WO1999010097A1 - Catalyseur d'hydroraffinage du petrole lourd, procede d'hydroraffinage, et procede de fabrication de ce catalyseur - Google Patents
Catalyseur d'hydroraffinage du petrole lourd, procede d'hydroraffinage, et procede de fabrication de ce catalyseur Download PDFInfo
- Publication number
- WO1999010097A1 WO1999010097A1 PCT/JP1998/003786 JP9803786W WO9910097A1 WO 1999010097 A1 WO1999010097 A1 WO 1999010097A1 JP 9803786 W JP9803786 W JP 9803786W WO 9910097 A1 WO9910097 A1 WO 9910097A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- hydrorefining
- heavy oil
- concentration
- potassium
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 169
- 239000000295 fuel oil Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 23
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 41
- 239000011591 potassium Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 38
- 230000002093 peripheral effect Effects 0.000 claims abstract description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 8
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- -1 hetero compound Chemical class 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000003112 potassium compounds Chemical class 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 150000002736 metal compounds Chemical class 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000008188 pellet Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 12
- 229910052720 vanadium Inorganic materials 0.000 description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000004453 electron probe microanalysis Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007324 demetalation reaction Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- LSXOKVVFQJBURM-UHFFFAOYSA-H hydrogen phosphate rhodium(3+) Chemical compound [Rh+3].P(=O)(O)([O-])[O-].P(=O)(O)([O-])[O-].P(=O)(O)([O-])[O-].[Rh+3] LSXOKVVFQJBURM-UHFFFAOYSA-H 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
Definitions
- the porous inorganic oxide support is made of at least one kind of hydrogenated activated gold selected from Group 6, Group 8, Group 9, and Group 10 elements of the periodic table.
- a method for producing a catalyst comprising impregnating a solution containing a group element component and a phosphoric acid compound, and then impregnating a solution containing a potassium compound.
- the catalyst obtained by this production method is extremely suitable as a catalyst for hydrorefining heavy oil containing a large amount of metal because the concentration of potassium at the center is lower than the concentration of potassium at the periphery.
- the present invention provides a hydrorefining treatment catalyst produced by the production method according to the third aspect of the present invention.
- FIG. 5 is a diagram showing the results of EPMA analysis of the pellet cross section of the spent catalyst A used in the performance test.
- Ni indicates the X-ray intensity of nickel and V indicates the X-ray intensity of vanadium.
- X potassium concentration When the concentration of potassium near the center (R is the distance from the outer surface to the center and the range of 0.8 R to 1.0 R from the outer surface) is Xi, the value of Xi / Xo is 0 to 0. .8, particularly preferably in the range of 0 to 0.6.
- the potassium concentration can be determined by analyzing the cross section of the catalyst bed by an analytical method suitable for quantitative analysis of elements contained in a minute area, such as EPMA, Auger electron spectroscopy, and secondary ion mass spectrometry (S IMS). It can be obtained from the integrated value of the detected intensity in a predetermined range when the analysis is performed.
- the section to be analyzed is a section perpendicular to the axis of symmetry when the catalyst pellet can approximate a rotationally symmetric shape, and the axis of symmetry is the center of the section.
- the method of containing potassium in a higher concentration in the outer periphery of the catalyst pellet there are no particular restrictions on the method of strongly adsorbing the carrier such as citric acid, tartaric acid, oxalic acid, maleic acid, and acetic acid.
- This drying is preferably performed at a temperature in the range of 50 to 180 ° C., particularly 80 to 150 ° C., for 10 minutes to 24 hours.
- firing is performed in a temperature range of 400 to 600 ° C, particularly 450 to 550 ° C, and a heating time up to the firing temperature is 10 to 240 minutes, and a firing temperature.
- the holding time in is preferably 1 to 240 minutes.
- Phosphoric acid compounds are likely to be selectively distributed around the outer periphery of the catalyst, and the force zone also selectively binds to phosphorus. As a result, it is possible to distribute the force zone to the outer periphery of the catalyst. Used for reasons.
- the other demetalization catalyst or desulfurization catalyst may be a hydrotreating catalyst substantially containing no potassium and having a porous inorganic oxide carrier carrying a hydrogenation active metal element.
- a metal removal treatment may be performed prior to the hydrorefining treatment according to the present invention. That is, the catalyst of the present invention comprises a hydrorefining treatment step Can be used in any order in combination with other catalysts.
- the hydrorefining catalyst of the present invention and the method for producing the same will be described in detail with reference to Examples, but the present invention is not limited thereto.
- An aqueous solution prepared by dissolving 8.88 g of ammonium molybdate and 5.09 g of phosphoric acid in 150 g of a porous alumina carrier formed into a 1.3 mm diameter and 2-3 mm length (equivalent to the water absorption of the carrier) was spray impregnated and dried at 130 ° C. for 6 hours.
- An aqueous solution (equivalent to the amount of water absorbed by the carrier) prepared by dissolving 1.48 g of potassium hydroxide in a dried alumina carrier was spray impregnated. Thereafter, the temperature was raised to 500 ° C. in a rotary kiln over 30 minutes, and calcined for 30 minutes to prepare Catalyst A. Comparative example
- aqueous solution (equivalent to the amount of water absorbed by the carrier) prepared by dissolving 7.77 g of ammonium molybdate in 150 g of the same porous alumina carrier as in the example was spray-impregnated in the same manner as in the example, and subjected to a temperature of 130 ° C. For 6 hours. Thereafter, in the same manner as in the example, the temperature was raised to 500 ° C. over 30 minutes, and calcined for 30 minutes to prepare catalyst B.
