CN116060048A - Hydrogenation catalyst, preparation method and application thereof - Google Patents
Hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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- CN116060048A CN116060048A CN202111270774.2A CN202111270774A CN116060048A CN 116060048 A CN116060048 A CN 116060048A CN 202111270774 A CN202111270774 A CN 202111270774A CN 116060048 A CN116060048 A CN 116060048A
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- Prior art keywords
- phosphorus
- vib
- hydrogenation
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 119
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 90
- 239000002184 metal Substances 0.000 claims abstract description 90
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 89
- 239000011574 phosphorus Substances 0.000 claims abstract description 89
- 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 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 51
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 33
- 239000003630 growth substance Substances 0.000 claims description 30
- 238000006460 hydrolysis reaction Methods 0.000 claims description 29
- 238000001556 precipitation Methods 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
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- 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
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 108091028664 Ribonucleotide Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002336 ribonucleotide Substances 0.000 description 1
- 125000002652 ribonucleotide group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hydrogenation catalyst and a preparation method and application thereof, wherein the hydrogenation catalyst comprises a carrier, a hydrogenation active metal component and a carbon component which are loaded on the carrier, the content of the carbon component calculated by elements is 0.03-0.8% by weight based on the total amount of the hydrogenation catalyst, the content of the carrier is 40-85% by weight, and the hydrogenation active metal component satisfies the following relation:n (VIB)/n (VIB+VIII) is less than or equal to 0.25 and less than or equal to 0.35, wherein n (VIB) represents the amount of substances of the VIB group metal element, and n (VIB+VIII) represents the sum of the amounts of substances of the VIB group metal element and the VIII group metal element; the carrier is phosphorus-containing alumina, and in the IR spectrum of the phosphorus-containing alumina, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9 to 2.8; wherein I is 3670 3670cm ‑1 Peak height, I 3580 3580cm ‑1 Peak height, I 3770 3770cm ‑1 Peak height, I 3720 3720cm ‑1 Peak height. Compared with the prior art, the hydrogenation catalyst provided by the invention adopts a specific carrier, contains a certain amount of carbon components, has better hydrodenitrogenation and hydrodesulphurization performances, and has longer service life.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a hydrogenation catalyst containing a phosphorus-containing alumina carrier, a preparation method thereof and application thereof in hydrocarbon oil hydrogenation reaction, especially application in hydrogenation treatment of wax oil fractions.
Background
The increasing awareness of environmental protection and the increasingly stringent environmental regulations have forced the refinery to pay more attention to clean fuel production technology development. In the future, market fuels tend to be 'ultra-low sulfur', and fuels which cannot meet the emission standard cannot enter the market. The hydrogenation technology is used as an effective desulfurization means and plays an increasingly important role in the production of clean vehicle fuels, wherein the high-efficiency hydrogenation catalyst is a core technology of the hydrogenation technology, so that the development of a novel hydrogenation catalyst with higher activity and selectivity becomes one of the most urgent demands of the oil refining industry.
Alumina, especially gamma-alumina, is often used as a support for catalyst preparation due to its relatively good pore structure, specific surface area and heat stability. The precursor of alumina is hydrated alumina, such as pseudo-boehmite, and the particle size, morphology, crystallinity, impurity crystal content and the like of the alumina carrier have influence on the properties of pore volume, pore distribution, specific surface area and the like. In the prior art, by modulating the properties of particle size, morphology, crystallinity and the like of hydrated alumina, one can obtain an alumina carrier which can meet specific requirements.
The pore structure, surface acidity and thermal stability of the carrier can be changed by introducing phosphorus into the alumina, so that the activity of the hydrogenation catalyst can be improved. In the prior art, a great number of methods for introducing phosphorus are described, including introduction during alumina preparation, introduction during impregnation, introduction during molding, etc., but the performance and activity stability of the catalyst prepared by the method are still further improved when the catalyst is applied to hydrodesulfurization of distillate oil.
The organic dispersing agent or complexing agent is introduced in the preparation process of the hydrogenation catalyst, so that the obtained catalyst has better hydrofining performance, but the defects of too fast reduction of catalytic activity and too short service life of the catalyst exist. In addition, the amount of active metal in the hydrogenation catalyst and the ratio relationship between the active metal and the catalyst can influence the performance of the catalyst to a certain extent.
Disclosure of Invention
In order to further improve the performance of the hydrogenation catalyst, the inventor of the invention adopts a phosphorus-containing alumina carrier with specific infrared characteristics, and controls the carbon component content and the proportion of hydrogenation active metal components in the catalyst, so that the hydrogenation catalyst with better hydrodesulfurization and hydrodenitrogenation activities and activity stability can be obtained, and the service life of the catalyst is obviously prolonged, thereby the invention is made. Specifically, the present invention includes the following:
Firstly, the invention provides a hydrogenation catalyst, which comprises a carrier, a hydrogenation active metal component and a carbon component, wherein the hydrogenation active metal component is at least one metal element selected from VIB groups and at least one metal element selected from VIII groups; the content of the carbon component calculated by elements is 0.03-0.8 wt% based on the total amount of the hydrogenation catalyst, the content of the carrier is 40-85 wt%, and the hydrogenation active metal component satisfies the following relation: n (VIB)/n (VIB+VIII) is less than or equal to 0.25 and less than or equal to 0.35, wherein n (VIB) represents the amount of substances of the VIB group metal element, and n (VIB+VIII) represents the sum of the amounts of substances of the VIB group metal element and the VIII group metal element; the carrier is phosphorus-containing alumina, and in the IR spectrogram of the phosphorus-containing alumina,(I 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9 to 2.8; wherein I is 3670 3670cm -1 Peak height, I 3580 3580cm -1 Peak height, I 3770 3770cm -1 Peak height, I 3720 3720cm -1 Peak height.
Secondly, the invention provides a preparation method of the hydrogenation catalyst, which comprises the following steps:
(1) The inorganic aluminum-containing compound solution is contacted with acid or alkali to carry out precipitation reaction, or the organic aluminum-containing compound is contacted with water to carry out hydrolysis reaction, so as to obtain hydrated alumina containing phosphorus;
(2) Aging the obtained hydrated alumina containing phosphorus at pH 7-10.5;
(3) Roasting the solid product obtained by ageing in the step (2) to obtain phosphorus-containing aluminum oxide;
(4) Loading water-soluble salt of hydrogenation active metal component and organic complexing agent on the phosphorus-containing alumina carrier obtained in the step (3) by adopting an impregnation method, and then drying and roasting, wherein the hydrogenation active metal component is at least one metal element selected from VIB group and at least one metal element selected from VIII group, the dosage of the water-soluble salt of hydrogenation active metal component and the organic complexing agent and the roasting condition are such that the content of carbon component calculated by elements is 0.03-0.8 wt% based on the total amount of the finished catalyst, the content of carrier is 40-85 wt%, and the hydrogenation active metal component satisfies the following relation: n (VIB)/n (VIB+VIII) is less than or equal to 0.25 and less than or equal to 0.35, wherein n (VIB) represents the amount of substances of the VIB group metal element, and n (VIB+VIII) represents the sum of the amounts of substances of the VIB group metal element and the VIII group metal element;
the precipitation reaction or the hydrolysis reaction of the step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 7; the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes.
