CN106459781A - Regeneration and Utilization Method of Heavy Oil Desulfurization Catalyst - Google Patents
Regeneration and Utilization Method of Heavy Oil Desulfurization Catalyst Download PDFInfo
- Publication number
- CN106459781A CN106459781A CN201580016377.9A CN201580016377A CN106459781A CN 106459781 A CN106459781 A CN 106459781A CN 201580016377 A CN201580016377 A CN 201580016377A CN 106459781 A CN106459781 A CN 106459781A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- heavy oil
- oil desulfurization
- vanadium
- regeneration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 266
- 239000000295 fuel oil Substances 0.000 title claims abstract description 149
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 118
- 230000023556 desulfurization Effects 0.000 title claims abstract description 118
- 238000011069 regeneration method Methods 0.000 title claims description 73
- 230000008929 regeneration Effects 0.000 title claims description 63
- 238000000034 method Methods 0.000 title abstract description 61
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 65
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 239000008187 granular material Substances 0.000 claims description 16
- 238000009825 accumulation Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000001172 regenerating effect Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract 2
- KSECJOPEZIAKMU-UHFFFAOYSA-N [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] Chemical compound [S--].[S--].[S--].[S--].[S--].[V+5].[V+5] KSECJOPEZIAKMU-UHFFFAOYSA-N 0.000 abstract 1
- 238000003306 harvesting Methods 0.000 abstract 1
- 238000010899 nucleation Methods 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 36
- 229910052799 carbon Inorganic materials 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 241000772415 Neovison vison Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 238000006253 efflorescence Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 206010037844 rash Diseases 0.000 description 6
- 238000009418 renovation Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000003350 kerosene Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 208000012826 adjustment disease Diseases 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 208000020442 loss of weight Diseases 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000007324 demetalation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- SAEBCFDIJRQJQB-UHFFFAOYSA-N carbonic acid;nickel Chemical compound [Ni].OC(O)=O SAEBCFDIJRQJQB-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229940062043 nitrogen 50 % Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/20—Sulfiding
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/56—Hydrocarbons
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/72—Regeneration or reactivation of catalysts, in general including segregation of diverse particles
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G2300/70—Catalyst aspects
- C10G2300/706—Catalytic metal recovery
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- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The method for regenerating and utilizing a heavy oil desulfurization catalyst of the present invention is characterized by comprising the steps of removing a heavy oil desulfurization catalyst which is packed in 1 heavy oil desulfurization device and has a permissible metal amount MPr1 represented by the following formula (1) of less than 0, regenerating the removed heavy oil desulfurization catalyst, and packing the regenerated heavy oil desulfurization catalyst in at least 1 different heavy oil desulfurization device, and also characterized by including the steps of harvesting and seeding MPr1= (PV/2Vv) × {8 × 10 {5×(PD)1.3× (Sp/Vp) - (VA1+ VA2) where PV is the pore volume when a new catalyst is used, Vv is the volume when 1 mass% of vanadium is deposited on 1kg of a new catalyst and is regarded as vanadium sulfide, PD is the average pore diameter when a new catalyst is used, Sp is the average outer surface area of 1 particle when a new catalyst is used, Vp is the average volume of 1 particle when a new catalyst is used, VA1 is the amount (mass%) of vanadium deposited in the original apparatus, and VA2 is the amount of vanadium deposited when a regenerated catalyst is used in the same apparatus.
Description
Technical field
The present invention relates to the regeneration method of heavy oil desulfurization catalyst used in the hydrodesulfurization of heavy oil is processed.
Background technology
Exist in petroleum refinement multiple the step to refine various fractions is processed by hydrofinishing, develop various for this
Catalyst.In such catalyst, there is desulphurization and denitrification catalyst, the desulfurization of heavy light oil of Petroleum, kerosene and light oil etc.
Desulphurization and denitrification catalyst of denitrification catalyst, Cracking catalyst and residual oil and heavy oil etc. etc..Wherein, relatively low to boiling point and vanadium
Deng the substantially zeroed Petroleum of the content of metal impurities, kerosene and light oil etc. carry out when hydrofinishing is processed the catalyst that uses because
Using and the degradation that leads to is little.
Catalyst Petroleum, kerosene and light oil etc. being carried out use when hydrofinishing is processed will not be because of metal impurities such as vanadium
And deteriorate, the deterioration of catalyst is to be led to by the accumulation of a small amount of carbonaceous.Therefore, as long as by burning carbon from catalyst
Remove, then catalyst can be recycled.Further, for the removing of carbonaceous, because the amount of the carbonaceous on catalyst is few,
Therefore just can be with regenerated catalyst without tight Combustion System.Additionally, through use catalyst in also there is degradation
Such catalyst can directly be recycled by few catalyst without Regeneration Treatment.
Recently, the hydrofinishing for heavy light oil and decompression light oil etc. processes catalyst, is also carried out regeneration thus profit again
With establishing renovation process and the reuse method of this catalyst.For example, it is hydrogenated with used in heavy Unicracking-JHC technique
Cracking catalyst and for its pre-treatment hydrodenitrogenation catalyst activated by hydrogen or oxygen activation and be reproduced, recycle.This
The catalyst being used for the hydrofinishing process of distillate oil a bit is used for the few raw oil of metal impurities, and therefore the metal such as vanadium is in catalysis
Accumulation in agent is few.Additionally, the carbonaceous being piled up on catalyst is also few, the carbonaceous being piled up on catalyst is easily burnt.Therefore,
When being regenerated by burning, catalyst surface is not up to so high temperature, the catalyst therefore leading to because of Regeneration Treatment
Pore structure and active metal support state change little, heavy light oil and the decompression distillate oil such as light oil can be re-used for
Process (with reference to non-patent literature 1).
But, also comprise high boiling fraction or the heavy oil of the fraction that cannot distill comprise substantial amounts of asphalitine composition etc. easily
The composition of carbonization and metal impurities, the used catalyst after using in hydrofinishing is processed piles up substantial amounts of carbonaceous and gold
Belong to composition.Remove due to simply cannot have carbonaceous and the used catalyst of metal ingredient carbonaceous from accumulation simultaneously, because
This must remove carbonaceous at high combustion temperatures.Therefore, the pore structure of the catalyst leading to because of Regeneration Treatment and active metal
The change supporting state become big, the function of removing the catalyst after carbonaceous significantly reduces (with reference to non-patent literature 2 and non-patent
Document 3).Thus, used in the hydrofinishing of heavy oil is processed, catalyst is going out of use without in the case of recycling.
