CN106905997B - Catalyst used in series connection type boiling bed hydrogenation treatment process of inferior heavy oil - Google Patents
Catalyst used in series connection type boiling bed hydrogenation treatment process of inferior heavy oil Download PDFInfo
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- CN106905997B CN106905997B CN201710240112.8A CN201710240112A CN106905997B CN 106905997 B CN106905997 B CN 106905997B CN 201710240112 A CN201710240112 A CN 201710240112A CN 106905997 B CN106905997 B CN 106905997B
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- Prior art keywords
- catalyst
- hydrotreating catalyst
- aluminium hydroxide
- spherical
- hydroxide powder
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- 239000003054 catalyst Substances 0.000 title claims abstract description 184
- 239000000295 fuel oil Substances 0.000 title claims abstract description 36
- 238000009835 boiling Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000008569 process Effects 0.000 title claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 25
- 239000003921 oil Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000005299 abrasion Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims description 65
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 61
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 61
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 44
- 239000011324 bead Substances 0.000 claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 40
- 229910052719 titanium Inorganic materials 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 40
- 229910052746 lanthanum Inorganic materials 0.000 claims description 39
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 39
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 38
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000000149 penetrating effect Effects 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 230000033764 rhythmic process Effects 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 239000011280 coal tar Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- -1 siliceous Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 1
- 229940098458 powder spray Drugs 0.000 claims 1
- 238000004231 fluid catalytic cracking Methods 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 241000772415 Neovison vison Species 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 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
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009703 powder rolling Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001141 propulsive effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/635—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
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—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 with moving solid particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst adopted in an inferior heavy oil hydrotreating process, in particular to a catalyst adopted in a serial connection type inferior heavy oil boiling bed hydrotreating process. The catalyst comprises a spherical pre-hydrotreating catalyst and a spherical main hydrotreating catalyst, wherein inferior heavy oil firstly reacts under the action of the spherical pre-hydrotreating catalyst and then reacts under the action of the spherical main hydrotreating catalyst, the diameter of the spherical pre-hydrotreating catalyst is 0.82-1.15mm, the abrasion is less than 0.3 wt%, and the crushing strength is more than 8.0N per particle; the diameter of the spherical main hydrotreating catalyst is 0.82-1.15mm, the abrasion is less than 0.2 wt%, and the crushing strength is more than 9.0N/particle. The catalyst of the invention is used for treating inferior heavy oil, can meet the requirements of a subsequent fluid catalytic cracking device on raw oil, and overcomes the defects of a fixed bed reactor device and the adoption of a single boiling bed for hydrotreating inferior heavy oil.
Description
Technical field
The present invention relates to the catalyst that inferior heavy oil hydroprocessing technique uses, and in particular to a kind of tandem inferior heavy
The catalyst that matter oil boiling bed hydrogenation handling process uses.
Background technology
Inferior heavy oil takes traditional fixation because it contains substantial amounts of carbon residue, asphalitine, colloid and impurity metal ion
Bed hydroprocessing handling process is difficult to reach hydrofinishing, and the purpose of acceptable material is provided for fluid catalytic cracking (FCC) device.Using
Bubbling bed hydrotreating process is processing inferior heavy oil preferably one of means.
Chinese patent CN103102938A is disclosed " a kind of boiling bed hydrogenation processing method ", and this method uses at least two
Boiling bed hydrogenation treatment reactor is connected, and heavy raw oil and hydrogen enter first reactor from bottom, in heavy raw oil
Reacted under hydroprocessing condition, reacting rear material discharges first reactor from top, mixes with hydrogen and enters from bottom
Second reactor, is reacted under heavy raw oil hydroprocessing condition, and reacting rear material discharges reactor from top；The
The mixed catalyst of at least two catalyst is used in one boiling bed hydrogenation treatment reactor；Second boiling bed hydrogenation processing
Also the mixed catalyst of at least two catalyst is used in reactor.In the invention, each reactor loads two kinds of performances not
Same catalyst.The different catalyst of two kinds of aperture differences, tenors, its macroscopic density are inevitable different.In certain boiling
Under operating mode operating condition, under identical circulation rate, because the propulsive force of mink cell focus is identical, the big catalyst of macroscopic density
Expansion rate is relatively small, and the expansion rate of the small catalyst of macroscopic density certainly will more greatly, and this will cause in ebullated bed two kinds
The skewness of catalyst, it is difficult to reach the effect that two kinds of catalyst uniformly act synergistically.Four kinds of the other disclosure of the invention
Spheric catalyst particle diameter is small (0.3-0.4mm), rate of wear height (≤2%), under certain boiling regime operating condition, catalyst
Consumption can it is higher, catalyst adds online, the operation of outer row can it is more frequent, will cause boiling bed hydrogenation processing unit operate
Conditional fluctuation is larger, and operation is not convenient enough.In addition, catalyst fines caused by rate of wear height are largely mingled with generation oil
Heavy component oil the inside, the purified treatment to follow-up mink cell focus bring very big difficulty.
The boiling bed hydrogenation treatment catalyst that boiling bed hydrogenation device uses both at home and abroad at present, its active metallic element are basic
It is to be selected from tetra- kinds of elements of Mo, W, Ni, Co, is required according to the matching with special catalyst carrier, composition Mo-Ni, Mo-Co,
The collocation forms such as W-Ni, W-Mo-Ni, the tenor in catalyst are also not quite similar, rudimentary knowledge category known to category, catalysis
Agent carrier special preparation technique, the selection of special raw material and special nature are only the technological core that catalyst forms invention.Urge
Most of agent external form is a diameter of 1.0mm or so strip catalyst.Strip boiling-bed catalyst, wears away in a state of use
Rate is high, because catalyst is under working condition of seethe with excitement, between catalyst granules, catalyst and reactor inner member, reacts
Friction, collision often occur between wall.Stripe shape catalyst easily collides, wears the substantial amounts of fine powder of generation, these catalyst
Fine powder easily blocks pressure belonging to fluidized bed reactor, temperature measuring point position, blocking portion pipeline, valve, brings boiling
The larger potential safety hazard of bed hydroprocessing processing unit；These other catalyst fines are largely mingled with the heavy component of generation oil
Oily the inside, the purified treatment to follow-up mink cell focus bring very big difficulty.
