CN113426463A - In-situ preparation and application of high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst - Google Patents
In-situ preparation and application of high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 17
- 239000011733 molybdenum Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 7
- 230000023556 desulfurization Effects 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 33
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 claims 1
- XMAUFBKXKDZDLJ-UHFFFAOYSA-N 1-benzothiophene;dibenzothiophene Chemical compound C1=CC=C2SC=CC2=C1.C1=CC=C2C3=CC=CC=C3SC2=C1 XMAUFBKXKDZDLJ-UHFFFAOYSA-N 0.000 claims 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 claims 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims 1
- 229940078494 nickel acetate Drugs 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- 230000021615 conjugation Effects 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 230000037361 pathway Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- HNDMNBUITRNJKK-UHFFFAOYSA-N [Ni](=S)=S Chemical compound [Ni](=S)=S HNDMNBUITRNJKK-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C10G45/06—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 nickel or cobalt metal, or compounds thereof
- C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides an in-situ preparation method and application of a high-efficiency non-supported porous sulfidic nickel-molybdenum catalyst. The method is characterized in that a molybdenum source is dissolved in an organic solvent, a nickel source is doped in situ according to a certain proportion, then a reaction catalyst is added, then a mixed solution is reacted in a constant-temperature oven and is kept for a certain time, and the obtained product is naturally cooled, centrifuged, washed and dried in vacuum to obtain the non-supported porous sulfurized nickel-molybdenum catalyst. The high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst prepared by the invention has higher specific surface area and pore channel structure, and organic matters are captured through conjugation and the position of bimetal is accurately regulated and controlled. The non-supported porous sulfurized nickel-molybdenum bimetallic catalyst provided by the invention shows good catalytic activity and extremely high direct desulfurization reaction path ratio in the hydrodesulfurization application of sulfur-containing compounds, and the preparation process is simple and convenient to operate, low in cost, high in repeatability and good in application prospect in the aspect of oil product refining.
Description
Technical Field
The invention relates to an in-situ preparation method and application of a high-efficiency non-supported porous nickel-molybdenum sulfide catalyst, belonging to the technical field of synthesis and industrial catalysis application of molybdenum-based catalytic materials.
Background
The supported bimetallic catalyst plays an important role in oil refining due to excellent synergistic effect. The most widely used is gamma-Al2O3Supported nickel (cobalt) molybdenum catalysts (e.g., Zepeda T.A, Pawelec B, Obeso-Etrella R, et Al. comparative HDS and HDN reactions over NiMoS/HMS-Al catalysts: minimizing of the inhibition of HDS reactions by sub-catalytic modification with P, Applied Catalysis B Environmental,2016,180: 569-. The hydrodesulfurization performance of the catalyst is improved by regulating and controlling the metal composition, structure and shape size of the supported catalyst and improving the loading amount of the active metal or the dispersion degree of the active metal. But because of the limitation of the carrier structure, the metal loading capacity is difficult to promote, and the further optimization and upgrade of the performance of the supported molybdenum-based catalyst are restricted. In contrast, unsupported molybdenum-based catalysts are considered as potential catalysts due to their high content of active components, and their further development and industrial application are limited by the low metal utilization (low surface area, poor pore structure) coupled with the poor multi-metal coupling mechanism. In order to improve the metal utilization efficiency of the non-supported hydrofining catalyst, the preparation of the non-supported molybdenum-based catalyst with high specific surface area is the most direct and effective method for preparing the high-activity non-supported molybdenum-based catalyst. Up to now, there are only a few methods for preparing high specific surface areas (180- & ltSUB & gt 330 m)2Per g) molybdenum-based catalytic material: such as the hard template method (Shi Y.F., Wan Y, Liu R.L, et al. Synthesis of high order meso chromatography WS)2 and MoS2via a high-temperature reduced sulfuric acid route, Journal of the American Chemical Society,2007,129(30):9522-2Graphene compositions with an excellent electrochemical performance for lithium batteries, American Chemical Society Nano,2011,5(6):4720-,Berhault G,Aguilar A,et al.Characterization and HDS Activity of Mesoporous MoS2catalysts Prepared by in Situ Activation of Tetraalkylammonium Thiomolybdates, Journal of Catalysis,2002,208(2):359 369.). Among them, the template-free method is gradually receiving attention due to its low synthesis cost, but its precise preparation process still presents challenges. In addition, the mechanism of metal coupling of unsupported molybdenum-based multimetallic catalysts is unclear. The preparation of high-performance non-supported molybdenum-based catalysts and further oil refining applications are still in urgent need of research.