Finally, the invention also provides the hydrogenation catalyst and application of the hydrogenation catalyst prepared by the method in hydrocarbon oil hydrogenation reaction.
Compared with the prior art, the hydrogenation performance of the hydrogenation catalyst provided by the invention is obviously improved, and particularly the activity stability of the catalyst is obviously improved, thereby being beneficial to prolonging the service life of the catalyst. Especially when applied to wax oil hydrotreating reaction, the effect is more obvious.
Detailed Description
In order that those skilled in the art will better understand the invention, a detailed description of the invention will be provided below, but it should be noted that endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that the range or value should be understood to include values near the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The hydrogenation catalyst provided by the invention comprises a carrier, a hydrogenation active metal component and a carbon component, wherein the hydrogenation active metal component is at least one metal element selected from a VIB group and at least one metal element selected from a VIII group; the content of the carbon component calculated by elements is 0.03-0.8 wt% based on the total amount of the hydrogenation catalyst, the content of the carrier is 40-85 wt%, and the hydrogenation active metal component satisfies the following relation: n (VIB)/n (VIB+VIII) is less than or equal to 0.25 and less than or equal to 0.35, wherein n (VIB) represents the amount of substances of the VIB group metal element, and n (VIB+VIII) represents the sum of the amounts of substances of the VIB group metal element and the VIII group metal element; the carrier is phosphorus-containing alumina, and in the IR spectrum of the phosphorus-containing alumina, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9 to 2.8; wherein I is 3670 3670cm -1 Peak height, I 3580 3580cm -1 Peak height, I 3770 3770cm -1 Peak height, I 3720 3720cm -1 Peak height.
In the present invention, the IR spectrum is obtained by Nicolet, americaAnd (5) measuring by a model-II Fourier infrared spectrometer of the Nicolet 870. The method specifically comprises the following steps: the sample was pressed into a self-supporting sheet, placed in an infrared cell, and treated at 450℃for 3 hours under vacuum to determine the infrared spectrum of the sample. According to 3670cm on the spectrogram -1 Peak height at 3580cm -1 Peak height at 3770cm -1 Peak height at 3720cm -1 Calculation of the value of peak height (I 3670 +I 3580 )/(I 3770 +I 3720 ) Is a value of (2). Alumina carrier of the prior art (I) 3670 +I 3580 )/(I 3770 +I 3720 ) Typically lower than 1.8. Preferably, the phosphorus-containing alumina carrier (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 2-2.7.
The specific surface and pore volume of the phosphorus-containing alumina are not particularly required in the invention, and preferably, the pore volume of the nitrogen adsorption method of the phosphorus-containing alumina is 0.7-1.6 ml/g, the specific surface area of the BET nitrogen adsorption method is 250-380 square meters/g, and the diameter of pores can be 8-16 nanometers. The diameter of the holes refers to the diameter corresponding to the highest point of the hole distribution curve.
In the phosphorus-containing alumina of the present invention, preferably, al is contained in the total amount of the phosphorus-containing alumina 2 O 3 The content of (2) is 94-99 wt%, preferably 95-98 wt%; p (P) 2 O 5 The content of (2) is 1 to 6% by weight, preferably 2 to 5% by weight.
According to the invention, the phosphorus-containing alumina can be obtained by roasting phosphorus-containing pseudo-boehmite. The conditions of the firing are not particularly limited in the present invention, and preferably the conditions of the firing include: the temperature is 350-1000deg.C, preferably 500-750deg.C, and the time is 1-10 hr, preferably 2-6 hr.
The present invention is not particularly limited as long as the above-mentioned phosphorus-containing alumina having a specific structure can be obtained by calcination, and preferably, the phosphorus-containing pseudo-boehmite has h satisfying 1.7.ltoreq.h.ltoreq.3, wherein h=d (031)/D (020), D (031) represents the grain size of a crystal plane represented by 031 peak in the XRD spectrum of pseudo-boehmite crystal, D (020) represents the grain size of a crystal plane represented by 020 peak in the XRD spectrum of pseudo-boehmite crystal, 031 peak means a peak of 34 to 43 ° in 2 theta in the XRD spectrum, 020 peak means a peak of 10 to 15 ° in 2 theta in the XRD spectrum, d=kλ/(bcosθ), K is Scherrer constant, λ is the diffraction wavelength of the target material, B is the half-width of the diffraction peak, and 2 θ is the position of the diffraction peak. The use of such preferred embodiments is more advantageous in increasing the activity of the catalyst.
In the present invention, for different diffraction peaks, B and 2θ each take the value of the corresponding peak, for example, when D (031) is calculated, D (031) =kλ/(Bcos θ), where B is the half-peak width of the 031 diffraction peak and 2θ is the position of the 031 diffraction peak; when D (020) is calculated, D (020) =kλ/(bcosθ), where B is the half-width of the 020 diffraction peak and 2θ is the position of the 020 diffraction peak. More preferably, h of the pseudo-boehmite satisfies 1.9.ltoreq.h.ltoreq.3, and still more preferably satisfies 2.2.ltoreq.h.ltoreq.2.8. Within this preferred range, the hydrogenation activity of the resulting catalyst is better.
h, the phosphorus-containing aluminum oxide prepared by baking the phosphorus-containing pseudo-boehmite meeting the requirements has specific hydroxyl distribution, and is more beneficial to improving the hydrogenation activity of the hydrogenation catalyst prepared by taking the phosphorus-containing aluminum oxide as a carrier. In the pseudo-boehmite prepared by the prior art, h is generally 0.85-1.65.
According to the invention, the relative crystallinity of the phosphorus-containing pseudo-boehmite (based on the commercial SB powder of Condea company) is generally in the range of 45-77%, preferably 65-77%.
In the present invention, the crystal structure of pseudo-boehmite was measured using a D5005X-ray diffractometer from Siemens, germany, with a CuK alpha radiation of 44 kv, 40 mA, and a scanning speed of 2℃per minute.
According to the invention, the phosphorus-containing pseudo-boehmite contains phosphorus element and has a specific crystal structure, so that the hydrogenation catalyst obtained by loading the hydrogenation active metal component and the carbon component on the phosphorus-containing alumina carrier prepared from the phosphorus-containing pseudo-boehmite shows excellent hydrogenation activity and activity stability.
The hydrogenation active metal component is selected conventionally, the VIB group metal component is Mo and/or W, and the VIII group metal component is Co and/or Ni; the content of the carbon component calculated by elements is 0.04-0.6 wt%, the content of the carrier is 45-80 wt%, the group VIB metal component is Mo and/or W, the group VIII metal component is Co and/or Ni, and the hydrogenation active metal component satisfies the following relation: n (VIB)/n (VIB+VIII) is not less than 0.27 and not more than 0.32. In the preferred embodiment, the hydrogenation catalyst obtained has the best performance when the atomic ratio of the group VIII metal component to the total hydrogenation active metal component is 0.275-0.315, and particularly has the most remarkable effect when being applied to the hydrodesulphurisation and hydrodenitrogenation reactions of wax oil fractions.
The hydrogenation catalyst provided by the invention can also contain any auxiliary agent which can improve the performance of the hydrogenation catalyst, such as metal auxiliary agent, nonmetal auxiliary agent and the like, and can specifically contain at least one of IA, IIA, IIIA, IVA, VA, VIIA, IIB, IIIB group elements and rare earth metal elements, preferably at least one of boron, fluorine, silicon, sodium, magnesium, lithium, zinc, calcium, potassium, titanium, lanthanum and cerium, and the content of the auxiliary agent calculated as simple substance element is not more than 10 weight percent, preferably 0.5-6 weight percent based on the catalyst.