Can spherical boiling-bed catalyst be developed, one of technological difficulties of application success are that catalyst will have and meet boiling
Good mechanical strength and very low rate of wear under operating mode application state.This is also few spherical boiling-bed catalyst industrialization
Where the example reason of application.Compared with strip catalyst, spherical boiling-bed catalyst has to seethe with excitement in fluidized bed reactor
Evenly, with feedstock oil, hydrogen contacting efficiency is higher, catalytic activity of catalyst plays more fully advantage for state.Exist at present
In catalyst manufacturing field, the ball making method using aluminum oxide or aluminium hydroxide powder as primary raw material substantially have solution oil ammonia column into
The technologies such as ball, the balling-up of solution centrifugal method, powder rolling balling, the diameter of these methods manufacture is less than 1.0mm bead, through dry
After dry, roasting, the breaking strength of the alumina globule of manufacture is respectively less than 5N/ grains, and rate of wear is all higher than 2.0m%, it is difficult to meets ball
Most basic requirement of the shape boiling-bed catalyst to breaking strength and rate of wear.
The content of the invention
In view of the shortcomings of the prior art, at it is an object of the invention to provide a kind of tandem inferior heavy oil boiling bed hydrogenation
The catalyst that science and engineering skill uses, carries out processing to inferior heavy oil using the catalyst and disclosure satisfy that follow-up fluid catalytic cracking
(FCC) device is to the applicability technical requirements of feedstock oil, when solving fixed bed reactors device hydrotreating inferior heavy oil, dress
The drawbacks of putting the short cycle of operation, frequent shutting down, solve using single fluidized bed reactor, boiling bed hydrogenation treatment catalyst
The problem of deactivation rate is fast, catalyst adds online, efflux technology frequent operation.
The catalyst that tandem inferior heavy oil boiling bed hydrogenation handling process of the present invention uses, including it is spherical pre-
Hydrotreating catalyst and spherical main hydrotreating catalyst, inferior heavy oil is first in the work of spherical pre-hydrotreating catalyst
With lower reaction, then reacted in the presence of spherical main hydrotreating catalyst, spherical pre-hydrotreating catalyst it is a diameter of
0.82-1.15mm, abrasion are less than 0.3wt%, and breaking strength is more than 8.0N/ grains；Spherical main hydrotreating catalyst it is a diameter of
0.82-1.15mm, abrasion are less than 0.2wt%, and breaking strength is more than 9.0N/ grains；Spherical pre-hydrotreating catalyst is mounted in pre-add
In hydrogen processing fluidized bed reactor, spherical main hydrotreating catalyst is mounted in main hydrotreating fluidized bed reactor, pre- hydrogenation
Processing fluidized bed reactor is used in series with main hydrotreating fluidized bed reactor.
Preferably, a diameter of 0.85-0.95mm of spherical pre-hydrotreating catalyst, abrasion are less than 0.1wt%, crush strong
Degree is more than 10.0N/ grains.
Preferably, a diameter of 0.85-0.95mm of spherical main hydrotreating catalyst, abrasion are less than 0.08wt%, crush
Intensity is more than 11.0N/ grains.
Except spherical boiling-bed catalyst is considered under boiling regime application state, there is higher breaking strength and relatively low
Outside rate of wear, the particle diameter of bead is also critically important index.When the particle diameter of bead is less than 0.5mm, due to its outward appearance regularity compared with
Difference so that pellet crush strength is low, rate of wear is high, and catalyst efflorescence is more serious；In addition, when the particle diameter of bead is less than 0.7mm
When, limited by fluidized bed reactor inner member installation accuracy, catalyst easily leaks into fluidized bed reactor bottom out of reactor
In the high temperature circulation pump in portion, while cause the abrasion of catalyst and high temperature circulation pump.But when the particle diameter of bead is more than 1.2mm, though
So its outward appearance regularity is preferable, pellet crush strength is high, rate of wear is low, but its under boiling regime application state to inferior heavy
During oily hydrofinishing, what is showed is active undesirable.
Wherein：
Described inferior heavy oil is petroleum residual oil component oil inferior, the high temperature inferior that metals content impurity is less than 400ppm
The inferior heavy oil that the heavy constituent of coal tar is oily or petroleum residual oil component inferior and the heavy constituent of high temperature coal-tar inferior reconcile into.
Described spherical pre-hydrotreating catalyst uses the alumina globule containing rare earth element as carrier, loads nickel element
It is active component with molybdenum element.