But, in order to reduce garbage and cut down catalyst cost it is important that in the hydrofinishing of heavy oil
Used in process, catalyst is regenerated and is recycled.Reuse method as regenerated catalyst is it is known that such as patent is civilian
Offer the hydrodesulfurizationprocess process of the renovation process of catalyst for hydroprocessing of heavy oil described in 1 and the mink cell focus described in patent documentation 2.
The renovation process of the catalyst for hydroprocessing of heavy oil according to patent documentation 1, in mink cell focus hydrofinishing handling process
Regeneration Treatment is carried out to the catalyst inactivating because using, can be by by its pore volume, pore diameter, vanadium accumulating amount and unit
The metal allowance that the external surface area of volume calculates is the regeneration hydrotreating catalyst of particular value again in the hydrogenation of mink cell focus
Utilize in process.Additionally, the hydrodesulfurizationprocess process of the mink cell focus according to patent documentation 2, by because of the hydrogenation in mink cell focus etc.
In handling process using and inactivate thus unserviceable catalyst carries out Regeneration Treatment, such that it is able to effectively apply flexibly.
Prior art literature
Patent documentation
Patent documentation 1：No. 3708381 publications of Japanese Patent Publication No.
Patent documentation 2：No. 3527635 publications of Japanese Patent Publication No.
Non-patent literature
Non-patent literature 1：Stadies in Surface and Catalysis, volume 88, P199 (1994)
Non-patent literature 2：Catal.Today, rolls up the 17, the 4th phase, P539 (1993)
Non-patent literature 3：Catal.Rev.Sci.Eng., 33 (3 ＆ 4), P281 (1991).
Content of the invention
Problems to be solved by the invention
However, in the renovation process of catalyst for hydroprocessing of heavy oil described in patent documentation 1, becoming regenerated catalyst raw material
The physical property of used catalyst depends on raw material, operating condition, and reproducibility is caused with significant impact, therefore harsh for operating
For spending high device, not necessarily can serve as regenerated catalyst.Additionally, the hydrodesulfurization of the mink cell focus described in patent documentation 2
Method only proposes the renovation process that 1 table apparatus only carry out 1 time, not continuous and stable renovation process.Therefore, the present invention
Purpose is, provides making profits again of the heavy oil desulfurization catalyst that can effectively further used catalyst be recycled
Use method.
The means of solve problem
The present inventor etc. has made intensive studies, even it was found that in heavy-oil hydrogenation refinement treatment using and inactivate and
The catalyst of use cannot regenerated, by using outer by pore volume, pore diameter, vanadium accumulating amount and unit volume in the past
The metal allowance that surface calculates judging whether it can be used for the regenerated catalyst in other devices and applied, from
And can stably apply flexibly regenerated catalyst in multiple device entirety to greatest extent, thus complete the present invention.That is, the present invention
As described below.
[1] the regeneration method of heavy oil desulfurization catalyst is it is characterised in that possess following steps：
Taking-up is filled in the heavy oil desulfurization that the metal allowance MPr1 shown in 1 heavy oil desulfurization device and following formula (1) is less than 0 and urges
The step of agent；The step regenerating the heavy oil desulfurization catalyst being removed；And, by the heavy oil desulfurization catalyst filling through regeneration
To the step of other different at least one heavy oil desulfurization devices,
・MPr1=(PV/2Vv)×{8×105×(PD)1.3}×(Sp/Vp)-(VA1+VA2) …(1)
In formula (1), each symbol represents following implications respectively：
PV：Pore volume (m during raw catelyst3/kg)
Vv：When 1 mass % vanadium is piled up on 1kg raw catelyst, it is considered as volume=3.8 × 10 during vanadic sulfide-6(m3/%kg)
PD：Average pore diameter (m) during raw catelyst
Sp：The average outer surface of 1 granule during raw catelyst amasss (m2)
Vp：Average external volume (the m of 1 granule during raw catelyst3)
VA1：The vanadium accumulating amount (quality %) of accumulation in original device, it is in terms of raw catelyst benchmark
VA2：Use the vanadium accumulating amount (quality %) during the catalyst through regeneration in the same apparatus, it is in terms of raw catelyst benchmark.
[2] the regeneration method of the heavy oil desulfurization catalyst according to [1], wherein, the heavy oil through regeneration is being taken off
Sulfur catalyst is filled to the step of other different at least one heavy oil desulfurization devices, by the heavy oil desulfurization catalyst through regeneration
Fill to different heavy oil desulfurization devices so that the metal allowance MPr2 shown in following formula (2) reaches more than 0,
・MPr2=(PV/2Vv)×{8×105×(PD)1.3}×(Sp/Vp)-(VA1+VB1) … (2)
In formula (2), each symbol represents following implications respectively：
PV：Pore volume (m during raw catelyst3/kg)
Vv：When 1 mass % vanadium is piled up on 1kg raw catelyst, it is considered as volume=3.8 × 10 during vanadic sulfide-6(m3/%kg)
PD：Average pore diameter (m) during raw catelyst
Sp：The average outer surface of 1 granule during raw catelyst amasss (m2)
Vp：Average external volume (the m of 1 granule during raw catelyst3)
VA1：The vanadium accumulating amount (quality %) of accumulation in original device, it is in terms of raw catelyst benchmark
VB1：Using the vanadium accumulating amount (quality %) accumulated during catalyst through regeneration in new equipment, it is with raw catelyst benchmark
Meter.
[3] the regeneration method of the heavy oil desulfurization catalyst according to [2], wherein, fills and takes off to different heavy oil
Sulfur device is so that the metal allowance MPr2 shown in above-mentioned formula (2) reaches more than 1 and less than 5.
The effect of invention
According to the present invention it is possible to provide the heavy oil desulfurization catalyst that can effectively used catalyst be recycled again
Raw Application way.
Brief description
Fig. 1：Fig. 1 is for illustrating to decline the schematic diagram of flow pattern fixed bed reactors used in embodiments of the invention.