The invention also provides a preparation method of the hydrogenation catalyst, according to the method, the precipitation reaction or the hydrolysis reaction is carried out under the condition that the pH value is 4-7 in the presence of the grain growth regulator and the phosphorus-containing compound, so that the precipitation of phosphorus-containing hydrated alumina can be met, the lower pH value condition is maintained, the growth of pseudo-boehmite grains is prevented from being too fast under the high pH value, and the joint regulation effect of phosphorus and the growth regulator on the growth of the pseudo-boehmite is enhanced. The grain growth of pseudo-boehmite in the whole process of hydrated alumina generation and aging is carried out in the presence of phosphorus-containing compounds and grain regulators, so that the prepared pseudo-boehmite has a special crystal structure and is particularly suitable for serving as a carrier precursor of heavy oil hydrogenation catalysts.
According to one embodiment of the invention, step (1) comprises: the inorganic aluminum-containing compound solution, the phosphorus-containing compound, the grain growth regulator and acid or alkali are contacted for precipitation reaction, or the organic aluminum-containing compound, the phosphorus-containing compound and the grain growth regulator are subjected to hydrolysis reaction with water; controlling the pH of the precipitation reaction or the hydrolysis reaction to be 4-7.
According to a preferred embodiment of the present invention, the precipitation reaction or the hydrolysis reaction of step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 6.5. The precipitation reaction or the hydrolysis reaction is carried out at the preferable pH value, which is more beneficial to improving the hydrogenation activity of the prepared hydrogenation catalyst in heavy oil hydrogenation.
The present invention is not particularly limited in terms of the conditions other than pH of the precipitation reaction and the hydrolysis reaction. In the present invention, preferably, the temperature of the precipitation reaction and the hydrolysis reaction are each independently 30 to 90 ℃.
In the present invention, the conditions for the precipitation reaction are selected in a wide range, and preferably, the conditions for the precipitation reaction include: the reaction temperature is 40-90 ℃, and the reaction time is 10-60 minutes. Further preferably, the conditions of the precipitation reaction include: the reaction temperature is 45-80 ℃, and the reaction time is 10-30 minutes.
The conditions for the hydrolysis reaction are not particularly limited in the present invention, as long as water is brought into contact with the organic aluminum-containing compound to cause hydrolysis reaction to produce hydrated alumina. The water consumption in the hydrolysis reaction process is selected in a wider range, so long as the molar ratio of water to the organic aluminum-containing compound is greater than the stoichiometric ratio. Conditions under which hydrolysis specifically occurs are well known to those skilled in the art. Preferably, the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 2-20 hours.
In the present invention, the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes, preferably a substance capable of regulating the growth rate of grains on a 020 crystal plane and a 031 crystal plane. For example, various substances which can strongly adsorb with hydrated alumina can be used; preferably, the grain growth regulator is at least one of a polyhydric sugar alcohol and its carboxylate and sulfate; further preferably, the grain growth regulator is at least one selected from the group consisting of sorbitol, glucose, gluconic acid, gluconate, ribitol, ribonic acid, ribonate and sulfate. The gluconate, the gluconate and the sulfate may each be a soluble salt thereof, for example, may be one or more of a potassium salt, a sodium salt and a lithium salt.
In the present invention, the manner of adding the grain growth regulator is not particularly limited, and the grain growth regulator may be added alone, or the grain growth regulator may be mixed with one or more of the raw materials in advance, and then the raw materials containing the grain growth regulator may be reacted.
The amount of the grain growth regulator used in the present invention is not particularly limited, and preferably the amount of the grain growth regulator used in the precipitation reaction is 1 to 10% by weight, preferably 1.5 to 8.5% by weight, and more preferably 2 to 6% by weight, based on the weight of the inorganic aluminum-containing compound.
Preferably, the grain growth regulator is used in the hydrolysis reaction in an amount of 1 to 10% by weight, preferably 1.5 to 8.5% by weight, and more preferably 2 to 6% by weight, based on the weight of the organic aluminum-containing compound, based on the alumina.
In the present invention, the amounts of the grain growth regulator are calculated based on the weight of the corresponding alumina in the organic aluminum-containing compound and the inorganic aluminum-containing compound, respectively, unless otherwise specified.
In the present invention, the manner of adding the phosphorus-containing compound is not particularly limited, and the phosphorus-containing compound (or the phosphorus-containing compound aqueous solution) may be added alone, or the phosphorus-containing compound (or the phosphorus-containing compound aqueous solution) may be mixed with one or more of the raw materials in advance, and then the raw materials containing the phosphorus-containing compound are reacted, so long as the precipitation reaction or the hydrolysis reaction is ensured to be carried out in the presence of the phosphorus-containing compound. The preparation method provided by the invention can ensure the regulation effect of the phosphorus-containing compound on the grain growth.
The phosphorus-containing compound of the present invention may be a water-soluble inorganic phosphorus-containing compound, and preferably, the phosphorus-containing compound is at least one selected from phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and potassium phosphate.
In order to exert the effect of the phosphorus-containing compound on the regulation of the grain growth, it is preferable that the phosphorus-containing compound is used in such an amount that P is contained in the produced phosphorus-containing alumina based on the total amount of the phosphorus-containing alumina 2 O 5 The content of (2) is 1 to 6% by weight, preferably 2 to 5% by weight.
It is noted that the crystal grain growth regulator and the phosphorus-containing compound are added during the precipitation reaction or the hydrolysis reaction, which is more favorable for regulating the growth speed of the crystal grain on the 020 crystal face and the 031 crystal face, so that h is more than or equal to 1.7 and less than or equal to 3, preferably 1.9 and less than or equal to 3, and more preferably 2.2 and less than or equal to 2.8. The grain growth regulator and the phosphorus-containing compound are added during the precipitation reaction or the hydrolysis reaction, so that the aging reaction carried out later is also carried out in the presence of the grain growth regulator and the phosphorus-containing compound. Preferably, no grain growth regulator or phosphorus-containing compound is additionally added during the aging process.
According to the preparation method provided by the invention, in the step (1), the inorganic aluminum-containing compound is preferably an aluminum salt and/or aluminate. Accordingly, the inorganic aluminum-containing compound may be various aluminum salt solutions and/or aluminate solutions, and the aluminum salt solution may be various aluminum salt solutions, for example, may be one or more aqueous solutions of aluminum sulfate, aluminum chloride and aluminum nitrate. Because of its low cost, aluminum sulfate solution and/or aluminum chloride solution are preferred. The aluminum salt may be used alone or in combination of two or more. The aluminate solution is any aluminate solution, such as sodium aluminate solution and/or potassium aluminate solution. Sodium aluminate solution is preferred because of its ease of availability and low cost. The aluminate solutions may also be used alone or in mixtures. The concentration of the inorganic aluminum-containing compound solution is not particularly limited, and preferably the concentration of the inorganic aluminum-containing compound solution is 20 to 200 g/l in terms of aluminum oxide.