Disclosure of Invention
The invention aims to provide an in-situ preparation method of a high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst and improve the hydrodesulfurization performance of the catalyst in oil product refining. The invention adopts an organic solvent method to synthesize the porous nickel molybdenum sulfide catalyst, and realizes the microscopic assembly of the bimetallic sulfide by in-situ doping and organic coupling. On one hand, a nickel-molybdenum sulfide composite material with high specific surface area and rich pore structure is constructed, on the other hand, the overgrowth of sulfide is inhibited by using organic matters, and the nanoscale size of the product is controlled; the prepared non-supported porous sulfidic nickel-molybdenum catalyst shows good catalytic activity and extremely high direct desulfurization reaction path proportion in oil product refining-hydrodesulfurization reaction. The method has the advantages of simple synthesis steps, mild conditions, low synthesis cost, strong repeatability and good application prospect.
In order to achieve the purpose, the invention adopts the technical scheme that:
an in-situ solvothermal preparation method of an unsupported porous sulfidic nickel-molybdenum catalyst specifically comprises the following steps:
(1) dissolving ammonium tetrathiomolybdate into an organic solvent at room temperature, and continuously stirring until the ammonium tetrathiomolybdate is uniformly mixed to obtain a solution a;
(2) adding a nickel source into the solution a at room temperature, continuously stirring, and uniformly mixing to obtain a solution b;
(3) adding a catalyst into the solution b at room temperature, continuously stirring, and uniformly mixing to obtain a mixed solution;
(4) transferring the mixed solution into a reaction kettle, and placing the reaction kettle in a drying oven for heating reaction;
(5) and cooling to room temperature after the reaction is finished, and separating to obtain the high-efficiency non-supported porous sulfurized nickel-molybdenum catalytic material.
In the above preparation method, the ammonium tetrathiomolybdate in the step (1) is obtained by self-preparation according to the literature [ inorganic salt industry, 2007(05):12-15 ].
In the preparation method, the organic solvent in the step (1) is one or more of aniline, ethylenediamine and cyclohexylamine, the catalyst is one or more of thiourea and urea, and the molar ratio of the molybdenum content in the ammonium tetrathiomolybdate to the organic solvent is 1: 2-6.
In the preparation method, the nickel source in the step (2) is one or more of nickel acetate tetrahydrate, nickel nitrate hexahydrate and nickel chloride.
In the preparation method, the in-situ doping molar ratio of the nickel content of the nickel source in the step (2) to the molybdenum content of ammonium tetrathiomolybdate is 1: 0.2-2.
In the preparation method, the catalyst in the step (3) is one or more of thiourea or urea; the molar ratio of the addition amount of the catalyst to the molybdenum content of the ammonium tetrathiomolybdate is 0.5-2: 1.
In the preparation method, the reaction kettle in the step (4) is a 50mL crystallization kettle with a Teflon lining, and the filling degree of the crystallization kettle is 70-80%.
In the preparation method, the temperature rise reaction temperature in the step (4) is 170-200 ℃, and the reaction time is 10-20 hours.
In the above production method, the operation of separating the product described in the step (5) is centrifugation, washing and drying.
The non-supported porous nickel molybdenum in a sulfuration state prepared by the method is characterized in that: the specific surface area is 100-200 m2And/g, the metal nickel and the metal molybdenum exist in a sulfuration state, and the existence of the organic matter promotes the uniform dispersion of the metal sulfide.
The invention has the following advantages:
1. the nickel-molybdenum catalyst with the porous structure is obtained by in-situ doping the second metal by a solvothermal method, so that the specific surface area is increased, and the utilization rate of the active metal is increased.
2. The falling position between the metal sulfides can be accurately regulated and controlled through the organic matters, and the good bimetal synergistic effect is achieved.