Specific embodiment
The regeneration method of the heavy oil desulfurization catalyst of the present invention possesses following steps：Take out heavy oil desulfurization catalyst
Step, the regeneration step of heavy oil desulfurization catalyst and fill to the step of heavy oil desulfurization device.Hereinafter, describe this in detail
The regeneration method of bright heavy oil desulfurization catalyst.
[step taking out heavy oil desulfurization catalyst]
The step of the taking-up heavy oil desulfurization catalyst of the present invention is to take out to be filled in 1 heavy oil desulfurization device and following formula (1) institute
The step that the metal allowance MPr1 showing is less than 0 heavy oil desulfurization catalyst.
・MPr1=(PV/2Vv)×{8×105×(PD)1.3}×(Sp/Vp)-(VA1+VA2) …(1)
In formula (1), each symbol represents following implications respectively：
PV：Pore volume (m during raw catelyst3/kg)
Vv：When 1 mass % vanadium is piled up on 1kg raw catelyst, it is considered as volume=3.8 × 10 during vanadic sulfide-6(m3/%kg)
PD：Average pore diameter (m) during raw catelyst
Sp：The average outer surface of 1 granule during raw catelyst amasss (m2)
Vp：Average external volume (the m of 1 granule during raw catelyst3)
VA1：The vanadium accumulating amount (quality %) of accumulation in original device, it is in terms of raw catelyst benchmark
VA2：Use the vanadium accumulating amount (quality %) during the catalyst through regeneration in the same apparatus, it is in terms of raw catelyst benchmark.
(heavy oil desulfurization device)
The heavy oil desulfurization device of the present invention processes the hydrogenation that heavy oil is implemented with desulfurization, denitrogenation, deoxidation and hydrocarbon by hydrofinishing
And cracking.Additionally, heavy oil desulfurization device not only can implement the hydrofinishings such as desulfurization and denitrogenation, demetalization and drip can also be implemented
Being hydrocracked of blue or green matter.It is conceived to this aspect, heavy oil desulfurization device is not only provided purely for the purpose of heavy oil desulfurization, sometimes go back and slag
The residual oil process for upgrading such as oily fluid catalytic cracking (RFCC), coker, solvent deasphalting are applied in combination.Filled by heavy oil desulfurization
Product heavy oil obtained from putting for example is used as RFCC raw material, coker raw material and low sulfur product heavy oil.
Then, the hydrofinishing implemented in heavy oil desulfurizer is processed and illustrate.Implement in heavy oil desulfurization device
As long as hydrofinishing process can carry out desulfurization to heavy oil and just be not particularly limited, enumerate by adding that fixed bed reactors are carried out
To illustrate as a example hydrogen refinement treatment that the hydrofinishing implemented in heavy oil desulfurization device is processed.Become hydrofinishing and process raw material
Heavy oil includes the residue composition such as reduced crude and decompression residuum.But, heavy oil is not included only by kerosene, light oil and decompression light oil etc.
The composition that distillate oil is constituted.For example, heavy oil comprise more than sulfur composition 1 mass %, more than nitrogen component 200 mass ppm, residual carbon becomes
Divide more than more than 5 mass %, more than vanadium 5ppm and asphalitine composition 0.5 mass %.Heavy oil can be enumerated beyond such as reduced crude
Crude oil, coal tar, hot tearing carburetion, tar sand oil and their miscella etc..As long as becoming the heavy oil that hydrofinishing processes raw material
It is that heavy oil as above is just not particularly limited, reduced crude, decompression residuum, decompression residuum or coal tar and cracking light oil
Miscella etc. can be suitably used as the raw material of hydrofinishing process.
The reaction temperature that hydrofinishing is processed is preferably 300 ~ 450 DEG C, more preferably 350 ~ 420 DEG C, more preferably
370~410℃.The hydrogen partial pressure that hydrofinishing is processed is preferably 7.0 ~ 25.0MPa, more preferably 10.0 ~ 18.0MPa.Hydrogenation essence
The liquid hourly space velocity (LHSV) that system is processed is preferably 0.01 ~ 10h-1, more preferably 0.1 ~ 5h-1, more preferably 0.1 ~ 1h-1.Hydrogenation
Hydrogen/the raw oil of refinement treatment is than preferably 500 ~ 2,500Nm3/ kl, more preferably 700 ~ 2,000Nm3/kl.Should illustrate,
By hydrofinishing process obtained from generate the sulfur content of oil and the adjustment of metal ingredient (vanadium, nickel etc.) content can pass through example
Reaction temperature in processing as suitable adjustment hydrofinishing to be implemented.
(heavy oil desulfurization catalyst)
The heavy oil desulfurization catalyst of the present invention is that (catalyst being generally used for heavy oil desulfurization is included the catalysis through vulcanizing treatment
Agent) at least in the hydrofinishing of heavy oil is processed using catalyst obtained from once.Typically, carbon and vanadium etc. are because of use
Attachment is on a catalyst.As long as the hydrofinishing process that heavy oil desulfurization catalyst is used for heavy oil is just not particularly limited.For example, will
Support aluminium oxide catalyst obtained from molybdenum on the alumina support and be used as heavy oil desulfurization catalyst.Now, as promoter,
Cobalt or nickel can be used.
Alumina support can be containing at least one in phosphorus, silicon and boron.Phosphorus when being converted with oxide, silicon and boron
In at least one below the content in heavy oil desulfurization catalyst preferably 30.0 mass %, more preferably 0.1 ~ 10.0 mass %,
More preferably 0.2 ~ 5.0 mass %.Wherein, the content of at least one of the phosphorus in catalyst, silicon and boron is with more than 400 DEG C
At a temperature of carry out oxidation processes and the material of the loss of weight leading to because of heating will not be caused as Reference mass, with quality % Lai
Represent the content of at least one in phosphorus, silicon and boron.
The content of the molybdenum in heavy oil desulfurization catalyst is preferably 0.1 ~ 25.0 mass %, more preferably 0.2 ~ 8.0 mass %.This
Outward, the content of the cobalt in heavy oil desulfurization catalyst or nickel is preferably 0.1 ~ 10.0 mass %, more preferably 0.2 ~ 8.0 mass %.Should
Give explanation, the metal ingredient content in heavy oil desulfurization catalyst is to carry out oxidation processes and will not at a temperature of more than 400 DEG C
The material causing the loss of weight leading to because of heating, as Reference mass, represents the oxidation material of measure object metal with quality %
Amount.