The present invention spherical pre-hydrotreating catalyst main task be when handling the hydrofinishing of inferior heavy oil,
Remove it and contain substantial amounts of carbon residue, asphalitine, colloid and impurity metal ion, sulphur, the azepine element of part.De- carbon residue, pitch
When matter, colloid and impurity metal ion, catalyst does not need how high acidity, acid high to easily lead in mink cell focus
Resin and asphalt causes catalyst to lose activity quickly in catalyst surface coking.But catalyst needs have larger hole
Hold, aperture and specific surface area, carbon residue, asphalitine, colloid and the impurity metal ion for being advantageous to there is higher molecular volume it is interior
External diffusion.The aluminum oxide of relatively low sintering temperature manufacture has larger pore volume and specific surface area, but its apparent acidity is stronger, unfavorable
In hydrogenation de- carbon residue, asphalitine, colloid and impurity metal ion.High-temperature roasting aluminum oxide can greatly reduce the apparent of aluminum oxide
Acidity, improve its aperture, but because the thermal stability of pure alumina is poor, high-temperature roasting can cause aluminum oxide pore volume,
Specific surface area, which is shunk, becomes very little, it is impossible to meets hydrogenation de- carbon residue, asphalitine, colloid and impurity metal ion to catalyst pore volume
The requirement of product and specific surface area.One of the method for increasing thermal stability of alumina be added during its ball processed it is a certain amount of oxygen-containing
The raw material of SiClx, but the also larger apparent acidity for improving aluminum oxide while introducing silica.Therefore, the present invention is in manufacture ball
Rare earth element is with the addition of during shape pre-hydrotreating catalyst bead carrier, improves high-temperature calcination process oxidation well
The thermal stability of aluminium, and do not increase the acidity of alumina support.Under higher sintering temperature, spherical pre-hydrotreating catalysis
The apparent acidity of agent bead carrier has not only obtained preferable control, and still has larger pore volume, aperture and specific surface area,
There is good hydrofinishing activity to serve key effect to spherical pre-hydrotreating catalyst.
Described spherical pre-hydrotreating catalyst, rare earth element are lanthanum element, and the content of lanthanum element is 0.02-
0.06wt%；In terms of oxide, nickel oxide content 1.0-3.5wt%, oxidation molybdenum content is 8.0-15.0wt%.
Preferably, the content of lanthanum element is 0.03-0.05wt%；Nickel oxide content is 2.0-2.5wt%, aoxidizes molybdenum content
For 9.0-13.0wt%.
Described lanthanum element is using lanthanum nitrate or lanthanum acetate as raw material, preferred lanthanum nitrate.
Described nickel element is using nickel nitrate, nickel chloride, nickel sulfate or nickelous carbonate as raw material, preferred nickelous carbonate.
Described molybdenum element is using ammonium molybdate or molybdenum oxide as raw material, preferred molybdenum oxide.
Described spherical pre-hydrotreating catalyst is prepared using bonding-acidifying-spin ball making process, and specific steps are such as
Under：
(1) at room temperature, aluminium hydroxide powder is placed in the rotary drum of bowling machine, the aluminium hydrate powder under rotation into rotary drum
Body sprays into aluminum nitrate solution and the diluted nitric acid aqueous solution containing lanthanum element, aluminium hydrate powder made of above-mentioned aluminium hydroxide powder
Body forms microballoon in the presence of aluminum nitrate solution and diluted nitric acid aqueous solution, with aluminum nitrate solution and dilute nitre containing lanthanum element
The continuous penetrating of acid solution, the amount of the aluminium hydroxide powder of microballoon adhesion gradually increases, in the presence of solid bowl centrifuges power, microballoon
Volume become larger, formed the bead of aluminium hydroxide powder containing lanthanum, control solid bowl centrifuges power size and penetrating aluminum nitrate solution
With the speed rhythm of the diluted nitric acid aqueous solution containing lanthanum element, produce needed for particle diameter the bead of aluminium hydroxide powder containing lanthanum；
(2) bead of aluminium hydroxide powder containing lanthanum is transferred in magazine from the rotary drum of bowling machine, 100-120 DEG C in drying box
Temperature conditionss under dry 3-4 hours, dried bead is fitted into saggar, in roaster at a temperature of 850-950 DEG C, be calcined
After 2.5-3.5 hours, lanthanum containing alumina bead carrier is produced；
(3) lanthanum containing alumina bead carrier is loaded in the rotary drum of spray-stain machine, rotates spray-stain at room temperature and contain nickel, molybdenum element
Acidic aqueous solution, the lanthanum containing alumina bead carrier that spray-stain has nickel, molybdenum element is placed in drying box, 110-120 DEG C of temperature
Under the conditions of, 4-5 hours are dried, are then transferred in saggar, 450-550 DEG C of roasting 3-4 hour, produce spherical pre-hydrotreating catalysis
Agent.
In step (1), the specific surface area of described aluminium hydroxide powder is 240-300m2/ g, pore volume 0.75-
0.90mL/g。
In step (1), the quality of the described aluminium hydroxide powder for preparing aluminum nitrate solution use accounts for aluminium hydroxide powder
The 3-5% of gross mass.
In step (1), the size and penetrating aluminum nitrate solution and dilute nitre containing lanthanum element of described control solid bowl centrifuges power
The speed rhythm of aqueous acid is routine techniques, and those skilled in the art can easily control.
In step (3), containing nickel, the acidic aqueous solution of molybdenum element spray-stain amount by lanthanum containing alumina bead carrier water suction
Rate determines that the carrier dry and wet after nickel-loaded, molybdenum element is suitably defined.Nickel, molybdenum element are adjusted in spray-stain acidic aqueous solution
Concentration, to ensure the content of the nickel of spherical pre-hydrotreating catalyst, molybdenum oxide in required scope.
Described spherical main hydrotreating catalyst uses the alumina globule of siliceous, titanium, P elements as carrier, nickel-loaded
Element and molybdenum element are active component.
