CN108620117B - Low-temperature reduction preparation of high-dispersion load type Ni2Method for preparing P catalyst - Google Patents
Low-temperature reduction preparation of high-dispersion load type Ni2Method for preparing P catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000006185 dispersion Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 128
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 63
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 32
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000005470 impregnation Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229960004106 citric acid Drugs 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 10
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- LRZSAGKIMYFLHY-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;dihydrate Chemical compound O.O.OC(=O)CC(O)(C(O)=O)CC(O)=O LRZSAGKIMYFLHY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 238000007598 dipping method Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 abstract description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/106—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/7215—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a method for preparing high-dispersion load type Ni by reducing hypophosphite with hydrogen at low temperature2A method of P catalyst belongs to the technical field of preparation of nickel phosphide catalyst. The invention dissolves nickel salt and citric acid in deionized water to obtain impregnation liquid, the impregnation liquid is impregnated on a porous zeolite carrier, and solid powder is obtained after standing, drying and calcining. Then dipping ammonium hypophosphite solution on the solid powder, drying at low temperature, placing in hydrogen atmosphere, and heating and reducing at program temperature to obtain the supported Ni2And (3) a P catalyst. The preparation method is simple and convenient, the reduction temperature is low, and the prepared Ni2The P catalyst has the advantages of high dispersity, good hydrogenation activity and the like, and can be widely applied to reactions of hydrodesulfurization, denitrification and the like of oil products.
Description
Technical Field
The invention belongs to the technical field of preparation of nickel phosphide catalysts, and particularly relates to a method for preparing high-dispersion supported Ni by low-temperature reduction2A method of preparing P catalyst.
Background
The development of a high-activity hydrofining catalyst is the key to producing ultra-clean fuel oil. Currently, metal sulfidation is mainly used industriallyPhysical catalyst (CoMoS/gamma-Al)2O3And NiMoS/gamma-Al2O3) The fuel oil is subjected to catalytic hydrogenation treatment, but the deep desulfurization and deep dearomatization of the fuel oil are difficult to realize due to the low hydrogenation activity of the catalyst, and the ultra-clean fuel oil is difficult to produce. In recent years, transition metal phosphide catalysts have received great attention because of their excellent activity in hydrodesulfurization, hydrodearomatization and the like. In particular, Ni2The P catalyst has very high intrinsic hydrogenation activity and is considered to be a next generation hydrofinishing catalyst with promising substitution for metal sulfides.
The high-temperature programming reduction method is to prepare Ni2The P catalyst is prepared by a common method, because the P-O bond in the phosphate is stronger, the reduction temperature is higher (above 550 ℃, CN101168132A), and the prepared Ni2The P particles are relatively large and have poor dispersibility. Thermal cracking of hypophosphite and phosphite to produce Ni2P, although having a low decomposition temperature, generates phosphates during thermal cracking, and requires washing with water to remove impurities, thereby reducing Ni2Activity of P and inability to increase Ni2Dispersion of P (CN 101671009B; Applied Catalysis A General,2013, 462; 463(27): 247-.
The invention utilizes the complexation of citric acid and nickel species and the interaction of the acidic hydroxyl of the zeolite and the carboxyl in the citric acid molecule to highly disperse the nickel species complexed with the citric acid on the surface of the zeolite, and the citric acid and the nickel nitrate which are impregnated on the zeolite carrier form small-particle nickel species on the zeolite carrier after high-temperature calcination. Ammonium hypophosphite is impregnated onto a nickel-containing zeolite support, dried at low temperature, and directly reduced at relatively low temperature to obtain highly dispersed Ni2And (3) a P catalyst.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for preparing highly dispersed supported Ni by reducing hypophosphite with hydrogen by adopting a step-by-step impregnation method2A method of preparing P catalyst. The method comprises dissolving nickel nitrate and citric acid in deionized water according to molar ratio to obtain a soaking solution, and soakingImpregnated onto a porous zeolite support. And standing, drying and calcining to obtain solid powder containing nickel. Then dipping ammonium hypophosphite solution on the solid powder containing nickel, drying at low temperature, and directly reducing at low temperature in hydrogen atmosphere to obtain the load type Ni2And (3) a P catalyst.
The invention is characterized in that: the reduction temperature is low, no water washing is needed, and the prepared Ni2The P catalyst has small particles, good activity, high dispersity, simple operation and small particles of Ni2The P catalyst has excellent hydrogenation performance and can be widely applied to reactions of hydrodesulfurization, denitrification and the like of oil products.
