B (en) | 2020-07-09 | 2020-07-09 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111617785A true CN111617785A (en) | 2020-09-04 |
| CN111617785B CN111617785B (en) | 2021-10-15 |
Family
ID=72255732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010655245.3A Active CN111617785B (en) | 2020-07-09 | 2020-07-09 | Supported ruthenium-based phosphide catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111617785B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385205A (en) * | 2021-07-16 | 2021-09-14 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
| CN115254158A (en) * | 2022-08-22 | 2022-11-01 | 中国科学院兰州化学物理研究所 | Nanocluster metal phosphide-phosphorus-carbon catalyst and preparation and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408688A (en) * | 2001-09-20 | 2003-04-09 | 三菱化学株式会社 | Method for producing carbonyl compounds |
| CN101380587A (en) * | 2008-10-10 | 2009-03-11 | 东南大学 | Propane dehydrogenation catalyst to produce propylene and preparation method thereof |
| CN102427880A (en) * | 2009-04-01 | 2012-04-25 | Sk新技术株式会社 | Metal phosphorus compound for preparing biodiesel and method for preparing biodiesel using the same |
| CN104072335A (en) * | 2013-03-28 | 2014-10-01 | 中国石油大学(北京) | Method of cellulose catalytic conversion to prepare dihydric alcohol, hexahydric alcohol and gamma-valerolactone |
| CN105921155A (en) * | 2016-05-16 | 2016-09-07 | 北京化工大学 | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof |
| CN110639567A (en) * | 2019-10-10 | 2020-01-03 | 浙江工业大学 | Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof |
| CN111068648A (en) * | 2019-12-31 | 2020-04-28 | 大连理工大学 | Anti-carbon-deposition propylene preparation catalyst with L-acid alumina as carrier, preparation and application |
-
2020
- 2020-07-09 CN CN202010655245.3A patent/CN111617785B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408688A (en) * | 2001-09-20 | 2003-04-09 | 三菱化学株式会社 | Method for producing carbonyl compounds |
| CN101380587A (en) * | 2008-10-10 | 2009-03-11 | 东南大学 | Propane dehydrogenation catalyst to produce propylene and preparation method thereof |
| CN102427880A (en) * | 2009-04-01 | 2012-04-25 | Sk新技术株式会社 | Metal phosphorus compound for preparing biodiesel and method for preparing biodiesel using the same |
| CN104072335A (en) * | 2013-03-28 | 2014-10-01 | 中国石油大学(北京) | Method of cellulose catalytic conversion to prepare dihydric alcohol, hexahydric alcohol and gamma-valerolactone |
| CN105921155A (en) * | 2016-05-16 | 2016-09-07 | 北京化工大学 | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof |
| CN110639567A (en) * | 2019-10-10 | 2020-01-03 | 浙江工业大学 | Carbon-supported ruthenium phosphide nanocluster bifunctional catalyst and preparation method and application thereof |
| CN111068648A (en) * | 2019-12-31 | 2020-04-28 | 大连理工大学 | Anti-carbon-deposition propylene preparation catalyst with L-acid alumina as carrier, preparation and application |
Non-Patent Citations (5)
| Title |
|---|
| FURUKAWA, SHINYA ET AL: "Remarkable Enhancement in Hydrogenation Ability by Phosphidation of Ruthenium: Specific Surface Structure Having Unique Ru Ensembles", 《ACS CATALYSIS》 * |
| HADJIIVANOV, K ET AL: "FTIR study of CO interaction with Ru/TiO2 catalysts", 《JOURNAL OF CATALYSIS》 * |
| RICHARD H. BOWKER ET AL: "Synthesis and Hydrodeoxygenation Properties of Ruthenium Phosphide Catalysts", 《ACS CATALYSIS》 * |
| XU, YANLI ET AL: "Interaction between Cs and Ni2P/SiO2 for enhancing isobutane dehydrogenation in the presence of hydrogen", 《REACTION KINETICS MECHANISMS AND CATALYSIS》 * |
| 孙翠平: "磷化钌催化剂的制备及其加氢性能的研究", 《中国学位论文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113385205A (en) * | 2021-07-16 | 2021-09-14 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
| CN113385205B (en) * | 2021-07-16 | 2023-05-12 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
| CN115254158A (en) * | 2022-08-22 | 2022-11-01 | 中国科学院兰州化学物理研究所 | Nanocluster metal phosphide-phosphorus-carbon catalyst and preparation and application thereof |
| CN115254158B (en) * | 2022-08-22 | 2023-12-22 | 中国科学院兰州化学物理研究所 | Nanocluster metal phosphide-phosphorus-carbon catalyst and preparation and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111617785B (en) | 2021-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10913052B1 (en) | Supported bimetallic core-shell structure catalyst and its preparation method | |
| CN112044434B (en) | Single-atom noble metal/transition metal oxide composite material and preparation method and application thereof | |
| CN111617785B (en) | Supported ruthenium-based phosphide catalyst and preparation method thereof | |
| CN102553579A (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| Long et al. | Construction of trace silver modified core@ shell structured Pt-Ni nanoframe@ CeO 2 for semihydrogenation of phenylacetylene | |
| CN111185237A (en) | Selective hydrogenation catalyst, preparation method and application thereof | |
| CN108579750B (en) | Copper-doped Ni/SiO2Nano composite catalyst and preparation method thereof | |
| CN109718807B (en) | Methane dry reforming catalyst, preparation method and application thereof, and method for preparing synthesis gas by methane dry reforming | |
| Song et al. | Controlled synthesis of PtNi hexapods for enhanced oxygen reduction reaction | |
| Wu et al. | Well-defined metal nanoparticles for electrocatalysis | |
| JP2012041622A (en) | Pd-Fe ALLOY NANOPARTICLE, METHOD FOR PRODUCING THE SAME, AND EXHAUST EMISSION CONTROL CATALYST USING Pd-Fe ALLOY NANOPARTICLE | |
| CN114534722B (en) | Noble metal catalyst for preparing hydrogen from methanol and preparation method and application thereof | |
| You et al. | Pd/CNT with controllable Pd particle size and hydrophilicity for improved direct synthesis efficiency of H 2 O 2 | |
| CN105170153A (en) | SiO2 aerogel supported Co-based catalyst and application thereof | |
| CN108855104A (en) | A kind of ormolu support type grade porous aluminum oxide catalyst and preparation method thereof | |
| CN111013600B (en) | Shallow surface layer metal monatomic catalyst and preparation method and application thereof | |
| CN110867588B (en) | PdAu alloy nanoparticle catalyst with core-shell structure and preparation method thereof | |
| CN111359626A (en) | RuNi bimetal supported carbon dioxide methanation catalyst and preparation method thereof | |
| CN117123218B (en) | High-dispersion IrSn alloy catalyst, preparation method and application | |
| Chen et al. | Single‐Atom Heterogeneous Catalysts | |
| US20210245141A1 (en) | Nanocrystal composite | |
| CN108855209A (en) | A kind of ormolu support type grade hole titanium molecular sieve catalysis material and preparation method thereof | |
| CN114797816B (en) | Preparation method of polyhydroxy nano aluminum oxide with transition metal replacing Al framework | |
| CN115532272B (en) | Preparation method and application of NiY rare earth monoatomic alloy nano-catalyst | |
| CN113731407B (en) | TiO 22Base noble metal catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |