CN109277108A - Siliceous Hydrodemetalation catalyst and its preparation method and application - Google Patents
Siliceous Hydrodemetalation catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109277108A CN109277108A CN201710595286.6A CN201710595286A CN109277108A CN 109277108 A CN109277108 A CN 109277108A CN 201710595286 A CN201710595286 A CN 201710595286A CN 109277108 A CN109277108 A CN 109277108A
- Authority
- CN
- China
- Prior art keywords
- siliceous
- expanding agent
- physics expanding
- preparation
- physics
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 119
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 97
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 43
- 239000010703 silicon Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 14
- 238000002803 maceration Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 46
- 239000006229 carbon black Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 230000000274 adsorptive effect Effects 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 15
- 241001502050 Acis Species 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- -1 silicic acid aliphatic alcohol ester Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 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 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 20
- 239000011148 porous material Substances 0.000 abstract description 15
- 229910001593 boehmite Inorganic materials 0.000 abstract description 10
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 54
- 238000007598 dipping method Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007921 spray Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004898 kneading Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- WCJJSOKIRDOTGW-UHFFFAOYSA-N C(C)O.[Si](OC)(O)(O)O Chemical compound C(C)O.[Si](OC)(O)(O)O WCJJSOKIRDOTGW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007324 demetalation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- YFVKHKCZBSGZPE-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(propylamino)propan-1-one Chemical compound CCCNC(C)C(=O)C1=CC=C2OCOC2=C1 YFVKHKCZBSGZPE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019020 PtO2 Inorganic materials 0.000 description 1
- 229910019603 Rh2O3 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000009495 sugar coating Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/64—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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to field of catalyst preparation, disclose a kind of preparation method of siliceous Hydrodemetalation catalyst, this method comprises the following steps, (1) the first siliceous solution is carried out first with the first physics expanding agent to contact, the second siliceous solution is carried out second with the second physics expanding agent and is contacted；(2) by the first physics expanding agent after contact that step (1) obtains, the second physics expanding agent after contact with boehmite by mix, form, first dry, first roasts and obtains silicon-containing alumina carrier；(3) the silicon-containing alumina carrier for obtaining hydrogenation active component maceration extract and step (2) carries out third contact, and the silicon-containing alumina carrier after contact is dry through second, the second roasting, obtains siliceous Hydrodemetalation catalyst.The catalyst mechanical strength with higher of this method preparation, suitable pore structure, and active component and carrier effect is moderate, and hydrodemetallization with higher activity and activity stability.
Description
Technical field
The present invention relates to field of catalyst preparation, and in particular to a kind of preparation method of siliceous Hydrodemetalation catalyst.
Background technique
With the raising that raw material deep processing requires in world wide, main energy sources structure is gradually to macromolecular and high-carbon direction
Development, China of heaviness universal for crude oil are even more so.Resistance is spread effectively to solve heavy oil component in catalyst duct
Power is excessive, catalyst activity reduction or the problems such as inactivation caused by beavy metal impurity deposition and coking, and an urgent demand is in petroleum
The widely used alumina support of the industries such as chemical industry has the characteristic of macropore appearance and large aperture.Large aperture is conducive to macromolecular chemical combination
For object to spreading inside catalyst granules, big pore volume, which is then conducive to improve, holds metal or coke ability.
US4448896 discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and the catalyst is at least one
VIII race and/or VI B race metallic element are active component, are supported on a kind of large-pore alumina carrier.The de- gold of the residual hydrogenation
The preparation method of metal catalyst be boehmite and carbon black powder kneading is uniform, it is molding, dry, roasted in oxygen containing atmosphere
Alumina support is made, then impregnates VIII race and VI B race active metal component on this carrier, or by boehmite,
Carbon black powder and compound kneading containing VIII race and VI B race active metal component are uniform, molding, dry, in oxygen containing atmosphere
It roasts and Hydrodemetalation catalyst is made.This method improves catalyst macropore content by physics expanding agent of carbon black powder, but is catalyzed
Agent mechanical strength needs to be further increased.
CN1160602A discloses a kind of large-pore alumina carrier and preparation method thereof.Its preparation process is that will intend thin water aluminium
Stone is mixed with physics expanding agent such as carbon black and chemical enlargement agent such as phosphide, and mixed material is made through kneading, molding, drying, roasting
Obtain alumina support.This method can overcome the shortcomings that physics expanding agent and chemical enlargement agent is used alone, but carrier is mechanical strong
Degree needs to be further increased.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, and the catalyst is with VIII race
And/or VI B race metallic element be active component, be supported on a kind of large-pore alumina carrier.The residuum hydrogenating and metal-eliminating is urged
The preparation method of agent is to joined the carbon black powder that granular size is 30 microns as physics in boehmite kneading process
Expanding agent and the chemical enlargement agent that the phosphorous of chemical action, silicon or boron compound can occur with boehmite or aluminium oxide, are mixed
Object kneading is closed into plastic, extruded moulding, dry, the obtained carrier of roasting, then is loaded to spraying impregnation method for active component
On carrier, through drying, obtained catalyst is roasted.
In conclusion usually making during prior art preparation macropore alumina supporter and/or Hydrodemetalation catalyst
The aperture of carrier is improved with physics expanding agent, the addition of physics expanding agent can be such that alumina support macropore content increases really,
But adverse effect can be generated to the mechanical strength of carrier and catalyst.In addition, preparing in catalyst process at this stage, active component
Interaction between carrier remains to be further improved.
Summary of the invention
The purpose of the invention is to overcome the above problem of the existing technology, a kind of siliceous hydrodemetallization is provided and is urged
The preparation method of agent, this method preparation catalyst mechanical strength with higher, suitable pore structure, and active component with
Carrier function is moderate, and hydrodemetallization with higher activity and activity stability.
To achieve the goals above, one aspect of the present invention provides a kind of preparation method of siliceous Hydrodemetalation catalyst,
This method comprises the following steps,
(1) the first siliceous solution is carried out first with the first physics expanding agent to contact, by the second siliceous solution and the second object
It manages expanding agent and carries out the second contact；
(2) by the first physics expanding agent after contact that step (1) obtains, the second physics expanding agent after contact with intend it is thin
Diaspore obtains silicon-containing alumina carrier by mixing, molding, the first drying, the first roasting；
(3) the silicon-containing alumina carrier for obtaining hydrogenation active component maceration extract and step (2) carries out third contact, and will
Silicon-containing alumina carrier after contact obtains siliceous Hydrodemetalation catalyst through the second drying, the second roasting；
Wherein, the described first siliceous solution and the second siliceous solution contain esters of silicon acis, the first physics expanding agent
Partial size is 100-540 mesh, and the partial size of the second physics expanding agent is 900-2000 mesh.
Preferably, this method further includes following steps: the siliceous Hydrodemetalation catalyst that (4) obtain step (3) into
Row sealing heat treatment and third are dried.
It is highly preferred that the sealing heat treatment carries out under ammonia and water vapor mixture atmosphere.
It is highly preferred that it is 3-5MPa that the condition of the sealing heat treatment, which includes: gas pressure, wherein the partial pressure of ammonia is
30%-50%, remaining is water vapour, and heat treatment temperature is 100-150 DEG C, and the processing time is 5-10 hours.
It is highly preferred that it is 80-120 DEG C that the third drying condition, which includes: temperature, the time is 6-10 hours.
Preferably, the first physics expanding agent and the second physics expanding agent are respectively selected from carbon black powder, charcoal or sawdust
It is one or more；It is highly preferred that the first physics expanding agent and the second physics expanding agent are carbon black powder；It is highly preferred that
The weight ratio of the first physics expanding agent and the second physics expanding agent is 2-3:1, more preferably 2.5-3:1.It is highly preferred that institute
The additional amount for stating the first physics expanding agent is the 10-15 weight % of aluminium oxide butt；It is highly preferred that the second physics expanding agent
Additional amount be aluminium oxide butt 5-10 weight %.