The technical scheme adopted by the invention is as follows:
(1) weighing nickel salt and citric acid with corresponding mass according to the molar ratio of citric acid to nickel of 1-3: 1, and dissolving the nickel salt and citric acid in deionized water to obtain clear impregnation liquid;
citric acid is added as an organic complexing agent, and in addition to citric acid, some organic complexing agents containing carboxyl groups may be selected, such as 1, 2-cyclohexanediaminotetraacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid or ethylenediaminetetraacetic acid salts.
The nickel salt is one or more of analytically pure nickel nitrate, nickel chloride, nickel acetate and nickel acetylacetonate. The citric acid is citric acid monohydrate (C)6H8O7·H2O) and citric acid dihydrate (C)6H8O7·2H2O).
(2) And (2) adding the impregnation liquid obtained in the step (1) into a porous zeolite carrier for impregnation, drying for 6-12 hours at room temperature, drying for 10-14 hours at 80-120 ℃, calcining the dried solid in an air atmosphere, heating to 400-550 ℃ at a heating rate of 2-5 ℃/min, calcining for 3-5 hours to obtain a solid, and grinding to obtain the nickel-containing porous zeolite powder.
The porous zeolite is acidic silicon-aluminum zeolite, specifically one or more of porous ZSM-5 zeolite, porous mordenite, porous Y zeolite and porous Beta zeolite.
(3) According to the molar ratio of nickel atoms to phosphorus atoms in ammonium hypophosphite of 1: 1.5-3Weighing ammonium hypophosphite and dissolving the ammonium hypophosphite in deionized water to obtain an ammonium hypophosphite solution, dipping the ammonium hypophosphite solution onto the ground nickel-containing porous zeolite powder, drying the powder for 6 to 12 hours at room temperature, then placing the powder in an oven at 50 to 80 ℃ for drying for 10 to 24 hours, placing the dried substance in a hydrogen atmosphere at 300 to 400 ℃ for reduction for 2 to 4 hours, wherein the heating rate is 1 to 3 ℃/min, the hydrogen flow rate is 100 plus-air flow 200mL/min, naturally cooling the reduced substance to the room temperature, introducing 0.5vol% of O2/N2Passivating with passivating gas for 2 hours to obtain the high-dispersion load type Ni2And (3) a P catalyst.
The ammonium hypophosphite is analytically pure ammonium hypophosphite (NH)4H2PO2) (ii) a High dispersion supported Ni2The loading amount of nickel in the P catalyst is 1-30 wt% of the mass of the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the carrier is impregnated with impregnation liquid obtained by nickel salt and citric acid, so that substances in the impregnation liquid are fully adsorbed and diffused by the carrier, then the carrier is dried at low temperature and calcined, and the carrier is ground to obtain the nickel-based catalyst carrier; furthermore, the porous zeolite has a high specific surface area, which is also advantageous for preparing highly dispersed Ni2P particles;
(2) the method comprises the steps of dipping an ammonium hypophosphite aqueous solution into a nickel-based catalyst carrier, drying, and then reducing at 300-400 ℃ in a hydrogen atmosphere to obtain the supported nickel phosphide catalyst. The ammonium hypophosphite can be used as a phosphorus source and a reducing agent, and can be decomposed to generate phosphine or zero-valent phosphorus at a lower reduction temperature, and the phosphine reduces nickel species at a low temperature or the zero-valent phosphorus reacts with the zero-valent nickel to generate a nickel phosphide catalyst;
(3) the reduction temperature of the invention is 300-400 ℃, the reduction temperature is low, and the prepared Ni2Small P particle, Ni2P on a supportThe dispersity is high, and the operation is simple; produced small particles of Ni2The P catalyst has excellent hydrogenation performance and can be widely applied to reactions such as hydrodesulfurization, denitrification and the like of oil products;
(4) the invention prepares Ni2No water washing is needed in the process of the P catalyst, and Ni is avoided during water washing2P particles are agglomerated or oxidized, thus favoring Ni2Increase of P catalyst activity.
Drawings
FIG. 1 shows supported Ni synthesized in example 12Powder X-ray diffraction pattern of P catalyst.
FIG. 2 shows supported Ni synthesized in comparative example 12Powder X-ray diffraction pattern of P catalyst.
FIG. 3 shows supported Ni synthesized in comparative example 22Powder X-ray diffraction pattern of P catalyst.
FIG. 4 shows supported Ni synthesized in example 12Transmission electron micrograph of P catalyst.
FIG. 5 shows supported Ni synthesized in example 1, comparative example 1 and comparative example 22And P catalyst activity test result chart.
Detailed Description
The present invention is described in further detail below by way of examples. It should be noted that these examples are merely intended to illustrate the present invention and should not be construed as limiting the scope of the present invention in any way.