According to the preparation method provided by the invention, the organic aluminum-containing compound in the step (1) can be at least one of various aluminum alkoxides which can be subjected to hydrolysis reaction with water to generate hydrated alumina precipitate, and can be at least one of aluminum isopropoxide, aluminum isobutanol, aluminum triisopropoxide, aluminum trite-butoxide and aluminum isooctanoxide.
According to the production method provided by the present invention, the acid in step (1) may be various protonic acids or oxides acidic in an aqueous medium, for example, may be at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid, and preferably the protonic acid is at least one selected from nitric acid, sulfuric acid and hydrochloric acid. The carbonic acid may be generated in situ by passing carbon dioxide into the aluminum salt solution and/or the aluminate solution. The acid may be introduced in the form of a solution, and the concentration of the acid solution is not particularly limited, preferably H + The concentration of (2) is 0.2-2 mol/L.
According to the preparation method provided by the invention, the alkali in the step (1) can be hydroxide or salt which is hydrolyzed in an aqueous medium to make the aqueous solution alkaline, preferably, the hydroxide is at least one selected from ammonia water, sodium hydroxide and potassium hydroxide; preferably, the salt is selected from at least one of sodium metaaluminate, potassium metaaluminate, ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate. When sodium metaaluminate and/or potassium metaaluminate are used as the base, the amounts of the grain growth regulator and the phosphorus-containing compound are calculated, and the corresponding amounts of alumina in sodium metaaluminate and/or potassium metaaluminate are also considered.
Specifically, in order to regulate the pH of the hydrolysis reaction, an acid or a base may be introduced into the hydrolysis reaction, and the manner and kind of introduction of the acid or the base may be as described above, which will not be described herein.
Among them, the method of precipitating aluminum by controlling the pH with respect to the amount of alkali or acid in the reactant is well known to those skilled in the art, and will not be described herein.
The aging condition in the step (2) is selected in a wide range, so long as the aging condition is ensured to be performed under the condition that the pH is 7-10.5. Since the precipitation reaction or the hydrolysis reaction in step (1) is carried out at a pH of 4 to 7, it is preferable to introduce before aging is carried outA base is added to adjust the pH of the aging reaction. The base may be introduced in the form of a solution, and the concentration of the alkali solution is not particularly limited, and preferably OH - The concentration of (2) is 0.2-4 mol/L.
More preferably, the ageing of step (2) is carried out at a pH of 8-10.
The conditions of the aging other than pH in step (2) are selected in the present invention in a wide range, preferably the aging temperature is 50 to 95℃and preferably 55 to 90 ℃. The aging time is appropriately selected depending on the aging temperature, and preferably, the aging time is 0.5 to 8 hours, preferably 2 to 6 hours.
The invention also includes separating, washing and drying the aged product after the aging reaction. The separation according to the method provided by the present invention may be a method known in the art, such as filtration or centrifugation. The washing and drying method may be a method commonly used in the preparation of pseudo-boehmite, for example, the washing agent may be water and the drying may be at least one of drying, forced air drying, spray drying and flash drying. The drying temperature may be 100-350 ℃, preferably 120-300 ℃.
In the preparation method provided by the invention, the roasting process in the step (3) is not particularly limited. Preferably, the method provided by the invention further comprises shaping the solid product or the phosphorus-containing alumina before or after the firing. Preferably, the solid product obtained by aging in step (2) is dried after molding, preferably extrusion molding, and then the baking is performed. In order to ensure that the molding is carried out smoothly, water, an extrusion aid and/or an adhesive and optionally a pore-expanding agent can be added into the solid product obtained by aging in the step (2), wherein the types and the amounts of the extrusion aid, the peptizing agent and the pore-expanding agent are known to those skilled in the art; for example, the usual extrusion aid may be at least one selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol and polyethylene alcohol, the peptizing agent may be an inorganic acid and/or an organic acid, and the pore expanding agent may be at least one selected from starch, synthetic cellulose, a polymeric alcohol and a surfactant. Wherein the synthetic cellulose is preferably at least one of hydroxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymeric alcohol is preferably at least one of polyethylene glycol, polypropylene glycol and polyvinyl alcohol; the surfactant is preferably at least one of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, and acrylic alcohol copolymer and maleic acid copolymer with molecular weight of 200-10000. The drying conditions of step (3) preferably include: the drying temperature may be 40-350 ℃, more preferably 100-200 ℃; the drying time may be 1 to 24 hours, more preferably 2 to 12 hours.
In the preparation method provided by the present invention, the condition of the firing in the step (3) is not particularly limited, and preferably, the condition of the firing in the step (3) includes: the temperature is 350-1000deg.C, preferably 400-800deg.C, and the time is 1-10 hr, preferably 2-6 hr.
According to the method, the hydrogenation active metal component in the preparation method is conventionally selected, the VIB group metal component is Mo and/or W, and the VIII group metal component is Co and/or Ni; the molar ratio of the organic complexing agent to the hydrogenation active metal component is 0.03-2:1, preferably 0.08-1.5:1, a step of; the amount of each component is such that in the final hydrogenation catalyst, the carbon component content in terms of elements is 0.04-0.6 wt%, the carrier content is 45-80 wt%, and the hydrogenation active metal components satisfy the following relationship: the content of the hydrogenation active metal component calculated by oxide is 20-50 wt% and is less than or equal to 0.27 and less than or equal to n (VIB)/n (VIB+VIII) is less than or equal to 0.32. In another preferred embodiment, the components are added in amounts such that the resulting hydrogenation catalyst performs optimally when the atomic ratio of the group VIII metal component to the total hydrogenation active metal component is from 0.275 to 0315, especially when applied to hydrodesulphurisation and hydrodenitrogenation reactions of wax oil fractions.
The inventor of the present invention further found through research that the addition of an organic complexing agent during the impregnation process and the conversion thereof into a specific content of carbon by calcination not only can improve the activity of the catalyst, but also can effectively maintain the high activity of the catalyst for a long time, thereby greatly improving the service life of the catalyst. Presumably, the reason is that the existence of the organic complexing agent which is added in the dipping process prevents the aggregation of the active metal in the roasting process, so that the active metal is dispersed more uniformly; the roasting after impregnation can convert the metal compound into metal oxide and convert the organic complexing agent into carbon, so that the combination between the active metal and the carrier is firmer, and the activity and the stability of the catalyst are improved. Therefore, the technology can effectively solve the technical defects of the conventional impregnation method and the conventional complexation impregnation method.
According to the invention, the carbon component content in the finished catalyst is preferably 0.04 to 0.6% by weight, based on the total amount of the finished catalyst; to achieve this content, the firing conditions of step (4) of the present invention are further defined in that the above-mentioned char content can be obtained by controlling the firing temperature in the firing conditions and the amount of the introduction of the combustion-supporting gas, which may be one or more of various gases having an oxygen content of not less than 20% by volume, such as air, oxygen, and a mixture thereof. The ventilation amount of the combustion-supporting gas is not less than 0.2 liter/g.h. The combustion-supporting gas is introduced, so that on one hand, the combustion condition is met, the salt of the active metal component is converted into oxide, and the organic complexing agent is converted into carbon; on the other hand, carbon dioxide and water formed by combustion and other components can be discharged, so that the phenomenon that vacancies of an active phase are blocked by the catalyst are avoided. The amount of gas to be introduced is preferably 0.2 to 20 liters/(g.hr), more preferably 0.3 to 10 liters/(g.hr). "gram" herein refers to the weight of the carrier.