For spherical main hydrotreating catalyst in main hydrotreating fluidized bed reactor, its main function is to from above
The prerefining generation oil of pre-hydrotreating fluidized bed reactor further removes carbon residue, asphalitine, colloid and metal contained by it
Ionic impurity；Substantial amounts of removing sulphur, azepine constituent content.Spherical main hydrotreating catalyst require larger pore volume and
Specific surface area, while there is stronger apparent acidity.In the manufacture of main hydrotreating catalyst bead carrier, present invention choosing
Selected with raw material based on larger pore volume and specific surface area simultaneously siliceous, titanium aluminium hydroxide powder, it is manufactured it is siliceous,
What titanium, the alumina globule of P elements met that main hydrotreating catalyst has larger pore volume and specific surface area to it will
Ask, simultaneous oxidation silicon, titanium oxide and phosphorous oxide act synergistically so that there is bead carrier stronger apparent acidity to make major catalyst
Just there is very high catalytic activity under the conditions of relatively low reaction temperature, to the length of the catalytic activity of main hydrotreating catalyst
Time, stable performance served important function.
Described spherical main hydrotreating catalyst, in terms of oxide, silica content 1.0-5.0wt%, titanium oxide
Content is 2.0-7.0wt%, and oxidation phosphorus content is 2.5-5.5wt%, nickel oxide content 2.5-5.5wt%；Aoxidize molybdenum content
For 18.0-24.0wt%.
Preferably, silica content 2.0-4.0wt%, titanium oxide content 3.0-6.0wt%, oxidation phosphorus content are
3.0-5.0wt%, nickel oxide content 3.0-5.0wt%；Oxidation molybdenum content is 19.0-21.0wt%.
Described P elements are using phosphoric acid, sodium phosphate or ammonium phosphate as raw material, preferred phosphoric acid.
Described nickel element is using nickel nitrate, nickel chloride, nickel sulfate or nickelous carbonate as raw material, preferred nickelous carbonate.
Described molybdenum element is using ammonium molybdate or molybdenum oxide as raw material, preferred molybdenum oxide.
Described spherical main hydrotreating catalyst is prepared using bonding-acidifying-spin ball making process, and specific steps are such as
Under：
(1) at room temperature, siliceous, titanium aluminium hydroxide powder is placed in the rotary drum of bowling machine, under rotation into rotary drum
Siliceous, titanium aluminium hydroxide powder sprays into aluminum nitrate solution and the diluted acid containing P elements made of above-mentioned aluminium hydroxide powder
The aqueous solution, siliceous, titanium aluminium hydroxide powder are formed in the presence of aluminum nitrate solution and dilute acid solution containing P elements
Microballoon, the continuous penetrating of the dilute acid solution with aluminum nitrate solution and containing P elements, siliceous, titanium the hydrogen-oxygen of microballoon adhesion
The amount for changing aluminium powder body gradually increases, and in the presence of solid bowl centrifuges power, the volume of microballoon becomes larger, and forms siliceous, titanium, phosphorus member
The aluminium hydroxide powder bead of element, control the size of solid bowl centrifuges power and spray into aluminum nitrate solution and the diluted acid water containing P elements
The speed rhythm of solution, produce required the siliceous of particle diameter, titanium, the aluminium hydroxide powder bead of P elements；
(2) the aluminium hydroxide powder bead of siliceous, titanium, P elements is transferred in magazine from the rotary drum of bowling machine, dried
3-4 hours are dried in case under 100-120 DEG C of temperature conditionss, dried bead is fitted into saggar, 550-650 DEG C of temperature in roaster
Under degree, after being calcined 2.5-3.5 hours, the alumina globule carrier of siliceous, titanium, P elements is produced；
(3) the alumina globule carrier of siliceous, titanium, P elements is loaded in the rotary drum of spray-stain machine, rotates spray-stain at room temperature
Acidic aqueous solution containing nickel, molybdenum element, the alumina globule carrier that spray-stain has nickel, the siliceous of molybdenum element, titanium, P elements is put
In in drying box, under 110-120 DEG C of temperature conditionss, 4-5 hours are dried, it is small to be then transferred to 450-550 DEG C of roasting 3-4 in saggar
When, produce spherical main hydrotreating catalyst.
In step (1), the specific surface area of described siliceous, titanium aluminium hydroxide powder is 300-380m2/ g, pore volume are
0.90-1.20mL/g。
In step (1), the quality of the described aluminium hydroxide powder for preparing aluminum nitrate solution use accounts for aluminium hydroxide powder
The 3-5% of gross mass.
In step (1), described siliceous, titanium aluminium hydroxide powder is commercially available prod, can be according to catalyst to siliceous, titanium
The requirement of amount, the aluminium hydroxide powder that selection is siliceous, titanium amount is different.
In step (1), the size of described control solid bowl centrifuges power and spray into aluminum nitrate solution and contain the dilute of P elements
The speed rhythm of aqueous acid, is routine techniques, and those skilled in the art can easily control.
In step (3), the spray-stain amount containing nickel, the acidic aqueous solution of molybdenum element is small by the aluminum oxide of siliceous, titanium, P elements
The water absorption rate of balloon borne body determines that the carrier dry and wet after nickel-loaded, molybdenum element is suitably defined.Nickel, molybdenum element are adjusted in spray-stain
Concentration in acidic aqueous solution, to ensure the content of the nickel of spherical main hydrotreating catalyst, molybdenum oxide in required scope
It is interior.