3. The non-supported porous sulfurized nickel-molybdenum catalytic material prepared by the invention has high hydrodesulfurization activity, high stability and direct desulfurization path proportion in the hydrofining-hydrodesulfurization reaction, and has huge industrial application potential.
4. The preparation method of the non-supported porous sulfurized nickel-molybdenum catalytic material has the advantages of simple operation, short production period, high repeatability and safety and wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) diagram of a high-efficiency unsupported porous nickel molybdenum catalytic material in a sulfided state.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a high-efficiency unsupported porous nickel molybdenum catalytic material in a sulfuration state.
FIG. 3 is a Transmission Electron Microscope (TEM) image of the high-efficiency non-supported porous nickel molybdenum sulfide catalytic material.
FIG. 4 is a drawing of nitrogen adsorption and desorption of a high-efficiency non-supported porous nickel molybdenum sulfide catalytic material.
FIG. 5 is a diagram showing the results of a high-efficiency unsupported porous nickel molybdenum catalytic material in a catalytic reaction of dibenzothiophene hydrodesulfurization.
FIG. 6 is a reaction path proportion diagram of a high-efficiency non-supported porous nickel-molybdenum sulfide catalytic material in a dibenzothiophene hydrodesulfurization catalytic reaction.
Detailed Description
In order to make the preparation process, characteristics and advantages of the related catalyst of the present application clearer, the technical scheme will be completely described with reference to the attached drawings. It should be noted that the examples mentioned in the present invention are some examples of this experiment, but not all examples; the starting materials mentioned in the present invention are all purchased commercially and the procedures and synthetic procedures not mentioned are process steps or preparation methods well known to those skilled in the art. Any modification which does not depart from the spirit and scope of the invention is deemed to be within the scope of the invention.
Example 1:
1.30g of ammonium tetrathiomolybdate is dissolved into 20mL of cyclohexylamine solvent at room temperature; continuously adding 1.45g of nickel nitrate hexahydrate and continuously stirring; after mixing evenly, adding 0.76g of urea into the mixed solution; after being mixed uniformly, the mixture is transferred to a 50mL crystallization kettle and kept in a constant temperature oven at 200 ℃ for 20 hours. And after natural cooling, centrifuging the product by using absolute ethyl alcohol and deionized water successively, washing for five times, and drying in vacuum to obtain the non-supported porous sulfurized nickel-molybdenum catalytic material, wherein the nickel-molybdenum catalytic material is marked as Ni1Mo 1-1.
Example 2:
1.30g of ammonium tetrathiomolybdate is dissolved in 20mL of ethylenediamine solvent at room temperature; continuously adding 1.45g of nickel nitrate hexahydrate and continuously stirring; after mixing evenly, adding 0.76g of thiourea into the mixed solution; after being mixed uniformly, the mixture is transferred to a 50mL crystallization kettle and kept in a constant temperature oven of 180 ℃ for 20 hours. And after natural cooling, centrifuging the product by using absolute ethyl alcohol and deionized water successively, washing for five times, and drying in vacuum to obtain the non-supported porous sulfurized nickel-molybdenum catalytic material, wherein the nickel-molybdenum catalytic material is marked as Ni1Mo 1-2.
Example 3:
1.30g of ammonium tetrathiomolybdate was dissolved in 20ml of aniline solvent at room temperature; continuously adding 0.723g of nickel nitrate hexahydrate and continuously stirring; after mixing evenly, adding 0.76g of urea into the mixed solution; after being mixed uniformly, the mixture is transferred to a 50mL crystallization kettle and kept in a constant temperature oven at 200 ℃ for 20 hours. And after natural cooling, centrifuging the product by using absolute ethyl alcohol and deionized water successively, washing for five times, and drying in vacuum to obtain the non-supported porous sulfurized nickel-molybdenum catalytic material, wherein the nickel-molybdenum catalytic material is marked as Ni1Mo 2-1.
Example 4:
1.30g of ammonium tetrathiomolybdate is dissolved into 30ml of cyclohexylamine solvent at room temperature; continuously adding 1.45g of nickel nitrate hexahydrate and continuously stirring; after being mixed evenly, 1.52g of urea is added into the mixed solution as a catalyst; after being mixed uniformly, the mixture is transferred to a 50ml crystallization kettle and kept in a constant temperature oven at 200 ℃ for 20 hours. And after natural cooling, centrifuging the product by using absolute ethyl alcohol and deionized water successively, washing for five times, and drying in vacuum to obtain the non-supported porous sulfurized nickel-molybdenum catalytic material, wherein the nickel-molybdenum catalytic material is marked as Ni1Mo 3-1.