It is highly preferred that the solvent of the first siliceous solution and the second siliceous solution is respectively selected from ethyl alcohol, methanol and acetone
One of or it is a variety of；
Silicic acid aliphatic alcohol ester and/or metasilicic acid aliphatic alcohol ester it is highly preferred that the esters of silicon acis is positive；
It is highly preferred that the esters of silicon acis is in methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester and butyl silicate
It is one or more.
Preferably, in terms of silica, the amount ratio of the first siliceous solution and the second siliceous solution is 2-12:1.More
Preferably, in terms of silica, total dosage of the first siliceous solution and the second siliceous solution is aluminium oxide butt
2.5-7 weight %.
Preferably, the volume of the described first siliceous solution is the 30-50% of the saturated water adsorptive value of the first physics expanding agent.It is excellent
Selection of land, the volume of the second siliceous solution are the saturated water adsorptive value of the second physics expanding agent.
Preferably, extrusion aid and/or peptizing agent are additionally added when mixing in step (2).
Preferably, it is 100-130 DEG C that the described first dry condition, which includes: temperature, and the time is 1-10 hours；More preferably
Ground, first roasting includes: first to roast in a nitrogen atmosphere, is then roasted in air atmosphere；It is highly preferred that the nitrogen
Maturing temperature under atmosphere is 400-600 DEG C, and calcining time is 4-6 hours, and the maturing temperature under the air atmosphere is 600-
900 DEG C, calcining time is 4-8 hours.
Preferably, the hydrogenation active component maceration extract contains the metal of group VIB and group VIII.It is highly preferred that with
Oxide meter vib metals content is 7-15g/100mL, and group VIII tenor is 0.8-3g/ in terms of oxide
100mL。
Second aspect of the present invention provides the siliceous Hydrodemetalation catalyst of above method preparation.
Second aspect of the present invention provides application of the above-mentioned siliceous Hydrodemetalation catalyst in hydrodemetallization reaction.
Through the above technical solutions, silica precursor by being impregnated into the physics of two kinds of different-grain diameters by the method for the present invention
In expanding agent, then by the physics expanding agent and boehmite kneading and compacting after dipping, molding first roasts in a nitrogen atmosphere,
Then it roasts in air atmosphere again and silicon-containing alumina carrier is made, then impregnate active component and siliceous hydrodemetallisation catalyst is made
Agent.Silica and the aluminium oxide on surface act on when roasting under nitrogen atmosphere, in conjunction with formation composite oxides.It is roasted under air atmosphere
When burning, physics expanding agent is oxidized removing.On the one hand silica plays the role of skeletal support, on the one hand improve the anti-of catalyst
Carbon distribution and anti-caking power, to obtain having the siliceous hydrodemetallization of good mechanical properties, pore structure and catalytic effect to urge
Agent.Simultaneously as the gas that physics expanding agent is formed when aoxidizing can play good reaming effect, different-grain diameter is selected
Physics expanding agent can effectively adjust the pore structure of carrier.
Further, the application makes the degree of impregnation of silica precursor in the physics expanding agent of two kinds of different-grain diameters not
Together, guarantee that the first physics expanding agent of greater particle size not exclusively impregnates, and compared with the second physics expanding agent thorough impregnation of small particle.
Through the above technical solutions, playing good skeletal support to form silica shell in the first physics expanding agent and making
With, it is therefore prevented that the collapsing of macropore makes corresponding duct be conducive to mass transfer and the diffusion of reactant (such as residual oil molecule)；In the second object
Manage expanding agent in the silicon dioxide carried contact surface in the second physics expanding agent and alumina support, and with aluminium oxide phase interaction
With due to the presence of silica, reducing the acidity of carrier at resulting hole, improve the anti-carbon of corresponding catalyst and anti-
Caking power increases the service life of catalyst.