According to the invention, the calcination temperature is 350-500 ℃, preferably 360-450 ℃, and the calcination time is 0.5-8h, preferably 1-6h. The control of the roasting temperature in the above range can ensure that the organic complexing agent can form carbon on the carrier in the content range to obtain the finished catalyst.
In the present invention, the organic complexing agent is selected from one or more of oxygen-containing and/or nitrogen-containing organics. The oxygen-containing organic matter is preferably selected from one or more of organic alcohols and organic acids. The organic alcohol is preferably a polyhydric alcohol having two or more elements, more preferably a polyhydric alcohol having 2 to 6 carbon atoms or an oligomer or polymer thereof, such as one or more of ethylene glycol, glycerol, polyethylene glycol, diethylene glycol, and butanediol. The polyethylene glycol preferably has a molecular weight of 200-1500. The organic acid is preferably a C2-C7 compound containing one or more COOH groups, and can be one or more of acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid and malic acid. The nitrogen-containing organic matter is preferably selected from one or more of organic amine and organic ammonium salt. The organic amine is preferably a C2-C7 compound containing one or more NH groups, and may be a primary, secondary or tertiary amine, particularly preferably ethylenediamine. The organic ammonium salt is preferably EDTA.
In particular, it is particularly preferred according to the present invention that the organic complexing agent is one or more of ethylene glycol, glycerol, polyethylene glycol (molecular weight is preferably 200-1500), diethylene glycol, butylene glycol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid, ethylenediamine and EDTA. Preferably the organic complexing agent is selected from one or more of the group of organic acids, more preferably the organic complexing agent is selected from one or more of the group of C2-C7 fatty acids. By using an organic acid as an organic complexing agent, a hydrogenation catalyst having a higher activity can be obtained.
The drying conditions are not particularly limited, and may be various drying conditions commonly used in the art, and the drying temperature is preferably 100 to 250℃for 1 to 12 hours.
The application of the hydrogenation catalyst in the hydrogenation reaction of the hydrocarbon oil is provided, wherein the hydrocarbon oil is the hydrogenation catalyst provided by the invention or the hydrogenation catalyst prepared by the method provided by the invention.
The catalyst is suitable for the refining processes of hydrodesulfurization, hydrodenitrogenation and the like of various hydrocarbon oil raw materials, wherein the hydrocarbon oil raw materials can be gasoline, diesel oil, lubricating oil, kerosene and naphtha, can also be atmospheric residuum, vacuum residuum, petroleum wax and Fischer-Tropsch synthetic oil, and are especially suitable for wax oil fractions.
The conditions for the hydrogenation reaction of the present invention are not particularly limited and may beTo be a routine choice in the art. Generally, the hydrofinishing conditions include: the temperature can be 300-400 ℃; the pressure can be 1.0-8.0MPa based on gauge pressure; the liquid hourly space velocity can be 0.5-3.0 hours -1 The hydrogen oil volume ratio may be 100-700.
The catalysts provided by the present invention are preferably sulfided prior to use using methods conventional in the art. In general, the vulcanization conditions may include: presulfiding with one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or other sulfur-containing feedstock in the presence of hydrogen at a temperature of 180-450 ℃ for 2-4 hours. The presulfiding may be carried out outside the reactor or may be sulfided in situ within the reactor.
The following detailed description of the invention and the advantages that result from the specific examples are not intended to limit the scope of the invention in any way.
In the following examples, the content of each element in the catalyst was analyzed and measured by using an X-ray fluorescence spectrometer of 3271E, manufactured by Nippon Motor industry Co. The carbon content of the catalyst semifinished product was analyzed and measured using an EMIA-320V carbon sulfur analyzer manufactured by HORIBA Co., japan. XRD was measured on a SIMENS D5005X-ray diffractometer, with CuK alpha radiation, 44 kilovolts, 40 milliamps, scanning speed of 2/min. According to the Scherrer formula: d=kλ/(bcosθ) (D is the grain size, λ is the diffraction wavelength of the target material, B is the half-width of the corrected diffraction peak, and 2θ is the position of the diffraction peak), the grain size of (020) is calculated as D (020) with the parameters of the 2θ as 10-15 ° peak, the grain size of (031) is calculated as D (031) with the parameters of the 2θ as 34-43 ° peak, and h=d (031)/D (020) is calculated.
The IR spectrum was measured by a Nicolet 870 Fourier infrared spectrometer from Nicolet corporation, USA. The method specifically comprises the following steps: the sample was pressed into a self-supporting sheet, placed in an infrared cell, and treated at 450℃for 3 hours under vacuum to determine the infrared spectrum of the sample. According to 3670cm on the spectrogram -1 Peak height at 3580cm -1 Peak height at 3770cm -1 Peak height at 3720cm -1 Calculating the value of m at peak height, where m= (I) 3670 +I 3580 )/(I 3770 +I 3720 ) Is a value of (2).
In the following examples, the materials involved are commercially available unless otherwise indicated.
Example 1
This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.
In a 2L reaction tank, 5000 mL of aluminum sulfate solution with concentration of 60 g/L, 6.0 g of ribitol, 8.0mL of 85 wt% concentrated phosphoric acid and ammonia water solution with concentration of 6 wt% are added in parallel flow to carry out precipitation reaction, the reaction temperature is 50 ℃, the reaction time is 30 minutes, the flow rate of the ammonia water solution is controlled to enable the pH value of a reaction system to be 5.0, after the precipitation reaction is finished, a proper amount of ammonia water is added into slurry to enable the pH value of the slurry to be 8.7, the slurry is aged for 120 minutes at 70 ℃ and then filtered, a filter cake is pulped and washed by deionized water for 2 times, and the filter cake is dried for 24 hours at 120 ℃ to obtain hydrated aluminum oxide PA1, by XRD, PA1 has a pseudo-boehmite structure.
The h values calculated by XRD characterization to give PA1 are listed in Table 1. Relative crystallinity of PA1 and P 2 O 5 The content of (2) is also shown in Table 1. After baking at 600℃for 4 hours, the hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy, and the calculated m values are shown in Table 1.
1000 g of PA1 and 30 g of sesbania powder (produced by Shun trade Limited company in Jiangsu Feng county) are taken and mixed uniformly, then 920 ml of aqueous solution containing 28g of nitric acid is added for mixing, then a butterfly-shaped wet strip with the outer diameter of 1.7mm is extruded on a plunger type strip extruder, the butterfly-shaped wet strip is dried for 4 hours at 120 ℃, and then the carrier Z1 is obtained after roasting for 3 hours at 600 ℃. P in vector Z1 2 O 5 The content of (2) and the pore volume, specific surface area and pore diameter are shown in Table 2.
54 g of molybdenum trioxide, 21 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid are respectively weighed and put into 200 g of deionized water, heated, stirred and dissolved to obtain a clear impregnating solution, 200 g of the phosphorus-containing alumina carrier prepared in example 1 is impregnated with the solution by a saturated impregnation method for 2 hours, then dried at 150 ℃ for 2 hours, and then baked in a state of being introduced with air flow, wherein the baking temperature is 360 ℃, the time is 3 hours, and the gas-to-agent ratio is 10 liters/(g.h), so as to obtain the finished catalyst S1. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst S1 based on the total amount of the S1 are shown in Table 3.