Taking the sample Ni1Mo1-1 in the embodiment example 1 as a typical sample, the sample is subjected to X-ray diffraction, scanning electron microscope, transmission electron microscope, nitrogen adsorption and desorption and X-ray elemental analysis characterization and analysis.
FIG. 1 is an X-ray diffraction pattern of a Ni1Mo1-1 sample, and from FIG. 1, it can be found that the Ni1Mo1-1 sample shows XRD characteristic diffraction peaks of molybdenum disulfide at 14.4 ° (002), 33.2 ° (100) and 58.5 ° (110) and XRD characteristic diffraction peaks of nickel disulfide at 27.2 ° (111), 35.3 ° (210), 45.1 ° (220) and 53.5 ° (311). It is known that the catalytic material obtained according to the process of the invention is a mixed phase of molybdenum disulphide and nickel disulphide.
FIG. 2 is a scanning electron microscope image of a Ni1Mo1-1 sample, which shows that the catalytic material sample obtained by the method of the present invention is fluffy and hollow.
FIG. 3 is a transmission electron micrograph of a Ni1Mo1-1 sample, and it can be seen from FIG. 3 that the molybdenum disulfide layers have a spacing of 0.76nm and are stacked with the lattice stripes of nickel disulfide, and the catalytic material obtained by the method of the present invention is a mixed phase of two sulfides.
FIG. 4 shows the nitrogen desorption diagram of the Ni1Mo1-1 sample, and it can be seen that the nitrogen desorption isotherm of the obtained sample belongs to the IV-H3 type, which indicates the irregular lamellar stacking pores. The specific surface area reaches 220m2/g。
Example 4 of implementation:
hydrodesulfurization reaction of sulfur-containing compounds such as dibenzothiophene is carried out in a fixed bed microreactor. The raw material is an n-heptane solution containing 1 wt% of dibenzothiophene, and an industrial supported nickel-molybdenum-sulfur catalyst (NiMoS/gamma-Al) is selected as typified by the non-supported porous nickel-molybdenum catalyst Ni1Mo1-1 prepared in the embodiment example 12O3) For comparison, the catalytic performance was evaluated. The evaluation procedure was as follows:
step one, tabletting a sample Ni1Mo1-1, screening, and selecting 2mL of particles with 20-40 meshes as a catalyst.
And step two, sequentially filling the screened catalyst and quartz sand with the same mesh number into a reaction tube. After the installation, the fixed-bed microreactor was first checked for gas tightness and then heated (5 ℃/min) to 240 ℃ under the protection of nitrogen (30mL/min) and held for 3 hours. Then the reaction was started by switching to hydrogen while continuing to maintain the gas flow rate (30mL/min) and the reaction pressure at 2MPa, while feeding at 6 mL/h.
And step three, taking the temperature of every 20 ℃ as a detection temperature, and detecting the performance of the catalyst within the range of 240-320 ℃. The hydrodesulphurisation product obtained at each temperature point was analysed by gas chromatography agilent-7820.
Step four, using 2mL of contrast sample to industrially load the nickel-molybdenum-sulfur catalyst (NiMoS/gamma-Al)2O3) The above second to third steps were repeated in place of the sample Ni1Mo1-1 in the second step.
Two parallel pathways for dibenzothiophene hydrodesulfurization are known to have different respective products, namely a direct desulfurization pathway (DDS), the main product of which is Biphenyl (BP); hydrodesulfurization products of the hydrogenation pathway (HYD) are predominantly Cyclohexylbenzene (CHB) and phenylcyclohexane (BCH). The evaluation results are shown in fig. 5 and 6.