The catalyst that tandem inferior heavy oil boiling bed hydrogenation handling process of the present invention uses, only using spherical
Two kinds of catalyst of pre-hydrotreating catalyst and spherical main hydrotreating catalyst.Spherical pre-hydrotreating catalyst is mounted in pre-add
In hydrogen processing fluidized bed reactor, spherical main hydrotreating catalyst is mounted in main hydrotreating fluidized bed reactor.Each boiling
Rise and only load a kind of spherical boiling-bed catalyst in a reactor, it is easily more in device operational control, while to catalysis
The combination property of agent it is also proposed higher requirement.Under inferior heavy oil hydroprocessing condition, inferior heavy oil and hydrogen from
Pre-hydrotreating fluidized bed reactor bottom enters fluidized bed reactor, in the catalytic action of spherical pre-hydrotreating catalyst
Under, carbon residue, asphalitine, colloid and impurity metal ion contained by inferior heavy oil are largely removed, while are also had a certain amount of
Sulphur, nitrogen is removed.While inferior heavy oil is handled by preliminary hydrofinishing, the density that oil is generated after it is refined is also corresponding
Diminish.Refined generation oil flows out at the top of pre-hydrotreating fluidized bed reactor, and the master into series connection with it together with hydrogen adds
Hydrogen handles the bottom of fluidized bed reactor, further under the catalytic action of spherical main hydrotreating catalyst, carries out hydrogenation essence
System processing.In main hydrotreating fluidized bed reactor, the prerefining from pre-hydrotreating fluidized bed reactor generates oily quilt
Further hydrofinishing processing, further the carbon residue contained by removing prerefining generation oil, asphalitine, colloid and metal ion are miscellaneous
Matter；Substantial amounts of removing sulphur, azepine constituent content.
In summary, beneficial effects of the present invention are as follows：
(1) in main hydrotreating fluidized bed reactor, the prerefining generation from pre-hydrotreating fluidized bed reactor
Oily inferior heavy oil passes through spherical pre-hydrotreating catalyst and spherical main hydrotreating catalyst, connects in two reactors
Using under, joint catalytic action, oil quality has obtained good lifting, is entirely capable of meeting follow-up fluid catalytic cracking (FCC)
Technical requirements of the device to feedstock oil applicability；Solves fixed bed reactors device hydrotreating inferior heavy oil well
When, the drawbacks of plant running cycle is short, frequent shutting down；Also solve and use single fluidized bed reactor, at boiling bed hydrogenation
Manage the problem of catalyst inactivation speed is fast, and catalyst adds online, efflux technology frequent operation.
(2) present invention is using the ball making process of bonding-acidifying-spin, the spherical pre-hydrotreating catalyst and ball of preparation
The main hydrotreating catalyst of shape has been fully met under boiling applying working condition to catalyst breakage intensity and the technical requirements of rate of wear.
Brief description of the drawings
Fig. 1 is the small capacity double fluidized bed reactor series connection evaluating apparatus evaluation technological process that present invention evaluation catalyst uses
Figure；
In figure：1st, inferior heavy oil feed pipe；2nd, hydrogen gas lines a；3rd, pre-hydrotreating ebullated bed；4th, hydrogen gas lines b；5、
Main hydrotreating ebullated bed；6th, cold high score；7th, hot high score；8th, lighter hydrocarbons；9th, hydrogen gas lines c；10th, naphtha cut；11st, diesel oil evaporates
Point；12、>350 DEG C of tail oil fractions；13rd, hydrogen sulfide, ammonia；14th, fractionating column.
Embodiment
With reference to embodiment, the present invention will be further described.
All raw materials used in embodiment are purchased in market unless otherwise specified.
Embodiment 1
The preparation method of spherical pre-hydrotreating catalyst -1 is as follows：
(1) at room temperature, by specific surface area ＞ 240m2/ g, pore volume ＞ 0.75mL/g aluminium hydroxide powder are placed in spin
In the rotary drum of machine, the aluminium hydroxide powder under rotation into rotary drum sprays into the aluminum nitrate solution made of above-mentioned aluminium hydroxide powder
With the diluted nitric acid aqueous solution containing lanthanum element, aluminium hydroxide powder is formed in the presence of aluminum nitrate solution and diluted nitric acid aqueous solution
Microballoon, the continuous penetrating of the dilute nitric acid solution with aluminum nitrate solution and containing lanthanum element, the aluminium hydroxide powder of microballoon adhesion
Amount gradually increase, in the presence of solid bowl centrifuges power, the volume of microballoon becomes larger, formed aluminium hydroxide powder containing lanthanum it is small
Ball, control the size of solid bowl centrifuges power and spray into the speed rhythm of aluminum nitrate solution and the diluted nitric acid aqueous solution containing lanthanum element, i.e.,
The bead of aluminium hydroxide powder containing lanthanum of particle diameter needed for obtaining；
The quality of the described aluminium hydroxide powder for preparing aluminum nitrate solution use accounts for aluminium hydroxide powder gross mass
4%.
(2) bead of aluminium hydroxide powder containing lanthanum is transferred in magazine from the rotary drum of bowling machine, 110 ± 10 DEG C in drying box
Temperature conditionss under dry 4 hours, dried bead is fitted into saggar, in roaster at a temperature of 900 ± 50 DEG C, be calcined 3
After hour, lanthanum containing alumina bead carrier is produced；
(3) lanthanum containing alumina bead carrier is loaded in the rotary drum of spray-stain machine, rotates spray-stain at room temperature and contain nickel, molybdenum element
Acidic aqueous solution, the lanthanum containing alumina bead carrier that spray-stain has nickel, molybdenum element is placed in drying box, 110 ± 10 DEG C of temperature
Under the conditions of, dry 4 hours, be then transferred in saggar, 500 ± 50 DEG C be calcined 3 hours, produce spherical pre-hydrotreating catalyst-
1。
The preparation method of spherical main hydrotreating catalyst -1 is as follows：
(1) at room temperature, by specific surface area ＞ 300m2/ g, pore volume ＞ 0.90mL/g are siliceous, the aluminium hydroxide powder of titanium is put
In in the rotary drum of bowling machine, siliceous, titanium the aluminium hydroxide powder under rotation into rotary drum is sprayed into by above-mentioned aluminium hydroxide powder
Manufactured aluminum nitrate solution and the dilute acid solution containing P elements, siliceous, titanium aluminium hydroxide powder in aluminum nitrate solution and
Microballoon is formed in the presence of dilute acid solution containing P elements, the dilute acid solution with aluminum nitrate solution and containing P elements
Continuous penetrating, the amount of siliceous, titanium aluminium hydroxide powder of microballoon adhesion gradually increases, in the presence of solid bowl centrifuges power,
The volume of microballoon becomes larger, and forms siliceous, titanium, the aluminium hydroxide powder bead of P elements, controls the size of solid bowl centrifuges power
The speed rhythm of dilute acid solution with penetrating aluminum nitrate solution and containing P elements, produce required the siliceous of particle diameter, titanium, phosphorus member
The aluminium hydroxide powder bead of element；
The quality of the described aluminium hydroxide powder for preparing aluminum nitrate solution use accounts for aluminium hydroxide powder gross mass
4%.