Comparative example 1
The preparation of the support DZ1 and the hydrogenation catalyst DS1 was carried out in the same manner as in example 1, except that only 8.0mL of 85% strength by weight phosphoric acid was added to the aluminum sulfate solution without ribitol, to give hydrated alumina CPA1. CPA1 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA1, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After baking at 600℃for 4 hours, the hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy, and the calculated m values are shown in Table 1. The pore volume, specific surface area and pore diameters of the support DZ1 are shown in Table 2. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst DS1 based on the total amount of DS1 are shown in Table 3.
Comparative example 2
The carrier DZ2 and the hydrogenation catalyst DS2 were prepared as in example 1, except that the flow rate of the aqueous ammonia solution was directly controlled to adjust the pH of the reaction system to 8.7, and that after the precipitation reaction was completed, it was not necessary to add aqueous ammonia to the slurry to adjust the pH to obtain alumina hydrate CPA2. CPA2 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA2, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After baking at 600℃for 4 hours, the hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy, and the calculated m values are shown in Table 1. P in vector DZ2 2 O 5 The content of (2) and the pore volume, specific surface area and pore diameter are shown in Table 2. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst DS2 based on the total DS2 are shown in Table 3.
Comparative example 3
The preparation of the support DZ3 and the hydrogenation catalyst DC3 was carried out in the same manner as in example 1, except that only the aluminum sulfate solution was addedRibitol 6.0 g without concentrated phosphoric acid gives hydrated alumina CPA3. CPA3 has pseudo-boehmite structure as characterized by XRD according to the method of example 1, and the h values calculated by XRD characterization are shown in Table 1 for CPA3, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After baking at 600℃for 4 hours, the hydroxyl groups on the alumina surface were measured by infrared spectroscopy, and the calculated m values are shown in Table 1. P in vector DZ3 2 O 5 The content of (2) and the pore volume, specific surface area and pore diameter are shown in Table 2. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst DS3 based on the total DS3 are shown in Table 3.
Comparative example 4
The catalyst was prepared using the support of example 1 and following the procedure for preparing the hydrogenation catalyst in example 1, except that: no citric acid was added to the preparation of the impregnating solution. The catalyst obtained was DS4. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst DS4 based on the total DS4 are shown in Table 3.
Comparative example 5
The hydrogenation catalyst DS5 was prepared using the support of example 1, except that the amounts of hydrogenation-active metals used were varied, specifically: 54.5 g of molybdenum trioxide, 19 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid are put into 200 g of deionized water, heated, stirred and dissolved to obtain a clear impregnating solution, 200 g of the phosphorus-containing alumina carrier prepared in example 1 is impregnated with the solution by a saturated impregnating method, and the rest steps and conditions are the same, so that a finished catalyst DS5 is obtained. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst DS5 based on the total DS5 are shown in Table 3.
Example 2
This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.
In a 2L reactor, 4000 mL of an alumina solution containing 85 wt% concentrated phosphoric acid (22.1 mL) and sorbitol (4.52 g/L) and 1000 mL of a sodium metaaluminate solution containing 210 g of alumina (1.58) and having a caustic coefficient (80 ℃ C.) were added in parallel to carry out precipitation reaction, the reaction temperature was 80 ℃ C., and the reaction was adjustedThe flow rate is such that the neutralization pH value is 4.0, and the reaction residence time is 15 minutes; dilute ammonia water with the concentration of 5 weight percent is added into the obtained slurry to adjust the pH of the slurry to 9.0, the temperature is raised to 85 ℃, the aging is carried out for 3 hours, then a vacuum filter is used for filtering, and after the filtering is finished, 20 liters of deionized water (the temperature is 85 ℃) is added on a filter cake to wash the filter cake for about 30 minutes. And adding the qualified filter cake into 3.0 liters of deionized water, stirring to form slurry, pumping the slurry into a spray dryer for drying, controlling the outlet temperature of the spray dryer to be in the range of 100-110 ℃, and drying the material for about 2 minutes to obtain the hydrated alumina PA2. As characterized by XRD in accordance with the method of example 1, PA2 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA2, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After baking at 600℃for 4 hours, the hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy, and the calculated m values are shown in Table 1.
Carrier Z2 was prepared as in example 1, except that PA2 was used instead of PA1 and the calcination temperature was 650 ℃. P in vector Z2 2 O 5 The content of (2) and the pore volume, specific surface area and pore diameter are shown in Table 2.
54 g of molybdenum trioxide, 23 g of basic nickel carbonate, 13 g of phosphoric acid and 30 g of citric acid are respectively weighed and put into 200 g of deionized water, heated, stirred and dissolved to obtain a clear impregnating solution, 200 g of the phosphorus-containing alumina carrier prepared in example 1 is impregnated with the solution by a saturated impregnation method for 2 hours, then dried at 150 ℃ for 2 hours, and then baked in a state of being introduced with air flow, wherein the baking temperature is 400 ℃ for 2 hours, the gas-to-gas ratio is 2 liters/(g.h), the finished catalyst S2 is obtained, and the content of each component and the proportion of the active components of hydrogenation metal in the hydrogenation catalyst S2 are shown in a table 3 based on the total amount of the S2.
Example 3
This example is intended to illustrate the hydrogenation catalyst provided by the present invention and a method for preparing the same.
Into a2 liter three-necked flask equipped with a stirring and reflux condenser, 1000 g of an isopropyl alcohol-water azeotrope (water content: 15% by weight) was charged Adding 4.6mL of 85% concentrated phosphoric acid and 15g of ribonucleotide, adding ammonia water to adjust the pH to 5.1, heating to 60 ℃, slowly dripping 500 g of melted aluminum isopropoxide into a flask through a separating funnel, reacting for 2 hours, adding ammonia water to adjust the pH to 8.5, refluxing for 20 hours, evaporating dehydrated isopropanol, aging at 80 ℃ for 6 hours, evaporating the water-containing isopropanol while aging, filtering the aged hydrated alumina, and drying at 120 ℃ for 24 hours to obtain the hydrated alumina PA3. As characterized by XRD in accordance with the method of example 1, PA3 has a pseudo-boehmite structure, and the h values calculated by XRD characterization are shown in Table 1 for PA3, relative crystallinity and P 2 O 5 The content of (2) is also shown in Table 1. After baking at 600℃for 4 hours, the hydroxyl groups on the surface of the phosphorus-containing alumina were measured by infrared spectroscopy, and the calculated m values are shown in Table 1.
1000 g of PA3 were used to prepare the carriers Z3, Z3P by the method of example 1 2 O 5 The content of (2) and the pore volume, specific surface area and pore diameter are shown in Table 2.
Respectively weighing 60 g of molybdenum trioxide, 28 g of basic nickel carbonate, 15g of phosphoric acid and 30 g of citric acid, putting into 200 g of deionized water, heating, stirring and dissolving to obtain a clear impregnating solution, impregnating 200 g of the phosphorus-containing alumina carrier prepared in example 1 with the solution by a saturated impregnating method for 2 hours, drying at 150 ℃ for 2 hours, and roasting the carrier in a state of being introduced with air flow, wherein the roasting temperature is 400 ℃, the time is 2 hours, and the gas-to-agent ratio is 2 liters/(g.h), thus obtaining the finished catalyst S3. The contents of the components and the proportion of the hydrogenation metal active components in the hydrogenation catalyst S3 based on the total amount of the S3 are shown in Table 3.