Further, the catalyst after impregnating active component is carried out heat by the application under ammonia and water vapor mixture atmosphere
Processing, due to the effect of mixed atmosphere, dissolution redisperse occurs for the active component of carrier surface, changes active component and carrier
Between effect, while improving the dispersion degree of active component.In addition, under conditions of ammonia and water vapour sealing heat treatment,
Hydration and regrowth effect occur for alumina grain, improve the aperture of catalyst, have finally obtained catalyst higher
Activity and activity stability.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The preparation method of siliceous Hydrodemetalation catalyst of the invention, this method comprises the following steps,
(1) the first siliceous solution is carried out first with the first physics expanding agent to contact, by the second siliceous solution and the second object
It manages expanding agent and carries out the second contact；
(2) by the first physics expanding agent after contact that step (1) obtains, the second physics expanding agent after contact with intend it is thin
Diaspore obtains silicon-containing alumina carrier by mixing, molding, the first drying, the first roasting；
(3) the silicon-containing alumina carrier for obtaining hydrogenation active component maceration extract and step (2) carries out third contact, and will
Silicon-containing alumina carrier after contact obtains siliceous Hydrodemetalation catalyst through the second drying, the second roasting；Wherein, described
First siliceous solution and the second siliceous solution contain esters of silicon acis, and the partial size of the first physics expanding agent is 100-540 mesh, the
The partial size of two physics expanding agents is 900-2000 mesh.
According to the present invention, there is no particular limitation for the first physics expanding agent and the second physics expanding agent, can contain
Reaming effect is played in the preparation process of alumina support.From the specific surface area for improving obtained silicon-containing alumina carrier
From the aspect of Kong Rong, the first physics expanding agent and the second physics expanding agent are respectively selected from carbon black powder, charcoal or sawdust
It is one or more.From siliceous solution is fully absorbed, examined in terms of the pore structure convenient for controlling obtained silicon-containing alumina carrier
Consider, the first physics expanding agent and the second physics expanding agent are preferably all carbon black powder.From obtaining the angle in the different hole of size
Consider, it is preferable that the partial size of the first physics expanding agent is 200-400 mesh, and the partial size of the second physics expanding agent is 1300-
1800 mesh.
According to the present invention, the used in amounts of the first physics expanding agent and the second physics expanding agent will be according to being obtained
The property of silicon-containing alumina carrier determines.For specific surface area and the hole appearance etc. for improving silicon-containing alumina carrier, it is good to obtain performance
Good silicon-containing alumina carrier, it is preferable that the weight ratio of the first physics expanding agent and the second physics expanding agent is 2-3:1,
More preferably 2.5-3:1.
According to the present invention, for the property of the silicon-containing alumina carrier adjusted, it is preferable that the first physics reaming
The additional amount of agent is the 10-15 weight %, more preferably 12-14 weight % of aluminium oxide butt；It is highly preferred that second physics
The additional amount of expanding agent is the 5-10 weight %, further preferably 6-9 weight % of aluminium oxide butt.
In the present invention, aluminium oxide butt refers to the boehmite in terms of aluminium oxide, is equivalent to finally obtained contain
Aluminium oxide in alumina support.
According to the present invention, esters of silicon acis is contacted in the form of the first siliceous solution and the second siliceous solution with physics expanding agent,
It is intended that contacting esters of silicon acis uniformly with physics expanding agent, and it is sufficiently submerged in esters of silicon acis inside physics expanding agent.From
From the aspect of touch operation, it is preferable that the solvent of the first siliceous solution and the second siliceous solution is respectively selected from second
One of alcohol, methanol and acetone are a variety of, preferably ethyl alcohol.
According to the present invention, there is no particular limitation for the esters of silicon acis, it is preferable that the esters of silicon acis is positive silicic acid aliphatic alcohol ester
And/or metasilicic acid aliphatic alcohol ester.As the fat-based in above-mentioned positive silicic acid aliphatic alcohol ester and metasilicic acid aliphatic alcohol ester, Ke Yiwei
The fat-based of C1-C6, such as methyl, ethyl, propyl (n-propyl, isopropyl etc.), butyl (normal-butyl, tert-butyl, sec-butyl
Deng), amyl (n-pentyl, isopentyl, neopentyl etc.), hexyl (n-hexyl, 2- methyl amyl, 3- methyl amyl, 2,2- dimethyl
Butyl, 2,3- dimethylbutyl etc.).Preferably, the esters of silicon acis be methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester and
One of butyl silicate is a variety of.