(2) the aluminium hydroxide powder bead of siliceous, titanium, P elements is transferred in magazine from the rotary drum of bowling machine, dried
Dried 4 hours under 110 ± 10 DEG C of temperature conditionss in case, dried bead is fitted into saggar, 600 ± 50 DEG C of temperature in roaster
Under, after being calcined 3 hours, produce the alumina globule carrier of siliceous, titanium, P elements；
(3) the alumina globule carrier of siliceous, titanium, P elements is loaded in the rotary drum of spray-stain machine, rotates spray-stain at room temperature
Acidic aqueous solution containing nickel, molybdenum element, the alumina globule carrier that spray-stain has nickel, the siliceous of molybdenum element, titanium, P elements is put
In in drying box, under 110-120 DEG C of temperature conditionss, dry 4 hours, be then transferred in saggar 500 ± 50 DEG C and be calcined 3 hours, i.e.,
Obtain spherical main hydrotreating catalyst -1.
The physico-chemical property of spherical pre-hydrotreating catalyst -1 and spherical main hydrotreating catalyst -1 is shown in Table 1.
The physico-chemical property of 1 spherical pre-hydrotreating catalyst -1 of table and spherical main hydrotreating catalyst -1
| Catalyst | Spherical pre-hydrotreating catalyst -1 | Spherical main hydrotreating catalyst -1 |
| Particle size range, mm | 0.82-0.90 | 0.82-0.90 |
| Breaking strength, N/ grains | 8.2 | 9.2 |
| Abrasion, wt% | 0.25 | 0.11 |
| La wt% | 0.025 | - |
| SiO2Wt% | - | 1.5 |
| P2O5Wt% | - | 2.7 |
| TiO2Wt% | - | 2.6 |
| NiO wt% | 1.2 | 2.6 |
| MoO3Wt% | 8.3 | 18.2 |
Embodiment 2
The preparation of spherical pre-hydrotreating catalyst -2：
Except particle size range, lanthanum content, nickel oxide content and oxidation molybdenum content it is different from embodiment 1 in addition to, remaining and embodiment 1
It is identical.
The preparation of spherical main hydrotreating catalyst -2：
Except particle size range, silica content, titanium oxide content, oxidation phosphorus content, nickel oxide content and oxidation molybdenum content with
Embodiment 1 is different outer, and remaining is same as Example 1.
The physico-chemical property of spherical pre-hydrotreating catalyst -2 and spherical main hydrotreating catalyst -2 is shown in Table 2.
The physico-chemical property of 2 spherical pre-hydrotreating catalyst -2 of table and spherical main hydrotreating catalyst -2
Embodiment 3
The preparation of spherical pre-hydrotreating catalyst -3：
Except particle size range, lanthanum content, nickel oxide content and oxidation molybdenum content it is different from embodiment 1 in addition to, remaining and embodiment 1
It is identical.
The preparation of spherical main hydrotreating catalyst -3：
Except particle size range, silica content, titanium oxide content, oxidation phosphorus content, nickel oxide content and oxidation molybdenum content with
Embodiment 1 is different outer, and remaining is same as Example 1.
The physico-chemical property of spherical pre-hydrotreating catalyst -3 and spherical main hydrotreating catalyst -3 is shown in Table 3.
The physico-chemical property of 3 spherical pre-hydrotreating catalyst -3 of table and spherical main hydrotreating catalyst -3
| Catalyst | Spherical pre-hydrotreating catalyst -3 | Spherical main hydrotreating catalyst -3 |
| Particle size range, mm | 0.90-0.95 | 0.90-0.95 |
| Breaking strength, N/ grains | 9.8 | 12.1 |
| Abrasion, wt% | 0.08 | 0.06 |
| La wt% | 0.041 | - |
| SiO2Wt% | - | 2.5 |
| TiO2Wt% | - | 4.1 |
| P2O5Wt% | - | 3.8 |
| NiO wt% | 2.2 | 3.6 |
| MoO3Wt% | 10.5 | 20.5 |
Embodiment 4
The preparation of spherical pre-hydrotreating catalyst -4：
Except particle size range, lanthanum content, nickel oxide content and oxidation molybdenum content it is different from embodiment 1 in addition to, remaining and embodiment 1
It is identical.
The preparation of spherical main hydrotreating catalyst -4：
Except particle size range, silica content, titanium oxide content, oxidation phosphorus content, nickel oxide content and oxidation molybdenum content with
Embodiment 1 is different outer, and remaining is same as Example 1.
The physico-chemical property of spherical pre-hydrotreating catalyst -4 and spherical main hydrotreating catalyst -4 is shown in Table 4.