FIG. 5 is a graph showing the results of the high-efficiency unsupported porous sulfided nickel-molybdenum catalyst in the catalytic reaction of dibenzothiophene hydrodesulfurization, and it can be seen that the high-efficiency unsupported porous sulfided nickel-molybdenum catalyst (Ni1Mo1-1) synthesized by the present invention has higher hydrodesulfurization catalytic performance, and the hydrodesulfurization activity at low temperature is significantly higher than that of the industrial supported nickel-molybdenum-sulfur catalyst (NiMoS/gamma-Al)2O3)。
FIG. 6 is a reaction path ratio chart of the high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst in the catalytic reaction of dibenzothiophene hydrodesulfurization, which shows that the high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst synthesized according to the present invention (Ni1Mo1-1) is compared with the industrial supported nickel-molybdenum-sulfur catalyst (NiMoS/gamma-Al)2O3) Has higher direct desulfurization reaction path diameter ratio (S)DDS/HYD)。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An in-situ preparation method of a high-efficiency non-supported porous sulfuration state nickel-molybdenum catalyst comprises the following steps:
(1) dissolving ammonium tetrathiomolybdate into an organic solvent at room temperature, and continuously stirring until the ammonium tetrathiomolybdate is uniformly mixed to obtain a solution a;
(2) adding a nickel source into the solution a at room temperature, continuously stirring, and uniformly mixing to obtain a solution b;
(3) adding a catalyst into the solution b at room temperature, continuously stirring, and uniformly mixing to obtain a mixed solution;
(4) transferring the mixed solution into a reaction kettle, and placing the reaction kettle in a drying oven for heating reaction;
(5) and cooling to room temperature after the reaction is finished, and separating the product to obtain the non-supported porous sulfurized nickel-molybdenum catalytic material.
2. The in-situ preparation method of the high-efficiency unsupported porous nickel-molybdenum catalytic material according to claim 1, wherein the organic solvent in step (1) is one or more of aniline, ethylenediamine and cyclohexylamine solution; the molar ratio of the molybdenum content in the ammonium tetrathiomolybdate to the organic solvent is 1: 2-6.
3. The in-situ preparation method of the high-efficiency unsupported porous nickel-molybdenum catalytic material according to claim 1, characterized in that the nickel source in step (2) is one or more of nickel acetate, nickel nitrate hexahydrate and nickel chloride; the in-situ doping molar ratio of the nickel content of the nickel source to the molybdenum content of the ammonium tetrathiomolybdate is 1: 0.2-2.
4. The in-situ preparation method of the high-efficiency unsupported porous nickel-molybdenum catalytic material according to claim 1, wherein the catalyst in step (3) is one or more of thiourea and urea; the molar ratio of the addition amount of the catalyst to the molybdenum content of the ammonium tetrathiomolybdate is 0.5-2: 1.
5. The in-situ preparation method of the high-efficiency unsupported porous nickel-molybdenum catalytic material according to claim 1, wherein the reaction kettle in step (4) is a 50mL crystallization kettle with a Teflon liner, and the filling degree of the crystallization kettle is 70-80%.
6. The in-situ preparation method of the high-efficiency unsupported porous nickel-molybdenum catalytic material according to claim 1, wherein the temperature rise reaction temperature in step (4) is 170-200 ℃, and the reaction time is 10-20 hours.
7. The method for preparing the high-efficiency unsupported porous nickel-molybdenum catalytic material in the sulfurized state according to claim 1, wherein the separation of the product in step (5) is performed by centrifugation, washing and drying.
8. A high-efficiency unsupported porous sulfidic nickel-molybdenum catalytic material prepared in situ by the method of any one of claims 1 to 7, characterized in that the specific surface area of the material is 100 to 200m2And/g, the metal nickel and the metal molybdenum exist in a sulfuration state, and the existence of the organic matter promotes the uniform dispersion of the metal sulfide.
9. A high-efficiency unsupported porous nickel-molybdenum catalyst material prepared in situ by the method of any one of claims 1 to 7, wherein the high-efficiency unsupported porous nickel-molybdenum catalyst exhibits high desulfurization rate and direct desulfurization path ratio in the application of oil product refining reaction.
10. An application of the high-efficiency non-supported porous nickel-molybdenum catalytic material prepared in situ by the method of any one of claims 1 to 7 in hydrofining of oil products, wherein the oil products comprise one or more sulfur-containing compounds containing thiophene, benzothiophene dibenzothiophene or 4, 6-dimethyldibenzothiophene.
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