In the present invention, it is described first contact and second contact mode there is no particular limitation, can according to need into
Row selection, such as can be dipping, spray, spraying etc., as long as physics expanding agent is made to absorb the siliceous solution.In order to protect
Both exhibit manages the siliceous solution of surface homogeneous impregnation of expanding agent, and the modes such as stirring, rotation can be assisted in dipping process, make
Uniformly contact.Specifically, it can will be sprayed onto after solution atomization in the physics expanding agent of continuous rotary motion, atomization can pass through
The modes such as nozzle, ultrasonic wave and high-speed flow carry out, such as can specifically be carried out using equipment such as rotation rolling pot, sugar coating machines.
According to the present invention, in the contact process of siliceous solution and physics expanding agent, the dosage of siliceous solution can basis
It needs to be determined that more than can be for the saturated water adsorptive value of physics expanding agent, that is, physics expanding agent is made to fully absorb siliceous solution,
Reach saturation (hereinafter also referred to saturation dipping)；It might be less that the saturated water adsorptive value of physics expanding agent, that is, siliceous solution
(hereinafter also referred to unsaturated dipping) is only immersed in the partial interior hole of physics expanding agent.In the latter case, in order to contain
Silicon solution is uniformly contacted with all physics expanding agent particles, adds physics expanding agent under the states such as stirring, rotation
Siliceous solution it is highly preferred that being added in a manner of spraying, be atomized etc., such as carries out above-mentioned contact in a manner of spraying.In this way
The way of contact, make siliceous solution well into the pore interior of physics expanding agent；Wherein, it is less than object in the dosage of siliceous solution
When managing the saturated water adsorptive value of expanding agent, siliceous solution can only be made to enter the outer layer of physics expanding agent, without entering physics reaming
The kernel portion of agent, to obtain Silica Shell by roasting.
A preferred embodiment according to the present invention, the silicon-containing alumina with good pore size distribution is catalyzed in order to obtain
Agent, in terms of silica, the amount ratio of the first siliceous solution and the second siliceous solution is 2-12:1, preferably 4-10:1.
A preferred embodiment according to the present invention, the silicon-containing alumina with good mechanical strength is urged in order to obtain
Agent, in terms of silica, total dosage of the first siliceous solution and the second siliceous solution is the 2.5-7 of aluminium oxide butt
Weight %, preferably 3-6 weight %.
A preferred embodiment according to the present invention, in order to form silica shell by the first physics expanding agent
Layer, the first physics expanding agent carry out unsaturated dipping.It is highly preferred that the volume of the first siliceous solution is the first physics
The 30-50% of the saturated water adsorptive value of expanding agent, more preferably 30-40%.
According to the present invention, the second physics expanding agent can carry out unsaturated dipping or saturation dipping.In order to pass through the
Two physics expanding agents are sufficiently formed aperture, and the volume of the second siliceous solution is the saturated water adsorptive value of the second physics expanding agent
80% or more, more preferably 90% or more, further preferably 100%.
According to the present invention, there is no particular limitation for the boehmite added in the preparation of the silicon-containing alumina carrier,
Boehmite used in alumina support can be routinely prepared for this field, can be commercially available product, it can also be by existing
Method prepared.
According to the present invention, extrusion aid can also be added when mixing in step (2).It can be ability as the extrusion aid
Domain routinely prepares extrusion aid used in alumina support, can be for selected from one of sesbania powder, starch and methylcellulose
Or a variety of, preferably sesbania powder.Preferably, the additional amount of the extrusion aid is 3-5 the weight %, preferably 4- of aluminium oxide butt
5 weight %.