Heavy oil comprises substantial amounts of asphalitine and vanadium, heavy oil desulfurization catalyst used in therefore the hydrofinishing of heavy oil is processed
Upper accumulation has carbon component and vanadium.Carbon component covers the catalyst surface of heavy oil desulfurization catalyst, makes urging of heavy oil desulfurization catalyst
Change activity to reduce.But, Regeneration Treatment is processed etc. by solvent extraction and oxidizing fire, can remove and be piled up in heavy oil desulfurization and urge
Carbon component in agent, can make the catalysis activity of heavy oil desulfurization catalyst increase.Used heavy oil desulfurization before Regeneration Treatment
Carbon component content in catalyst is preferably 10 ~ 70 mass %, more preferably 0.2 ~ 8.0 mass %.If heavy oil desulfurization catalyst
In carbon component content be more than 70 mass %, even if then carrying out Regeneration Treatment, the activity that there is also catalyst will not fully increase,
Or need to carry out Regeneration Treatment at high temperature thus leading to the intensity decreases of catalyst to increase the activity of catalyst
Situation.Should illustrate, the carbon component content in heavy oil desulfurization catalyst with carry out at a temperature of more than 400 DEG C oxidation processes and
The material that the loss of weight leading to because of heating will not be caused, as Reference mass, represents that with quality % the carbon in object catalyst becomes
Sub-prime amount.
The content of vanadium in used heavy oil desulfurization catalyst before Regeneration Treatment is preferably below 35 mass %, more preferably
Below 20 mass %.If content of vanadium is more than 35 mass %, even if carrying out Regeneration Treatment, the activity that there is also catalyst will not be filled
Divide and increase or need to carry out Regeneration Treatment at high temperature thus leading to the intensity of catalyst to increase the activity of catalyst
Situation about reducing.The vanadium being piled up on heavy oil desulfurization catalyst generally cannot be removed by Regeneration Treatment.
Content of vanadium in used catalyst will not change before and after Regeneration Treatment substantially.Therefore, based on use
Content of vanadium in used catalyst and the metal allowance MPr1 that calculates, can identify before Regeneration Treatment and can regenerate
Even if the catalyst that the catalyst using and regeneration also cannot use.Even if the catalyst that regeneration also cannot be used regenerates
Process is insignificant, also cannot make even if screening from used catalyst therefore preferably before Regeneration Treatment and removing regeneration
Catalyst.
For hydrofinishing process used in catalyst and through for Regeneration Treatment oxidation processes, particularly fire
Burn the catalyst processing, lead to the pore structure of catalyst and active metal because of heatable catalyst when processing supports state
Change, catalysis activity reduces sometimes.As evaluating their index, there are specific surface area, the pore capacity of catalyst.Urge
The specific surface area of agent and pore capacity slowly reduce because of the attachment of hydrofinishing process and impurity, even if carrying out Regeneration Treatment
Also easily reduce.The specific surface area of used heavy oil desulfurization catalyst and pore volume are preferably respectively the specific surface of raw catelyst
Amass more than 70% with pore volume.The specific surface area of used heavy oil desulfurization catalyst is preferably 60 ~ 220m2/ g, more preferably
100~200m2/g.Additionally, the pore volume of used heavy oil desulfurization catalyst preferably 0.3 ~ 1.2cc/g, more preferably 0.4 ~
0.8cc/g.
Should illustrate, raw catelyst is to manufacture as catalyst and be never catalyzed used in hydrofinishing process
Agent.Further, raw catelyst also include once in hydrofinishing process using but because of device in terms of fault etc. and minor interruptions
Using and again directly use catalyst.That is, raw catelyst includes following catalyst：Even if temporary transient use, without special
The activation processing or Regeneration Treatment such as take out and screened, washed and aoxidized from reactor, still fully possesses and envisioned originally
Hydrogenation activity and the catalyst that can directly use.Raw catelyst can be commercially available catalyst or special preparation
Catalyst.Additionally, raw catelyst can be the sulfuration implementing as the front process for the purpose of using in hydrotreating
Catalyst obtained from process.
(metal allowance)
Can the metal allowance MPr1 of above-mentioned formula (1) be for judging be catalyzed regeneration used in heavy oil desulfurization device
Catalyst obtained from agent is in same heavy oil desulfurization device using the index of stipulated time.Metal allowance MPr1 is compared with 0
Bigger, more can allow the accumulation of a large amount of vanadium, with therefore being rich in leeway by this catalyst in same heavy oil desulfurization device
Using the stipulated time.On the other hand, when MPr1 is less than 0 (that is, when being negative value), reach the stipulated time in the use time of catalyst
Before, the activity leading to regenerated catalyst due to the accumulation of vanadium becomes not fill for using in this heavy oil desulfurization device
Point.Therefore, by using metal allowance MPr1, can be from because of the vanadium accumulation heavy oil desulfurization catalyst inactivating on a catalyst
In screen out do not possess the heavy oil desulfurization catalyst that can bear used in above-mentioned heavy oil desulfurization device activity it may be determined that
Heavy oil desulfurization catalyst used in above-mentioned heavy oil desulfurization device.And, in the present invention, will be low for metal allowance MPr1
Catalyst in 0 is judged as the catalyst taking out from heavy oil desulfurization device.Hereinafter, describe above-mentioned formula (1) in detail.
The metal allowance MPr1 of above-mentioned formula (1) is to inactivate thus permissible reaching the life-span to catalyst because vanadium piles up
The index of the vanadium accumulating amount further allowing for.This value is less, then become more to allow vanadium to pile up.In the present invention, take off from heavy oil
The MPr1 of the catalyst taking out in sulfur device is less than 0.Should illustrate, the MPr1 value of commercial catalyst is in vanadium accumulating amount (VA1+
VA2) for (raw catelyst) when 0% also usually less than 50, it is 20 ~ 35 in the case of catalyst for demetalation, in desulphurization catalyst
In the case of be 10 ~ 25.