TABLE 1
Note that: m represents (I) 3670 +I 3580 )/(I 3770 +I 3720 ) Values of (2)
TABLE 2
TABLE 3 Table 3
As can be seen from the results of Table 1, the phosphorus-containing pseudo-boehmite prepared by the method provided by the invention has the characteristic that h is less than or equal to 1.7 and less than or equal to 3, preferably 2.2 and less than or equal to 2.8, and the h values of the pseudo-boehmite prepared by the prior art method and the method in the comparative example are all less than 1.7. The phosphorus-containing pseudo-boehmite prepared by the method of the invention is roasted at 600 ℃ to obtain the IR characterization spectrogram of the alumina, and the hydroxyl group has the characteristics (I) 3670 +I 3580 )/(I 3770 +I 3720 ) From 1.9 to 2.8, preferably from 2 to 2.7, with pseudo-boehmite prepared by the methods of the prior art and those of the comparative examples, by roasting at 600℃to give an IR profile of alumina, hydroxyl group characteristics (I 3670 +I 3580 )/(I 3770 +I 3720 )<1.8。
Evaluation example
In this test example, desulfurization activity and denitrification activity of the hydrofinishing catalyst prepared by the method provided by the present invention and the hydrofinishing catalyst provided by the comparative example were evaluated according to the following methods. The property of the Qingdao wax oil is as follows:
the desulfurization and denitrification activity of the catalyst was evaluated on a 120 ml wax oil hydrogenation unit. Before the reaction, the catalyst is presulfided, the catalyst is filled with 100mL, and presulfiding conditions are as follows: 6.4MPa,290 ℃ and 4 hours, wherein the volume ratio of hydrogen to oil is 300:1, and the oil inlet speed of vulcanized oil is 150mL/h. The reaction conditions are as follows: hydrogen partial pressure 8.0MPa, reaction temperature 355 ℃, hydrogen-oil volume ratio 800 and liquid hourly space velocity 1.4h -1 . Taking samples of 2 nd day and 12 th day after reaction, respectively, and measuring hydrodesulfurization and hydrodenitrogenation by gas chromatographyThe sulfur and nitrogen contents in the raw materials and the obtained products.
The relative hydrodesulfurization activity of the reference agent DS1 was used to evaluate the hydrodesulfurization activity of the catalyst, the hydrodesulfurization reaction was treated as a 1.65 stage reaction, and the reaction rate constant k (X) for catalyst X was calculated according to formula (1) HDS ：
In the formula (1), LHSV is the liquid hourly space velocity of hydrocarbon oil when the hydrofining reaction is carried out.
Hydrodesulfurization Activity with catalyst DS1 [ denoted as k (D1) ] HDS ]Based on the relative hydrodesulphurisation activity of catalyst X is calculated according to formula (2):
the hydrodenitrogenation activity of the catalyst was evaluated by using the relative hydrodenitrogenation activity with respect to the reference DS1, and the hydrodesulfurization reaction was treated as a 1-stage reaction, and the reaction rate constant k (X) of the catalyst X was calculated according to the formula (3) HDN ：
In the formula (1), LHSV is the liquid hourly space velocity of hydrocarbon oil when the hydrofining reaction is carried out.
Hydrodenitrogenation Activity of catalyst DS1 [ denoted as k (D1) ] HDN ]Based on the relative hydrodenitrogenation activity of catalyst X was calculated according to formula (4):
the results of the hydrorefining evaluation of the catalysts prepared in each of the examples and comparative examples are shown in Table 4.
The sulfur content in the oil sample is determined by using an electric quantity method (the specific method is shown in RIPP62-90 of petrochemical analysis method). The nitrogen content of the oil sample is determined by using a chemiluminescence method (the specific method is shown in the petrochemical analysis method RIPP SH 0704-Z).
The results in Table 4 demonstrate that the catalyst provided by the present invention has significantly improved hydrodesulfurization activity as well as hydrodenitrogenation activity over the hydrogenation catalysts prepared by prior art methods. In addition, as can be seen from comparing the data of the relative hydrodesulfurization activity and the relative hydrodenitrogenation activity on the 12 th day of the reaction in table 4, the catalyst activity provided by the invention is obviously improved compared with the catalyst activity of the comparative example D1 after the long-time reaction, so that the catalyst prepared by the method provided by the invention obviously prolongs the service life of the catalyst and has obvious effect.
TABLE 4 Table 4
Note that: in table 4, "-" indicates that no detection was performed.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (14)
1. A hydrogenation catalyst comprises a carrier, a hydrogenation active metal component and a carbon component, wherein the hydrogenation active metal component is at least one metal element selected from VIB group andat least one metal element selected from group VIII metals; the content of the carbon component calculated by elements is 0.03-0.8 wt% based on the total amount of the hydrogenation catalyst, the content of the carrier is 40-85 wt%, and the hydrogenation active metal component satisfies the following relation: n (VIB)/n (VIB+VIII) is less than or equal to 0.25 and less than or equal to 0.35, wherein n (VIB) represents the amount of substances of the VIB group metal element, and n (VIB+VIII) represents the sum of the amounts of substances of the VIB group metal element and the VIII group metal element; the carrier is phosphorus-containing alumina, and in the IR spectrum of the phosphorus-containing alumina, (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 1.9 to 2.8; wherein I is 3670 3670cm -1 Peak height, I 3580 3580cm -1 Peak height, I 3770 3770cm -1 Peak height, I 3720 3720cm -1 Peak height.
2. The hydrogenation catalyst according to claim 1, wherein the carbon component content is 0.04-0.6 wt% in terms of elements, the carrier content is 45-80 wt%, the group VIB metal component is Mo and/or W, the group VIII metal component is Co and/or Ni, and the hydrogenation active metal component satisfies the following relationship: n (VIB)/n (VIB+VIII) is not less than 0.27 and not more than 0.32.
3. The hydrogenation catalyst of claim 1, wherein (I) 3670 +I 3580 )/(I 3770 +I 3720 ) 2-2.7; the pore volume of the nitrogen adsorption method of the phosphorus-containing alumina is 0.7-1.6 ml/g, the specific surface area of the BET nitrogen adsorption method is 250-380 square meters/g, and the diameter of a few pores is 8-16 nanometers; al based on the total amount of the phosphorus-containing aluminum oxide 2 O 3 The content of (2) is 94-99 wt%, preferably 95-98 wt%; p (P) 2 O 5 The content of (2) is 1 to 6% by weight, preferably 2 to 5% by weight.
4. The hydrogenation catalyst of claim 1, wherein the phosphorus-containing alumina is obtained by calcination of phosphorus-containing pseudo-boehmite;
preferably, h of the phosphorus-containing pseudo-boehmite satisfies 1.7.ltoreq.h.ltoreq.3, wherein h=d (031)/D (020), wherein D (031) represents a crystal grain size of a crystal plane represented by 031 peak in an XRD spectrum of pseudo-boehmite crystal grain, D (020) represents a crystal grain size of a crystal plane represented by 020 peak in an XRD spectrum of pseudo-boehmite crystal grain, 031 peak is a peak of 34-43 ° in the XRD spectrum, 020 peak is a peak of 10-15 ° in the XRD spectrum, d=kλ/(Bcos θ), K is Scherrer constant, λ is a diffraction wavelength of a target material, B is a half-width of the diffraction peak, and 2θ is a position of the diffraction peak; more preferably, h of the pseudo-boehmite satisfies 1.9.ltoreq.h.ltoreq.3, preferably satisfies 2.2.ltoreq.h.ltoreq.2.8;
Preferably, the relative crystallinity of the phosphorus-containing pseudo-boehmite is 45-77%.