- the heavy oil used in the reaction was a mixture of Middle Eastern atmospheric residual oil and vacuum residual oil in equal weight.
- the properties are as shown in Table 3.
- the analysis of metal-containing hetero compounds contained in heavy oil was performed by GPC-ICP analysis.
- the analysis target is fractionated by molecular weight difference by GPC (gel 'permeation' chromatography), and each hetero atom is ICP0CP or ICP-AES: Inductively coupled plasma emission spectroscopy, SPS manufactured by Seiko Denshi Kogyo -1500).
- the hetero-containing compound containing vanadium and nickel with a molecular weight of 300000 (molecular weight in terms of polystyrene in GPC analysis) or more was contained at 78 ppm by weight as a metal component.
- the catalysts A and B used in the performance test were taken out, and the results of EPA analysis of the pellet cross section in the radial direction are shown in FIGS. 5 and 6, respectively.
- the X-ray intensities in FIGS. 5 and 6 are each on an arbitrary scale, they are represented by the same scale between FIGS. 5 and 6. From the profiles of vanadium in the graphs of FIGS. 5 and 6, it can be seen that a relatively large amount of vanadium diffuses deeper into the pellet in catalyst A than in catalyst B. Also, from the nickel profiles in the graphs of Figs. 5 and 6, it can be seen that the deposition rate of nickel is higher in the inside of the pellet than in the outer periphery of the pellet in catalyst A, and vice versa in the profile of catalyst B. .
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
L'invention concerne un catalyseur d'hydroraffinage du pétrole lourd. Ce catalyseur renferme un excipient d'oxyde inorganique poreux, sur lequel on a formé un dépôt d'au moins un élément actif métallique hydrogéné, choisi parmi les métaux des groupes 6, 8, 9, et 10 du tableau périodique. Ce catalyseur renferme également 0,1 à 3 % en poids de potassium. On répartit ce potassium de manière à ce que la partie périphérique dudit catalyseur présente une concentration de potassium supérieure à celle de la partie centrale. Le potassium étant néanmoins présent sur la partie périphérique du catalyseur, les composés métalliques contenus dans le pétrole lourd sont décomposés en produits à faible poids moléculaire. Les pores sont donc bouchés moins facilement, et lesdits composés métalliques à faible poids moléculaire éliminés même à l'intérieur du catalyseur, dont on peut ainsi entretenir longtemps l'activité.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51418599A JP4057654B2 (ja) | 1997-08-26 | 1998-08-26 | 重質油の水素化精製処理用触媒、水素化精製処理方法及び触媒の製造方法 |
| US09/512,879 US6383974B1 (en) | 1997-08-26 | 2000-02-25 | Hydrorefining catalyst and method for manufacturing hydrorefining catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9/243529 | 1997-08-26 | ||
| JP24352997 | 1997-08-26 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/512,879 Continuation US6383974B1 (en) | 1997-08-26 | 2000-02-25 | Hydrorefining catalyst and method for manufacturing hydrorefining catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999010097A1 true WO1999010097A1 (fr) | 1999-03-04 |
Family
ID=17105266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1998/003786 WO1999010097A1 (fr) | 1997-08-26 | 1998-08-26 | Catalyseur d'hydroraffinage du petrole lourd, procede d'hydroraffinage, et procede de fabrication de ce catalyseur |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4057654B2 (fr) |
| WO (1) | WO1999010097A1 (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172140A1 (fr) * | 1999-02-26 | 2002-01-16 | Japan Energy Corporation | Catalyseur pour le traitement par hydrodesulfuration, procede de traitement par hydrodesulfuration et procede de preparation du catalyseur |
| JP2010006677A (ja) * | 2008-06-30 | 2010-01-14 | Yasuo Ishikawa | 水素発生用触媒及びその製造方法並びに水素発生装置 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58153539A (ja) * | 1982-03-09 | 1983-09-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | 水素化脱硫触媒 |
| JPH0929094A (ja) * | 1994-11-22 | 1997-02-04 | China Petro Chem Corp | 水素化脱金属触媒およびその調製 |
-
1998
- 1998-08-26 JP JP51418599A patent/JP4057654B2/ja not_active Expired - Lifetime
- 1998-08-26 WO PCT/JP1998/003786 patent/WO1999010097A1/fr active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58153539A (ja) * | 1982-03-09 | 1983-09-12 | Nippon Shokubai Kagaku Kogyo Co Ltd | 水素化脱硫触媒 |
| JPH0929094A (ja) * | 1994-11-22 | 1997-02-04 | China Petro Chem Corp | 水素化脱金属触媒およびその調製 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1172140A1 (fr) * | 1999-02-26 | 2002-01-16 | Japan Energy Corporation | Catalyseur pour le traitement par hydrodesulfuration, procede de traitement par hydrodesulfuration et procede de preparation du catalyseur |
| EP1172140A4 (fr) * | 1999-02-26 | 2002-06-12 | Japan Energy Corp | Catalyseur pour le traitement par hydrodesulfuration, procede de traitement par hydrodesulfuration et procede de preparation du catalyseur |
| JP2010006677A (ja) * | 2008-06-30 | 2010-01-14 | Yasuo Ishikawa | 水素発生用触媒及びその製造方法並びに水素発生装置 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4057654B2 (ja) | 2008-03-05 |
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