Example 1
0.2972g of nickel nitrate (Ni (NO) was added at room temperature3)2·6H2O) is added into 1mL of deionized water, after dissolution, 0.4202g of citric acid monohydrate (CA) is added into the nickel nitrate solution, and the dipping solution is obtained, wherein the molar ratio of Ni to CA is 1: 2. The resulting impregnation solution was added to 1g of a porous ZSM-5 zeolite (ZSM-5-M) support. After standing at room temperature for 12 hours, the mixture was dried at 100 ℃ for 12 hours, and the dried solid powder was calcined at 500 ℃ for 4 hours in an air atmosphere. Then, a solution containing 0.1661g of ammonium hypophosphite (NH)4H2PO2) Is impregnated into the above calcined solid powder in a molar ratio of Ni to P of 1:2Drying at 50 deg.C for 12 hr to obtain catalyst precursor. The temperature was raised from room temperature to 400 ℃ at a temperature raising rate of 2 ℃/min under a hydrogen atmosphere and maintained at that temperature for 3 hours (hydrogen flow rate of 100mL/min), and then cooled to room temperature. To prevent Ni2The P is in contact with air to generate violent oxidation reaction, and 0.5vol% of O is used before the sample is in contact with air2/N2Passivating with passivating gas for 2 hours. Then the supported Ni with the Ni loading of 6 wt.% can be obtained2P catalyst, labelled Ni2P/ZSM-5-M。
Example 2
0.4955g of nickel nitrate (Ni (NO) was added at room temperature3)2·6H2O) was added to 1mL of deionized water, and after dissolution, 0.3572g of citric acid (C) was added to the nickel nitrate solution6H8O7·H2O) to obtain an impregnation liquid, wherein the molar ratio of Ni to CA is 1:1, and adding the obtained impregnation liquid to 1g of porous ZSM-5 zeolite carrier. Standing at room temperature for 12 hours, drying at 100 ℃ for 12 hours, and calcining the dried solid powder at 500 ℃ for 4 hours in an air atmosphere. Then, the solution containing 0.2823g of ammonium hypophosphite (NH)4H2PO2) Is impregnated into the calcined solid powder in a molar ratio of Ni to P of 1:2, and dried at room temperature and 50 ℃ for 12 hours to obtain a catalyst precursor. Under a hydrogen atmosphere, the temperature was raised from room temperature to 400 ℃ at 2 ℃/min and maintained at that temperature for 3 hours (hydrogen flow rate 100mL/min), and then cooled to room temperature. To prevent Ni2The P is in contact with air to generate violent oxidation reaction, and 0.5vol% of O is used before the sample is in contact with air2/N2Passivating with passivating gas for 2 hours. Then the supported Ni with the Ni loading of 10 wt.% can be obtained2And (3) a P catalyst.
Example 3
1.4864g of nickel nitrate (Ni (NO) was added at room temperature3)2·6H2O) was added to 1mL of deionized water, and after dissolution, 2.1435g of citric acid (C) was added to the nickel nitrate solution6H8O7·H2O) to obtain a dipping solution, wherein the molar ratio of Ni to CA is 1:2, adding the obtained dipping solution into1g of ZSM-5-M carrier. Standing at room temperature for 12 hours, drying at 100 ℃ for 12 hours, and calcining the dried solid powder in an air atmosphere at 500 ℃ for 4 hours. Then, a solution containing 0.8469g of ammonium hypophosphite (NH)4H2PO2) Is impregnated into the calcined solid powder in a molar ratio of Ni to P of 1:2, and dried at room temperature and 50 ℃ for 12 hours to obtain a catalyst precursor. Under a hydrogen atmosphere, the temperature was raised from room temperature to 400 ℃ at 2 ℃/min and maintained at that temperature for 3 hours (hydrogen flow rate of 160mL/min), and then cooled to room temperature. To prevent Ni2The P is in contact with air to generate violent oxidation reaction, and 0.5vol% of O is used before the sample is in contact with air2/N2Passivating with passivating gas for 2 hours. Thus obtaining the supported Ni with the Ni loading of 30 wt%2And (3) a P catalyst.