According to the present invention, peptizing agent can also be added when mixing in step (2).It can be ability as the peptizing agent
Domain routinely prepares peptizing agent used in alumina support, can for selected from one of formic acid, acetic acid, citric acid and nitric acid or
It is a variety of.The additional amount of the peptizing agent can be determined according to required molding effect.Preferably, the additional amount of the peptizing agent is oxygen
Change the 3-10 weight %, preferably 5-7 weight % of aluminium butt.For the ease of the mixing of peptizing agent, can be incited somebody to action with solvent appropriate
It after above-mentioned peptization dilution agent, adds and is mixed with other materials, water etc. can be used for example and be diluted.
In the present invention, the second physics expanding agent after the first physics expanding agent, contact and boehmite can be with
The preparation that silicon-containing alumina carrier is carried out by the existing method that can be used in preparing alumina support, specifically can successively lead to
Cross mixing, molding, first dry, the first roasting obtain.
The mixing can be carried out using the existing equipment that can be used in material mixing, such as mixing machine, blender, institute
Stating the condition of mixing, also there is no particular limitation, reaches mixed uniformly purpose.
The molding can be carried out using the existing molding equipment of carrier that can be used in, such as banded extruder, tablet press machine, can
It is specifically chosen with support shapes as needed.
The condition dry as described first, there is no particular limitation, makes raw material drying after molding.Such as it is described
First drying condition may include: that temperature is 100-130 DEG C, and the time is 1-10 hours, it is preferable that and temperature is 110-120 DEG C, when
Between be 4-6 hours.
As the condition of first roasting, it may include: first to roast in a nitrogen atmosphere, then roast in air atmosphere
It burns.Specifically, the maturing temperature under the nitrogen atmosphere is 400-600 DEG C, preferably 450-500 DEG C；Time is 4-6 hours,
Preferably 5-6 hours.Maturing temperature under the air atmosphere is 600-900 DEG C, preferably 700-800 DEG C；Time is that 4-8 is small
When, preferably 5-7 hours.
Above-mentioned first roasting can carry out in tube furnace, before the first roasting, calcination atmosphere be made to be full of entire tube furnace,
The equipment that other can certainly be selected suitably to be able to carry out baking operation.
According to the present invention, in step (3), there is no particular limitation for the hydrogenation active component maceration extract, can be according to mesh
Mark catalyst composition is prepared.As the hydrogenation active component in hydrogenation active component maceration extract, can containing group VIB and
The metal of group VIII.It, can be selected from one of Cr, Mo and W or a variety of as vib metals；As group VIII gold
Belong to, it can be selected from one of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt or a variety of.Wherein, vib metals are preferably Mo
And/or W, group VIII metal are preferably Co and/or Ni.
In the hydrogenation active component maceration extract, above-mentioned hydrogenation active component can be added with concentration appropriate, for example,
Vib metals content is 7-15g/100mL in terms of oxide, and group VIII tenor is 0.8-3g/ in terms of oxide
100mL, it is preferable that vib metals content is 8-12g/100mL in terms of oxide, and group VIII metal contains in terms of oxide
Amount is 1-2g/100mL.As above-mentioned vib metals or the oxide of group VIII metal, specifically, the oxide of Mo refers to
MoO3, the oxide of Cr refers to CrO3, the oxide of W refers to WO3, the oxide of Ni refers to that NiO, the oxide of Fe refer to FeO, the oxidation of Co
Object refers to that CoO, the oxide of Ru refer to RuO2, the oxide of Rh refers to Rh2O3, the oxide of Pd refers to that PdO, the oxide of Os refer to OsO4, Ir
Oxide refer to IrO2, the oxide of Pt refers to PtO2。
In the present invention, the mode as third contact, there is no particular limitation, can according to need and is selected
It selects, such as can be dipping, spray etc., it is preferred to use impregnation method carries out.
It is 80-120 DEG C that the condition dry as above-mentioned second, which may include: temperature, and the time is 6-10 hours；Preferably,
Temperature is 90-110 DEG C, and the time is 6-8 hours.
As the condition of second roasting, temperature is 400-600 DEG C, and the time is 3-6 hours；Preferably, temperature is
450-550 DEG C, the time is 4-6 hours.