Vanadium during the 1st of above-mentioned formula (1) expression raw catelyst piles up allowance, and it is by the pore volume etc. of raw catelyst
Initial stage physical property, to determine, does not change because of the use of catalyst and Regeneration Treatment.PV is pore volume during raw catelyst.Vv is
When 1 mass % vanadium is piled up on 1kg raw catelyst, this vanadium is regarded as vanadium volume during vanadic sulfide, is constant 3.8 × 10-6(m3/%
kg).Should illustrate, it is believed that vanadium is piled up in the form of vanadic sulfide in common hydrofinishing process.When PD is raw catelyst
Average pore diameter.Constant 8 × 105×(PD)1.3It is to be existed by the vanadium obtained from analysis result of the various catalyst studied
Diffusion depth in the pore of catalyst.Diffusion depth is typically considered to and (diffusion coefficient/rate constant)-0.5Become ratio
Example, diffusion coefficient proportional to the pore diameter of catalyst (with reference to the 5th edition revision chemistry engineering brief guide the 27th chapter).But, root
According to the present inventor etc. research find, in this catalyst, its as described above with (catalyst pore diameter PD)1.3Proportional.
Sp is the external surface area of 1 granule during raw catelyst, the value actually in terms of meansigma methodss.Additionally, Vp is new
The volume of 1 granule during catalyst, is equally meansigma methodss with Sp.(Sp/Vp) be each catalyst in terms of averagely unit
The external surface area of volume, it to be determined by the shape manufacturing during raw catelyst.
The VA1 of the 2nd be by raw catelyst heavy oil desulfurization device (in order to can be different from other described later at least 1
Individual heavy oil desulfurization device is distinguish between, below by this heavy oil desulfurization device referred to as " A device ") in using the stipulated time when accumulate
The measured value of vanadium accumulating amount (raw catelyst benchmark (quality %)) or predictive value.VA2 is that regeneration is new used in A device
Regenerated catalyst obtained from catalyst in A device using necessary time when the vanadium accumulating amount (raw catelyst benchmark (matter accumulated
Amount %)) measured value or predictive value.When VA1 is less than 0.5 mass %, the vanadium in catalyst is piled up few, even if do not regenerate can also be right
Used catalyst is recycled.Therefore, carry out Regeneration Treatment used catalyst VA1 be preferably 1.0 mass % with
On.Should illustrate, although VA1 and VA2 is expressed as the vanadium accumulating amount being piled up on catalyst, the vanadium comprising in catalyst can
Need not be piled up on catalyst.For example, the above-mentioned accumulating amount of vanadium also include in the pore enter to catalyst, in catalyst or
The vanadium amount that person and catalyst component etc. react.VA1 the and VA2 value of used catalyst is generally mostly 0 ~ 70 mass %.This
Outward, in the upstream portion of the conversion zone of A device, VA1 and VA2 value is the value of up to 30 ~ 70 mass %.
[step of regeneration heavy oil desulfurization catalyst]
In the step of regeneration heavy oil desulfurization catalyst of the present invention, the heavy oil desulfurization being removed catalyst is regenerated.Regeneration
The Regeneration Treatment implemented in the step of heavy oil desulfurization catalyst is included for example：Wash to remove oil etc. by solvent；By oxygen
Change processes and to remove carbon component, sulfur composition and nitrogen component etc.；And screened by removing the catalyst of consolidated block or grain refined
Catalyst of normal shape etc..Oxidation processes are carried out preferably outside reactor.
In the preferred Regeneration Treatment of the used catalyst being attached with a large amount of carbon components, wash use with solvent first
The catalyst crossed.Preferably solvent has such as petroleum-type such as toluene, acetone, alcohol and Petroleum, kerosene and light oil etc..This washing
In process, for example, when catalyst is in hydrofinishing treatment reactor, circulation light oil is thus washing catalyst, Ran Houliu
The gases such as logical 50 ~ 300 DEG C about of nitrogen are thus dry catalyst.Or, can be in circulation light oil thus directly taking after washing
Go out, in order to prevent heat release, spontaneous combustion and make the state moistening catalyst with light oil in advance, and be dried when needed.Additionally,
Also there are following methods：Pulverizing, efflorescence catalyst and the oxidation of block is removed from the used catalyst taking from reactor
Skin etc., it is washed with light oil, is washed with Petroleum further, so that catalyst is easily dried.Used catalyst is few
During amount, it is suitable for completely removing oil from catalyst with the method for toluene washing catalyst.
In order that the catalysis activity being removed the catalyst of oil and impurity by washing is recovered, need to pass through further oxidation
Process and remove the carbon component being piled up in catalyst.Oxidation processes generally by the controlled burn processing of ambient temperature and oxygen concentration Lai
Carry out.If ambient temperature is too high or oxygen concentration is too high, catalyst surface reaches a high temperature, and there is crystal formation and the load of carrying metal
Load state change or carrier pore reduce thus catalysis activity reduce situation.If additionally, ambient temperature is too low
Or oxygen concentration is too low, then existing becomes insufficient, catalysis activity by the removing of carbon component that burning is carried out and will not be thus capable of sufficiently recovering
Situation.The ambient temperature of burn processing is preferably 200 ~ 800 DEG C, more preferably 300 ~ 600 DEG C.
Oxygen concentration in burn processing is preferably with corresponding to combustion method, particularly the contact shape with catalyst for the burning gases
The mode of state is controlling.For example, the oxygen concentration in burn processing is preferably 1 ~ 21 volume %.Importantly, in adjustment burn processing
The flow velocity of ambient temperature, oxygen concentration and atmosphere gas etc. controlling the surface temperature of catalyst, urging during suppression burn processing
The supporting the change of state or prevent the specific surface area of catalyst of the crystal structure of the metals such as the molybdenum in agent and crystal grain
Reduce with pore capacity.
It is desirable that, remove the catalyst of efflorescence from the catalyst through burn processing etc., only by the catalysis of normal shape
Agent is used as regenerated catalyst.If the catalyst of efflorescence remains in the catalyst, cause in the catalyst layer in reactor
Fluid pressure loss in blocking and bias current, or reactor becomes big, thus there are the feelings that reactor cannot persistently run well
Condition.
[filling to the step of heavy oil desulfurization device]
The filling of the present invention, to the step of heavy oil desulfurization device, the heavy oil desulfurization catalyst through regeneration is filled to other differences
At least one heavy oil desulfurization device.Thus, even heavy oil desulfurization cannot be taken out in the step taking out heavy oil desulfurization catalyst
The used catalyst being recycled in the heavy oil desulfurization device of catalyst, it is also possible to be recycled, can have further
Used catalyst is recycled by effect ground.