Example 4
0.9909g of nickel nitrate (Ni (NO) was added at room temperature3)2·6H2O) was added to 1mL of deionized water, and after dissolution, 2.1435g of citric acid (C) was added to the nickel nitrate solution6H8O7·H2O) to obtain an impregnation liquid, wherein the molar ratio of Ni to CA is 1:3, and adding the obtained impregnation liquid to 1g of ZSM-5-M carrier. The mixture was allowed to stand at room temperature for 12 hours, dried at 100 ℃ for 12 hours, and the dried solid powder was calcined at 500 ℃ for 4 hours in an air atmosphere. Then, a solution containing 0.5646g of ammonium hypophosphite (NH)4H2PO2) Is impregnated into the above calcined solid powder with a molar ratio of Ni to P of 1:2, and dried at 50 ℃ for 12 hours to obtain a catalyst precursor. Under a hydrogen atmosphere, the temperature was raised from room temperature to 400 ℃ at 2 ℃/min and maintained at that temperature for 3 hours (hydrogen flow rate of 160mL/min), and then cooled to room temperature. To prevent Ni2The P is in contact with air to generate violent oxidation reaction, and 0.5vol% of O is used before the sample is in contact with air2/N2Passivating with passivating gas for 2 hours. Thus obtaining the supported Ni with the Ni loading of 20 wt%2And (3) a P catalyst.
Comparative example 1
0.2972g of nickel nitrate (Ni (NO) was added at room temperature3)2·6H2O) was added to 1mL of deionized water, and after dissolution, 0.4203g of citric acid (C) was added to the nickel nitrate solution6H8O7·H2O) to obtain an impregnation solution, wherein the molar ratio of Ni to CA is 1:2, adding the obtained impregnation solution to 1gSiO2On a carrier. The mixture was allowed to stand at room temperature for 12 hours, dried at 100 ℃ for 12 hours, and the dried solid powder was calcined at 500 ℃ for 4 hours in an air atmosphere. Then, a solution containing 0.1661g of ammonium hypophosphite (NH)4H2PO2) Is impregnated into the above calcined solid powder with a molar ratio of Ni to P of 1:2, and dried at 50 ℃ for 12 hours to obtain a catalyst precursor. Under a hydrogen atmosphere, the temperature was raised from room temperature to 400 ℃ at 2 ℃/min and maintained at that temperature for 3 hours (hydrogen flow rate 100mL/min), and then cooled to room temperature. To prevent Ni2The P is in contact with air to generate violent oxidation reaction, and 0.5vol% of O is used before the sample is in contact with air2/N2Passivating with passivating gas for 2 hours. Then the supported Ni with the Ni loading of 6 wt.% can be obtained2P catalyst, labelled Ni2P/SiO2。
Comparative example 2
Preparation of supported Ni by temperature programmed high-temperature reduction method2P catalyst: 0.2972g of nickel nitrate (Ni (NO) was added at room temperature3)2·6H2O) was added to 2mL of 10 wt% dilute nitric acid, after dissolution, 0.2641g of diammonium phosphate ((NH) was added to the solution4)2HPO4) To obtain an impregnation solution, wherein the molar ratio of Ni to P is 1:2, and adding the obtained impregnation solution to 1g of porous ZSM-5 zeolite carrier. The mixture was allowed to stand at room temperature for 12 hours, dried at 100 ℃ for 12 hours, and the dried solid powder was calcined at 500 ℃ for 4 hours in an air atmosphere. The calcined solid powder was raised from room temperature to 100 ℃ at 2 ℃/min in a hydrogen atmosphere (hydrogen flow rate of 160mL/min) and held at that temperature for 1 hour, then raised from 100 ℃ to 400 ℃ at 2 ℃/min and held at that temperature for 1 hour, then raised from 400 ℃ to 500 ℃ at 2 ℃/min and held at that temperature for 3 hours, and then cooled to room temperature. To prevent Ni2P is in contact with air to generate violent oxidation reactionBefore the sample is exposed to air, 0.5vol% of O is used2/N2Passivating with passivating gas for 2 hours. Then the supported Ni with the Ni loading of 6 wt.% can be obtained2And (3) a P catalyst.
FIG. 1 is a supported Ni prepared according to example 12P catalyst and standard Ni2X-ray powder diffraction pattern of P phase, as can be seen from FIG. 1, only characteristic diffraction peak of ZSM-5 zeolite can be observed in XRD diffraction pattern of catalyst of example 1, and no obvious Ni can be observed2Characteristic diffraction peak of P phase, which shows that highly dispersed and smaller Ni is formed on the surface of porous ZSM-5 zeolite2P particles. And FIG. 2 is a supported Ni prepared according to comparative example 12P catalyst and standard Ni2Powder X-ray diffraction pattern of P phase, as can be seen from FIG. 2, significant Ni was observed on silica2P characteristic diffraction peak; indicating that large Ni is formed on the surface of the silica2P particles. FIG. 3 is supported Ni prepared according to comparative example 22P catalyst and standard Ni2As is clear from FIG. 3, the X-ray diffraction pattern of the P phase not only shows the characteristic diffraction peak of ZSM-5 zeolite but also shows significant Ni2P characteristic diffraction peak, which shows that Ni is prepared by high-temperature reduction method even if porous ZSM-5 zeolite is used as a carrier2P catalyst, too, does not give highly dispersed, small-particle Ni2And (3) a P catalyst.