The physico-chemical property of 4 spherical pre-hydrotreating catalyst -4 of table and spherical main hydrotreating catalyst -4
| Catalyst | Spherical pre-hydrotreating catalyst -4 | Spherical main hydrotreating catalyst -4 |
| Particle size range, mm | 0.95-1.00 | 0.95-1.00 |
| Breaking strength, N/ grains | 10.2 | 12.8 |
| Abrasion, wt% | 0.07 | 0.02 |
| La wt% | 0.044 | - |
| SiO2Wt% | - | 3.0 |
| TiO2Wt% | - | 5.8 |
| P2O5Wt% | - | 4.2 |
| NiO wt% | 2.5 | 4.2 |
| MoO3Wt% | 11.5 | 21.1 |
Embodiment 5
The preparation of spherical pre-hydrotreating catalyst -5：
Except particle size range, lanthanum content, nickel oxide content and oxidation molybdenum content it is different from embodiment 1 in addition to, remaining and embodiment 1
It is identical.
The preparation of spherical main hydrotreating catalyst -5：
Except particle size range, silica content, titanium oxide content, oxidation phosphorus content, nickel oxide content and oxidation molybdenum content with
Embodiment 1 is different outer, and remaining is same as Example 1.
The physico-chemical property of spherical pre-hydrotreating catalyst -5 and spherical main hydrotreating catalyst -5 is shown in Table 5.
The physico-chemical property of 5 spherical pre-hydrotreating catalyst -5 of table and spherical main hydrotreating catalyst -5
The embodiment 1-5 spherical pre-hydrotreating catalysts prepared and spherical main hydrotreating catalyst are evaluated,
Using the evaluation feedstock oil provided in table 6, (see Fig. 1) on small capacity double fluidized bed reactor series connection evaluating apparatus, it is hydrogenated with
Refined pretreatment Performance Properties Evaluation experiment.Appreciation condition is as follows：
Pre-hydrotreating fluidized bed reactor：
1) pre-hydrotreating catalyst charge weight 100mL；
2) 375 DEG C of reaction temperature；
3) liquid air speed (v/v) 0.8h-1；
4) system stagnation pressure 15.0MPa；
5) hydrogen-oil ratio (v/v) 800/1.
Main hydrotreating fluidized bed reactor：
1) main hydrotreating catalyst charge weight 100mL；
2) 395 DEG C of reaction temperature；
3) liquid air speed (v/v) 0.8h-1；
4) system stagnation pressure 15.0MPa；
5) hydrogen-oil ratio (v/v) 800/1.
Presulfurization processing has been carried out before two kinds of catalyst uses.Evaluation test is carried out continuously 100 hours.Feedstock oil is through ball
After shape pre-hydrotreating catalyst and spherical main hydrotreating catalyst Unionfining processing, 350 DEG C of weights of ＞ in generation oil
The analyze data of oil ingredient is included in table 6.
Applicating evaluating example as a comparison, from the spherical main hydrotreating catalyst in embodiment 4, only with rear ebullated bed
Reactor, in catalyst charge 100mL；395 DEG C of reaction temperature；Liquid air speed (v/v) 0.8h-1；System stagnation pressure 15.0MPa；Hydrogen
Oil is than under (v/v) 800/1 the same terms, applicating evaluating is carried out with the evaluation that table 6 provides with feedstock oil.Before evaluation, catalyst enters
Presulfurization processing is gone.Evaluation test is carried out continuously 100 hours, and the analyze data of 350 DEG C of heavy oil components of ＞ also exists in generation oil
Listed in table 6.
The catalyst Performance Properties Evaluation result of table 6
As can be seen from Table 6, through spherical pre-hydrotreating catalyst and spherical main hydrotreating catalyst Unionfining essence
After system processing, the quality of 350 DEG C of heavy oil component generation oil of ＞ is significantly enhanced, and has reached current typical fluidized catalytic cracking
Change (FCC) feedstock oil applicability index.Using single spherical main hydrotreating boiling-bed catalyst, under the same conditions to identical
Feedstock oil carries out hydrofinishing processing, and it generates the analyze data of 350 DEG C of heavy oil components of ＞ in oil and can not show a candle to series connection using spherical
The analyze data of the associated form of pre-hydrotreating catalyst and spherical main hydrotreating catalyst.