As long as wadding warp regeneration the heavy oil desulfurization device of heavy oil desulfurization catalyst with take out heavy oil desulfurization catalyst
Step in take out the different heavy oil desulfurization device of heavy oil desulfurization device of heavy oil desulfurization catalyst, be just not particularly limited.This
Outward, the heavy oil desulfurization device of the heavy oil desulfurization catalyst of wadding warp regeneration can be 1 or more than 2.Fill to weight
Heavy oil desulfurization device in the step of oily desulfurizer is same with the device of explanation in the step of taking-up heavy oil desulfurization catalyst
Heavy oil desulfurization device, therefore omit heavy oil desulfurization device explanation.
In the present invention, the heavy oil desulfurization catalyst through regeneration can be filled to heavy oil desulfurization device, so that following
Metal allowance MPr2 shown in formula (2) reaches more than 0.It is therefore desirable to, can properly select and can urge used
Other heavy oil desulfurization devices that agent is recycled.
・MPr2=(PV/2Vv)×{8×105×(PD)1.3}×(Sp/Vp)-(VA1+VB1) … (2)
In formula (2), each symbol represents following implications respectively：
PV：Pore volume (m during raw catelyst3/kg)
Vv：When 1 mass % vanadium is piled up on 1kg raw catelyst, it is considered as volume=3.8 × 10 during vanadic sulfide-6(m3/%kg)
PD：Average pore diameter (m) during raw catelyst
Sp：The average outer surface of 1 granule during raw catelyst amasss (m2)
Vp：Average external volume (the m of 1 granule during raw catelyst3)
VA1：The vanadium accumulating amount (quality %) of accumulation in original device, it is in terms of raw catelyst benchmark
VB1：Using the vanadium accumulating amount (quality %) accumulated during catalyst through regeneration in new equipment, it is with raw catelyst benchmark
Meter.
Can the metal allowance MPr2 of above-mentioned formula (2) be for judging will regenerate in heavy oil desulfurization device (A device)
The catalyst obtained from catalyst using is in the heavy oil desulfurization device different from above-mentioned heavy oil desulfurization device (A device) (below
Be denoted as B device) in using the stipulated time index.Allowance MPr2 is bigger compared with 0 for metal, then with more being rich in leeway will
This catalyst is in B device using the stipulated time.On the other hand, when MPr2 is less than 0, reach regulation in the use time of catalyst
Before time, due to the accumulation of vanadium, the activity of regenerated catalyst becomes insufficient for using in this B device.But,
In the case of such as VA2 ＞ VB1, even if cannot be using it is also possible to can use in B device in A device.Can pass through
Index using metal allowance MPr2 carries out rational judgment to it.Metal allowance MPr2 in B device is more than 0, excellent
Elect more than 1 and less than 5, more preferably more than 3 and less than 5 as.Should illustrate, in above-mentioned formula (2), except by " VA1+
VA2 " is altered to outside " VA1+VB1 ", all identical with above-mentioned (1), therefore omits the explanation of above-mentioned formula (2).Additionally, VB1 be by
Raw catelyst in B device using the stipulated time when measured value of vanadium accumulating amount (raw catelyst Reference mass %) accumulated or pre-
Measured value.
Metal allowance MPr1 due to previously described formula (1) is less than 0, therefore cannot be using used catalyst in device A.
But, because the metal allowance MPr2 of above-mentioned formula (2) is more than 0, therefore can be using used catalyst in device B.
Like this, the metal allowance MPr2 based on catalyst, can properly select and can use the use that cannot use in device A
The device of the catalyst crossed.Additionally, VA1 can be defined as repeatedly regenerating and using after accumulative vanadium accumulation, MPr2 also may be used
For can judge catalyst using multiple Regeneration Treatment and after using.Should illustrate, from urging that A device takes out and regenerates
Agent not necessarily must use in a B device, as long as meeting the condition shown in above-mentioned MPr2, then can be split and be used in combination
In multiple devices.
Embodiment
Then, further describe the present invention by embodiment, but the present invention is not subject to any limit of these embodiments
System.
[character of raw material heavy oil]
For raw material heavy oil used in each embodiment and comparative example, carry out following evaluation.Raw material heavy oil uses reduced crude.
(density)
According to JIS K 2249, the density of the reduced crude at measuring 15 DEG C.
(kinematic viscosity)
According to JIS K 2283, the kinematic viscosity of the reduced crude at measuring 50 DEG C.
(content of residual carbon component)
According to JIS K 2270, measure the content of the residual carbon component of reduced crude.
(content of asphalitine composition)
According to IP 143, measure the content of the asphalitine composition of reduced crude.
(content of sulfur composition)
According to JIS K 2541, measure the content of the sulfur composition of reduced crude.
(content of nitrogen component)
According to JIS K 2609, measure the content of the nitrogen component of reduced crude.
(content of vanadium)
According to institute of Petroleum's method JPI-5S-10-79, measure the content of the vanadium of reduced crude.
(content of nickel)
According to institute of Petroleum's method JPI-5S-11-79, measure the content of the nickel of reduced crude.
(distillation character)
According to JIS K 2254, measure the distillation character of reduced crude.
[character of catalyst]
For catalyst used in each embodiment and comparative example, carry out following evaluation.
With regard to the elementary analysiss of vanadium etc., after calcining 1 hour at 650 DEG C, for molybdenum and vanadium, after ash is dissolved with acid,
It is analyzed with the luminous absorptiometric analysis of inductively coupled plasma, additionally, being directed to cobalt and nickel, by high-frequency heating ash and four
The mixture of Lithium biborate, thus making globule (bead), is analyzed with fluorescent x-ary analysis.With regard to carbon content it is desirable to be
15% (the carbon component content in catalyst to carry out oxidation processes to no longer decrement more than 400 DEG C by object catalyst
The material obtaining, as benchmark, is represented with quality % of the carbon in object catalyst, identical below) below, preferably 10% with
Under.The stage that carbon content finishes in use is mostly 10 ~ 70% about, but is removed carbon component from catalyst by Regeneration Treatment
Go, its content can be reduced.If carbon component is excessive, its covering catalyst surface so that catalysis activity reduces, but as long as
Reduce carbon content by Regeneration Treatment, then can make activation recovering.Should illustrate, carbon, the analysis of sulfur are to be analyzed with C-S simultaneously
Count and to analyze pulverizing sample.For the average length of catalyst, measure the vertical of 10 granules randomly selecting with slide gauge
In the length in the direction in section, and carry out average.The shape that the average outer surface of 1 granule amasss and average external volume is amassed by grain section
Shape and average length are calculated thus obtaining.