To further illustrate Ni prepared according to example 12The P has high dispersibility and small particle size, and the catalyst prepared in example 1 is further characterized by a transmission electron microscope (figure 4), and Ni less than 3nm can be seen from the figure2The P particles are well dispersed on the surface of the zeolite support.
To compare the hydrogenation activity of the catalysts of example 1, comparative example 1 and comparative example 2, we compared the phenylacetylene selective hydrogenation activity of the three catalysts in a parr tank under the following reaction conditions: 100mL of absolute ethyl alcohol, 5mL of phenylacetylene, 0.5g of catalyst, 1MPa of hydrogen pressure, 100 ℃ of reaction temperature and 700 rpm. The results of the activity test are shown in FIG. 5. The hydrogenation activity of the catalyst of example 1 is much higher than that of the catalysts of comparative example 1 and comparative example 2.
Claims (7)
1. Low-temperature reduction preparation of high-dispersion load type Ni2The method for preparing the P catalyst is characterized by comprising the following specific preparation steps:
(1) weighing citric acid and nickel salt with corresponding mass according to the molar ratio of the citric acid to the nickel atoms of 1-3: 1, and dissolving the citric acid and the nickel salt in deionized water to obtain clear impregnation liquid;
(2) adding the impregnation liquid to a porous zeolite carrier for impregnation, drying for 6-12 hours at room temperature, then drying for 10-14 hours at 80-120 ℃, calcining the dried solid in air atmosphere, and grinding the calcined solid to obtain nickel-containing porous zeolite powder;
the porous zeolite carrier is acidic silicon-aluminum zeolite, and specifically is one or more of porous ZSM-5 zeolite, porous mordenite, porous Y zeolite or porous Beta zeolite;
(3) according to the molar ratio of nickel atoms to phosphorus atoms in ammonium hypophosphite of 1: 1.5-3, weighing ammonium hypophosphite, dissolving the ammonium hypophosphite in deionized water to obtain an ammonium hypophosphite solution, soaking the ammonium hypophosphite solution on the ground nickel-containing porous zeolite powder, drying at room temperature, then placing the powder in an oven for drying, placing the dried substance in a hydrogen atmosphere at 300-400 ℃ for reduction for 2-4 hours, naturally cooling to room temperature, and then introducing 0.5vol% of O2/N2Passivating with passivating gas for 2 hours to obtain the high-dispersion load type Ni2And (3) a P catalyst.
2. The method for preparing high-dispersion supported Ni by low-temperature reduction according to claim 12A process for the preparation of a P catalyst, characterized in that: the citric acid in the step (1) is citric acid monohydrate (C)6H8O7∙H2O) or citric acid dihydrate (C)6H8O7∙2H2O) is selected; the nickel salt is one or more of analytically pure nickel nitrate, nickel chloride, nickel acetate or nickel acetylacetonate.
3. The method for preparing high-dispersion supported Ni by low-temperature reduction according to claim 12A process for the preparation of a P catalyst, characterized in that: the temperature rise rate of the calcination in the step (2) is 2-5 ℃/min, the calcination temperature is 400-550 ℃, and the calcination time is 3-5 hours.
4. The method for preparing high-dispersion supported Ni by low-temperature reduction according to claim 12A process for the preparation of a P catalyst, characterized in that: the ammonium hypophosphite mentioned in the step (3) is analytically pure ammonium hypophosphite (NH)4H2PO2）。
5. The method for preparing high-dispersion supported Ni by low-temperature reduction according to claim 12A process for the preparation of a P catalyst, characterized in that: drying at room temperature for 6-12 hours in the step (3); the drying temperature of the oven is 50-80 ℃, and the drying time of the oven is 10-24 hours.
6. The method for preparing high-dispersion supported Ni by low-temperature reduction according to claim 12A process for the preparation of a P catalyst, characterized in that: the reduction heating rate in the step (3) is 1-3 ℃/min, and the hydrogen flow rate is 100-200 mL/min.
7. The method for preparing high-dispersion supported Ni by low-temperature reduction according to claim 12A process for the preparation of a P catalyst, characterized in that: the high-dispersion supported Ni2The loading amount of nickel in the P catalyst is 1-30 wt% of the mass of the catalyst.
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