Claims (4)
- A kind of 1. catalyst that tandem inferior heavy oil boiling bed hydrogenation handling process uses, it is characterised in that：Including spherical Pre-hydrotreating catalyst and spherical main hydrotreating catalyst, inferior heavy oil is first in spherical pre-hydrotreating catalyst Effect is lower to react, and is then reacted in the presence of spherical main hydrotreating catalyst, the diameter of spherical pre-hydrotreating catalyst For 0.82-1.15mm, abrasion are less than 0.3wt%, and breaking strength is more than 8.0N/ grains；Spherical main hydrotreating catalyst it is a diameter of 0.82-1.15mm, abrasion are less than 0.2wt%, and breaking strength is more than 9.0N/ grains；Spherical pre-hydrotreating catalyst is mounted in pre- hydrogenation Handle in fluidized bed reactor, spherical main hydrotreating catalyst is mounted in main hydrotreating fluidized bed reactor, at pre- hydrogenation Reason fluidized bed reactor is used in series with main hydrotreating fluidized bed reactor；Described spherical pre-hydrotreating catalyst uses the alumina globule containing rare earth element as carrier, loads nickel element and molybdenum Element is active component, and rare earth element is lanthanum element, and the content of lanthanum element is 0.02-0.06wt%；In terms of oxide, nickel oxide Content is 1.0-3.5wt%, and oxidation molybdenum content is 8.0-15.0wt%；Described spherical pre-hydrotreating catalyst is prepared using bonding-acidifying-spin ball making process, is comprised the following steps that：（1）At room temperature, aluminium hydroxide powder is placed in the rotary drum of bowling machine, the aluminium hydroxide powder spray under rotation into rotary drum Enter aluminum nitrate solution and the diluted nitric acid aqueous solution containing lanthanum element, aluminium hydroxide powder made of above-mentioned aluminium hydroxide powder to exist Microballoon is formed in the presence of aluminum nitrate solution and diluted nitric acid aqueous solution, the dust technology with aluminum nitrate solution and containing lanthanum element is molten The continuous penetrating of liquid, the amount of the aluminium hydroxide powder of microballoon adhesion gradually increases, in the presence of solid bowl centrifuges power, the body of microballoon Product becomes larger, and forms the bead of aluminium hydroxide powder containing lanthanum, controls the size of solid bowl centrifuges power and sprays into aluminum nitrate solution and contain The speed rhythm of the diluted nitric acid aqueous solution of lanthanum element, produce the bead of aluminium hydroxide powder containing lanthanum of required particle diameter；（2）The bead of aluminium hydroxide powder containing lanthanum is transferred in magazine from the rotary drum of bowling machine, 100-120 DEG C of temperature in drying box 3-4 hours are dried under the conditions of degree, dried bead is fitted into saggar, in roaster at a temperature of 850-950 DEG C, is calcined 2.5- After 3.5 hours, lanthanum containing alumina bead carrier is produced；（3）Lanthanum containing alumina bead carrier is loaded in the rotary drum of spray-stain machine, rotate the acid that spray-stain contains nickel, molybdenum element at room temperature The property aqueous solution, the lanthanum containing alumina bead carrier that spray-stain has nickel, molybdenum element is placed in drying box, 110-120 DEG C of temperature conditionss Under, 4-5 hours are dried, are then transferred in saggar, 450-550 DEG C of roasting 3-4 hour, produce spherical pre-hydrotreating catalyst；Described spherical main hydrotreating catalyst uses the alumina globule of siliceous, titanium, P elements as carrier, loads nickel element It is active component with molybdenum element, in terms of oxide, silica content 1.0-5.0wt%, titanium oxide content 2.0-7.0wt%, Oxidation phosphorus content is 2.5-5.5wt%, nickel oxide content 2.5-5.5wt%；Oxidation molybdenum content is 18.0-24.0wt%；Described spherical main hydrotreating catalyst is prepared using bonding-acidifying-spin ball making process, is comprised the following steps that：（1）At room temperature, siliceous, titanium aluminium hydroxide powder is placed in the rotary drum of bowling machine, under rotation into rotary drum it is siliceous, The aluminium hydroxide powder of titanium sprays into made of above-mentioned aluminium hydroxide powder aluminum nitrate solution and the diluted acid containing P elements is water-soluble Liquid, siliceous, titanium aluminium hydroxide powder form microballoon in the presence of aluminum nitrate solution and dilute acid solution containing P elements, The continuous penetrating of dilute acid solution with aluminum nitrate solution and containing P elements, siliceous, titanium the aluminium hydroxide of microballoon adhesion The amount of powder gradually increases, and in the presence of solid bowl centrifuges power, the volume of microballoon becomes larger, and forms siliceous, titanium, P elements Aluminium hydroxide powder bead, control the size of solid bowl centrifuges power and spray into aluminum nitrate solution and the dilute acid solution containing P elements Speed rhythm, produce needed for the siliceous of particle diameter, titanium, the aluminium hydroxide powder bead of P elements；（2）The aluminium hydroxide powder bead of siliceous, titanium, P elements is transferred in magazine from the rotary drum of bowling machine, in drying box 3-4 hours are dried under 100-120 DEG C of temperature conditionss, dried bead is fitted into saggar, 550-650 DEG C of temperature in roaster Under, after being calcined 2.5-3.5 hours, produce the alumina globule carrier of siliceous, titanium, P elements；（3）The alumina globule carrier of siliceous, titanium, P elements is loaded in the rotary drum of spray-stain machine, rotate spray-stain at room temperature and contain The acidic aqueous solution of nickel, molybdenum element, by spray-stain have nickel, the siliceous of molybdenum element, titanium, P elements alumina globule carrier be placed in it is dry In dry case, under 110-120 DEG C of temperature conditionss, 4-5 hours are dried, are then transferred to 450-550 DEG C of roasting 3-4 hour in saggar, i.e., Obtain spherical main hydrotreating catalyst.
- 2. the catalyst that tandem inferior heavy oil boiling bed hydrogenation handling process according to claim 1 uses, it is special Sign is：Described inferior heavy oil is petroleum residual oil component oil inferior, the high temperature inferior that metals content impurity is less than 400ppm The inferior heavy oil that the heavy constituent of coal tar is oily or petroleum residual oil component inferior and the heavy constituent of high temperature coal-tar inferior reconcile into.
- 3. the catalyst that tandem inferior heavy oil boiling bed hydrogenation handling process according to claim 1 uses, it is special Sign is：The preparation process of spherical pre-hydrotreating catalyst（1）In, the specific surface area of described aluminium hydroxide powder is 240- 300m2/ g, pore volume 0.75-0.90mL/g.
- 4. the catalyst that tandem inferior heavy oil boiling bed hydrogenation handling process according to claim 1 uses, it is special Sign is：The preparation process of spherical main hydrotreating catalyst（1）In, the ratio table of described siliceous, titanium aluminium hydroxide powder Area is 300-380m2/ g, pore volume 0.90-1.20mL/g.
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