5. A method for preparing a hydrogenation catalyst, the method comprising the steps of:
(1) The inorganic aluminum-containing compound solution is contacted with acid or alkali to carry out precipitation reaction, or the organic aluminum-containing compound is contacted with water to carry out hydrolysis reaction, so as to obtain hydrated alumina containing phosphorus;
(2) Aging the obtained hydrated alumina containing phosphorus at pH 7-10.5;
(3) Roasting the solid product obtained by ageing in the step (2) to obtain phosphorus-containing aluminum oxide;
(4) Loading water-soluble salt of hydrogenation active metal component and organic complexing agent on the phosphorus-containing alumina carrier obtained in the step (3) by adopting an impregnation method, and then drying and roasting, wherein the hydrogenation active metal component is at least one metal element selected from VIB group and at least one metal element selected from VIII group, the dosage of the water-soluble salt of hydrogenation active metal component and the organic complexing agent and the roasting condition are such that the content of carbon component calculated by elements is 0.03-0.8 wt% based on the total amount of the finished catalyst, the content of carrier is 40-85 wt%, and the hydrogenation active metal component satisfies the following relation: n (VIB)/n (VIB+VIII) is less than or equal to 0.25 and less than or equal to 0.35, wherein n (VIB) represents the amount of substances of the VIB group metal element, and n (VIB+VIII) represents the sum of the amounts of substances of the VIB group metal element and the VIII group metal element;
The precipitation reaction or the hydrolysis reaction of the step (1) is carried out in the presence of a grain growth regulator and a phosphorus-containing compound at a pH of 4 to 7; the grain growth regulator is a substance capable of regulating the growth rate of grains on different crystal planes.
6. The production process according to claim 5, wherein the precipitation reaction or the hydrolysis reaction in step (1) is carried out in the presence of a crystal grain growth regulator and a phosphorus-containing compound at a pH of 4 to 6.5; the temperatures of the precipitation reaction and the hydrolysis reaction are each independently 30-90 ℃;
preferably, the conditions of the precipitation reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 10-60 minutes, preferably 10-30 minutes; the conditions of the hydrolysis reaction include: the reaction temperature is 40-90 ℃, preferably 45-80 ℃, and the reaction time is 2-30 hours, preferably 2-20 hours.
7. The production method according to claim 5 or 6, wherein the grain growth regulator is a substance capable of regulating a growth rate of grains in a 020 crystal plane and a 031 crystal plane; the grain growth regulator is at least one of polyhydroxy sugar alcohol, carboxylate and sulfate;
In the precipitation reaction, the grain growth regulator is used in an amount of 1 to 10 wt%, preferably 1.5 to 8.5 wt%, based on the weight of the inorganic aluminum-containing compound;
the grain growth regulator is used in the hydrolysis reaction in an amount of 1 to 10% by weight, preferably 1.5 to 8.5% by weight, based on the weight of the organic aluminum-containing compound, based on the aluminum oxide.
8. The production method according to claim 5 or 6, wherein the phosphorus-containing compound is selected from at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate, and potassium phosphate; the phosphorus-containing compound is used in an amount such that P in the prepared phosphorus-containing alumina is based on the total amount of the phosphorus-containing alumina 2 O 5 The content of (2) is 1 to 6% by weight, preferably 2 to 5% by weight.
9. The preparation method according to any one of claims 5 to 8, wherein the aging of step (2) is performed at a pH of 8 to 10; the aging temperature is 50-95 ℃; aging for 0.5-8 hours; the roasting conditions in the step (3) comprise: the temperature is 350-1000deg.C, preferably 400-800deg.C, and the time is 1-10 hr, preferably 2-6 hr.
10. The production method according to any one of claims 5 to 9, wherein the inorganic aluminum-containing compound is an aluminum salt and/or an aluminate; the organic aluminum-containing compound is at least one of aluminum alkoxides which can generate hydrated aluminum oxide precipitation through hydrolysis reaction with water; the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid; the alkali is at least one of sodium metaaluminate, potassium metaaluminate, sodium hydroxide, potassium hydroxide and ammonia water.
11. The method of any one of claims 5-10, wherein the group VIB metal component is Mo and/or W and the group VIII metal component is Co and/or Ni; the molar ratio of the organic complexing agent to the hydrogenation active metal component is 0.03-2:1, preferably 0.08-1.5:1, a step of; the amount of each component is such that in the final hydrogenation catalyst, the carbon component content in terms of elements is 0.04-0.6 wt%, the carrier content is 45-80 wt%, and the hydrogenation active metal components satisfy the following relationship: the content of the hydrogenation active metal component calculated by oxide is 20-50 wt% and is less than or equal to 0.27 and less than or equal to n (VIB)/n (VIB+VIII) is less than or equal to 0.32.
12. The preparation method according to any one of claims 5 to 11, wherein the organic complexing agent is selected from one or more of oxygen-containing and/or nitrogen-containing organic substances selected from one or more of organic alcohols, organic acids, and nitrogen-containing organic substances selected from one or more of organic amines, organic ammonium salts; further preferably, the organic complexing agent is one or more of organic acids having 2 to 7 carbon atoms.
13. The process according to claim 5, wherein the calcination in step (4) is carried out under the condition of introducing a gas at a temperature of 350 to 500 ℃, preferably 360 to 450 ℃, for a time of 0.5 to 8 hours, preferably 1 to 6 hours, and an amount of the gas introduced is 0.2 to 20 liters/(g.h), preferably 0.3 to 10 liters/(g.h).
14. Use of a hydrogenation catalyst according to any one of claims 1 to 4 or a hydrogenation catalyst obtainable by a process according to any one of claims 5 to 13 in a hydrocarbon oil hydrogenation reaction.
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| WO2015146822A1 (en) * | 2014-03-27 | 2015-10-01 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrodesulfurization catalyst for hydrocarbon oil |
| US20180104676A1 (en) * | 2015-05-27 | 2018-04-19 | Jgc Catalysts And Chemicals Ltd. | Hydrotreating catalyst for hydrocarbon oil, process for producing same, and hydrotreating method |
| CN108421557A (en) * | 2017-02-15 | 2018-08-21 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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| US20050109674A1 (en) * | 2003-11-20 | 2005-05-26 | Advanced Refining Technologies Llc | Hydroconversion catalysts and methods of making and using same |
| WO2015146822A1 (en) * | 2014-03-27 | 2015-10-01 | Ｊｘ日鉱日石エネルギー株式会社 | Hydrodesulfurization catalyst for hydrocarbon oil |
| US20180104676A1 (en) * | 2015-05-27 | 2018-04-19 | Jgc Catalysts And Chemicals Ltd. | Hydrotreating catalyst for hydrocarbon oil, process for producing same, and hydrotreating method |
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