[generating the character of oil]
For in each embodiment and comparative example by hydrofinishing process and obtained by raw material heavy oil generation oil, carry out with above-mentioned
The Character Evaluation identical of raw material heavy oil is evaluated.Generate the Character Evaluation method of oil and the Character Evaluation method of above-mentioned raw materials heavy oil
Identical, therefore omit the explanation of the Character Evaluation method generating oil.
[manufacture of raw catelyst used in each embodiment and comparative example]
The alkaline carbonic acid nickel malic acid 180g of 630g molybdenum oxide and 150g in terms of NiO conversion is dissolved in ion exchange water,
Make 2000 milliliters of infiltration liquid.Made in the way of the water quantities making this infiltration liquid is consistent with the water absorption of following carriers
Standby, make 4,000g tetra- blade profile alumina support (specific surface area 230m2/ g, 120 angstroms of average fine pore, pore capacity 0.69ml/g)
It is infiltrated in 15 minutes in this infiltration liquid.The alumina support being impregnated with infiltration liquid is dried 3 hours at 120 DEG C, at 500 DEG C
Calcining 5 hours, thus obtain raw catelyst 1.
[manufacture of regenerated catalyst used in each embodiment and comparative example]
(embodiment 1)
- based on raw catelyst hydrofinishing process-
As shown in figure 1, being divided into 4 beds (4 deciles are carried out with volume reference) by declining flow pattern fixed bed reactors, to most upstream
Commercially available catalyst for demetalation filled by the bed (referred to as " the 1st ", identical below) in portion, to remaining 3 beds (the 2nd ~ the 4th)
Filling raw catelyst 1.Should illustrate, the physical property of raw catelyst 1 and metal allowance are shown in table 1 below.Carry out common pre- sulfur
After change is processed, using the reduced crude 1 of character shown in table 2 below, under the reaction condition 1 shown in Table 3 below, adjustment reaction temperature
Degree is so that sulfur composition reaches constant (below 0.3 mass %), and the hydrofinishing carrying out 330 days is processed.The reaction of the 330th day
Temperature is 396 DEG C.Processed by hydrofinishing thus table 4 below is shown in by the character generating oil 1 that reduced crude 1 obtains.
- Regeneration Treatment-
Catalyst 1 in above-mentioned reactor is washed with light oil, after circulate further nitrogen and drying and cooling, from reactor
The 2nd ~ the 4th in take out used catalyst, be sufficiently mixed and obtain used catalyst 1.Should illustrate, used urge
The physical property of agent 1 and metal allowance are shown in table 1 below.Then, by screening from used catalyst 1 remove block and
Efflorescence thing.Using rotary calciner (rotary speed：5 revs/min), 100% nitrogen is supplied with the flow of 100cc/ minute, and
And under 300 DEG C of heating-up temperature, drying in 1 hour is carried out to the about 300g used catalyst 1 removing block and efflorescence thing
Process.Then, the mixed gas of 50% nitrogen -50% air are supplied with the flow of 100cc/ minute, and in 450 DEG C of calcining temperature
The lower calcining of degree 3 hours, after the used catalyst 1 through calcining is cooled down, is removed block from used catalyst 1 by screening
Thing and efflorescence thing, thus obtain regenerated catalyst 1.The physical property of regenerated catalyst 1 and metal allowance are shown in table 1 below.Should
Illustrate, VA2 value uses the V2 value of aftermentioned comparative example 1.
- based on regenerated catalyst hydrofinishing process-
It is divided into 4 beds (4 deciles are carried out with volume reference) by declining flow pattern fixed bed reactors, commercially available de- to the 1st filling
Metallic catalyst, to immediately the 2nd ~ the 4th filling regenerated catalyst 1 under it.After common presulfurization process is carried out to it,
Using the reduced crude 2 of character shown in table 2 below, under the reaction condition 2 shown in Table 3 below, adjustment reaction temperature is so that sulfur
Composition reaches constant (below 0.3 mass %), and the hydrofinishing carrying out 330 days is processed.The reaction temperature of the 330th day is 398
℃.Processed by hydrofinishing thus table 4 below is shown in by the character generating oily 2A that reduced crude 2 obtains.Should illustrate, under
Used in fall flow pattern fixed bed reactors are processed with the hydrofinishing based on raw catelyst, reactor is identical, but by containing vanadium
Amount is used as raw material heavy oil less than the reduced crude 2 of reduced crude 1, this reactor can be regarded as vanadium and pile up few other reactions
Device.
- Regeneration Treatment-
By the Regeneration Treatment identical method with above-mentioned used catalyst 1, used regenerated catalyst 1 is carried out at regeneration
Reason, thus obtain regenerated catalyst 2A.The physical property of regenerated catalyst 2A and metal allowance are shown in table 1 below.
(comparative example 1)
- based on raw catelyst hydrofinishing process-
In the way of similarly to Example 1, using reduced crude 1 and the raw catelyst 1 of character shown in table 2 below, in Table 3 below
Carry out hydrofinishing process under shown reaction condition 1.
- Regeneration Treatment-
In the way of similarly to Example 1, used catalyst 1 is regenerated, thus obtaining regenerated catalyst 1.
- based on regenerated catalyst hydrofinishing process-
It is divided into 4 beds (4 deciles are carried out with volume reference) by declining flow pattern fixed bed reactors, commercially available de- to the 1st filling
Metallic catalyst, to immediately the 2nd ~ the 4th filling regenerated catalyst 1 under it.After common presulfurization process is carried out to it,
Using the reduced crude 1 of character shown in table 2 below, under the reaction condition 1 shown in Table 3 below, adjustment reaction temperature is so that sulfur
Composition reaches constant (below 0.3 mass %), and the hydrofinishing carrying out 330 days is processed.The reaction temperature of the 330th day is 408
℃.Processed by hydrofinishing thus table 4 below is shown in by the character generating oily 2B that reduced crude 1 obtains.
- Regeneration Treatment-
By the Regeneration Treatment identical method with above-mentioned used catalyst 1, used regenerated catalyst 1 is carried out at regeneration
Reason, thus obtain regenerated catalyst 2B.The physical property of regenerated catalyst 2B and metal allowance are shown in table 1 below.
From the result of embodiment 1 and comparative example 1, even MPr1 value is less than 0 used catalyst, by
MPr2 value reaches in more than 0 other devices and uses, can be by used catalyst further using the stipulated time.Should say
Bright, the ratio of the sulfur composition generating oily 2A of embodiment 1 is more than the ratio of the sulfur composition generating oily 2B of comparative example 1, but right
In the low device of the load of catalyst, the desired value generating the sulfur composition of oil is high, is therefore directed to the used catalyst of embodiment 1
Use for there is no problem.On the other hand, it is contemplated that to catalyst in the case of the used catalyst of comparative example 1
The high device of load, the desired value generating the sulfur composition of oil is also low, therefore comparative example 1 generate oily 2B character insufficient.
Description of reference numerals
1 the 1st
2 the 2nd
3 the 3rd
4 the 4th
Claims (3)
1. the regeneration method of heavy oil desulfurization catalyst is it is characterised in that possess following steps：
Taking-up is filled in the heavy oil desulfurization that the metal allowance MPr1 shown in 1 heavy oil desulfurization device and following formula (1) is less than 0 and urges
The step of agent；
The step of the heavy oil desulfurization catalyst being removed described in regeneration；And
The described heavy oil desulfurization catalyst through regeneration is filled to the step of other different at least one heavy oil desulfurization devices,
・MPr1=(PV/2Vv)×{8×105×(PD)1.3}×(Sp/Vp)-(VA1+VA2) …(1)
In formula (1), each symbol represents following implications respectively：
PV：Pore volume (m during raw catelyst3/kg)
Vv：When 1 mass % vanadium is piled up on 1kg raw catelyst, it is considered as volume=3.8 × 10 during vanadic sulfide-6(m3/%kg)
PD：Average pore diameter (m) during raw catelyst
Sp：The average outer surface of 1 granule during raw catelyst amasss (m2)
Vp：Average external volume (the m of 1 granule during raw catelyst3)
VA1：The vanadium accumulating amount (quality %) of accumulation in original device, it is in terms of raw catelyst benchmark
VA2：Use the vanadium accumulating amount (quality %) during the catalyst through regeneration in the same apparatus, it is in terms of raw catelyst benchmark.
2. the regeneration method of heavy oil desulfurization catalyst according to claim 1, wherein, by described through regeneration weight
Oily desulphurization catalyst is filled to the step of other different at least one heavy oil desulfurization devices,
The described heavy oil desulfurization catalyst through regeneration is filled to different heavy oil desulfurization devices so that following formula (2) is shown
Metal allowance MPr2 reach more than 0,
・MPr2=(PV/2Vv)×{8×105×(PD)1.3}×(Sp/Vp)-(VA1+VB1) … (2)
In formula (2), each symbol represents following implications respectively：
PV：Pore volume (m during raw catelyst3/kg)
Vv：When 1 mass % vanadium is piled up on 1kg raw catelyst, it is considered as volume=3.8 × 10 during vanadic sulfide-6(m3/%kg)
PD：Average pore diameter (m) during raw catelyst
Sp：The average outer surface of 1 granule during raw catelyst amasss (m2)
Vp：Average external volume (the m of 1 granule during raw catelyst3)
VA1：The vanadium accumulating amount (quality %) of accumulation in original device, it is in terms of raw catelyst benchmark
VB1：Using the vanadium accumulating amount (quality %) accumulated during catalyst through regeneration in new equipment, it is with raw catelyst benchmark
Meter.
3. the regeneration method of heavy oil desulfurization catalyst according to claim 2, wherein, fills and takes off to different heavy oil
Sulfur device is so that the metal allowance MPr2 shown in described formula (2) reaches more than 1 and less than 5.
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| JP2014065540A JP6335575B2 (en) | 2014-03-27 | 2014-03-27 | Recycling method of heavy oil desulfurization catalyst |
| PCT/JP2015/059504 WO2015147222A1 (en) | 2014-03-27 | 2015-03-26 | Method for regenerating and utilizing heavy-oil desulfurization catalyst |
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| US12071592B2 (en) | 2017-02-12 | 2024-08-27 | Magēmā Technology LLC | Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US10655074B2 (en) | 2017-02-12 | 2020-05-19 | Mag{hacek over (e)}m{hacek over (a)} Technology LLC | Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil |
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| CN102773107A (en) * | 2011-05-10 | 2012-11-14 | 中国石油化工股份有限公司 | Regeneration method for metallic Ni hydrogenation catalyst |
| CN103272653A (en) * | 2013-06-09 | 2013-09-04 | 神华集团有限责任公司 | Deactivated catalyst regeneration and density grading system and process thereof |
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| JP3527635B2 (en) | 1998-05-26 | 2004-05-17 | 出光興産株式会社 | Hydrodesulfurization method for heavy oil |
| JP3708381B2 (en) | 1998-09-30 | 2005-10-19 | 出光興産株式会社 | Regeneration method of heavy oil hydrotreating catalyst and regenerated hydrotreating catalyst |
| TW548329B (en) * | 1998-09-30 | 2003-08-21 | Idemitsu Kosan Co | Regenerated hydrogenation catalyst and methods of hydrogenating heavy oil |
| JP2000129271A (en) * | 1998-10-27 | 2000-05-09 | Idemitsu Kosan Co Ltd | Method for packing and extracting catalyst |
| JP2013212447A (en) * | 2012-03-30 | 2013-10-17 | Idemitsu Kosan Co Ltd | Method for regenerating and using heavy oil hydrotreating catalyst, and the heavy oil hydrotreating catalyst |
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| CN102773107A (en) * | 2011-05-10 | 2012-11-14 | 中国石油化工股份有限公司 | Regeneration method for metallic Ni hydrogenation catalyst |
| CN103272653A (en) * | 2013-06-09 | 2013-09-04 | 神华集团有限责任公司 | Deactivated catalyst regeneration and density grading system and process thereof |
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