A preferred embodiment according to the present invention, in order to further improve the duct knot of silicon-containing alumina carrier
Structure, this method further include following steps: the siliceous Hydrodemetalation catalyst that step (3) obtains is sealed heat treatment by (4)
It is dried with third.It is highly preferred that the sealing heat treatment carries out under ammonia and water vapor mixture atmosphere.By in ammonia
And closing heat treatment is carried out under water vapor mixture atmosphere, the crystal grain of silicon-containing alumina carrier can be made to further increase, expand and carry
Body aperture, and the interaction of metal active constituent and carrier can be improved, make final catalyst activity with higher and
Activity stability.
Specifically, it is 3-5MPa that the condition as the sealing heat treatment, which may include: gas pressure, wherein point of ammonia
Pressure is 30%-50%, remaining is water vapour, and heat treatment temperature is 100-150 DEG C, and the processing time is 5-10 hours.
The condition dry as the third, there is no particular limitation, such as may include: temperature is 80-120 DEG C,
Time is 6-10 hours, it is preferable that temperature is 90-110 DEG C, and the time is 8-10 hours.
The present invention also provides the siliceous Hydrodemetalation catalysts of above method preparation.
The present invention also provides application of the above-mentioned siliceous Hydrodemetalation catalyst in hydrodemetallization reaction, such as
Application in residuum hydrogenating and metal-eliminating reaction.
The present invention will be described in detail by way of examples below.In following embodiment, carbon black powder is that Tianjin tongue is net
The active carbon powder that the cocoanut active charcoal of water material Science and Technology Ltd. production obtains after pulverizing and sieving.
Use N2Physics suction-desorption method characterizes the alumina support pore structure that following embodiment and comparative examples obtain, and uses
ASAP-2420 type N2Instrument progress is inhaled-be desorbed to physics.Concrete operations are as follows: taking a small amount of sample to be vacuum-treated 3-4 at 300 DEG C small
When, finally product is placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test.Wherein, surface area is according to BET
Equation obtains, and pore-size distribution and pore volume are obtained according to BJH model.
The alumina support ingredient obtained using x ray fluorescence spectrometry (XRF) characterization embodiment and comparative example, it is specific to grasp
Make as follows: using Japan's RIGAKU company ZSX-100e type Xray fluorescence spectrometer, performance indicator: X-ray tube Be window thickness: 30 μ
m；Power: 4kW；Output voltage: 20-60kV；Export electric current: 2-150mA；2 0.0001 ° of the angle θ reproducibilities；2 angle θ accuracys
0.0002°。
Embodiment 1
1) weighing partial size is that 400 15 grams of the first carbon black powders of purpose are placed in spray rolling pot, in 90 revs/min of rotary state
Under, spray the ethanol solution 7.5mL of ethyl orthosilicate in a manner of unsaturated dipping to the first carbon black powder with nozzle atomization mode
(dosage is the 50% of the first carbon black powder saturated water adsorptive value, wherein being equivalent to containing 4 grams of silica).
2) weighing partial size is that 1,300 5 grams of the second carbon black powders of purpose are placed in spray rolling pot, in 90 revs/min of rotary state
Under, spray the ethanol solution 5mL (dosage of ethyl orthosilicate in a manner of being saturated dipping to the second carbon black powder by atomizing type
Two carbon black powder saturated water adsorptive values, wherein being equivalent to containing 0.5 gram of silica).
3) by above-mentioned steps 1) the second carbon black powder after the obtained dipping of the first carbon black powder after obtained dipping, step 2)
It is abundant with 150 grams of boehmites (Wenzhou essence crystal alumina factory produces, and aluminium oxide contents on dry basis is 65 weight %), 2g sesbania powder
Mixing, then into above-mentioned material, addition 85mL is uniform dissolved with the aqueous solution kneading of 2g acetic acid, extruded moulding.By wet object after molding
Expect 8 hours dry in 110 DEG C.Material after drying is placed in tube furnace, nitrogen is passed through into tube furnace makes nitrogen full of whole
A burner hearth, 400 DEG C roast 6 hours, and then nitrogen leak is passed through air, 600 DEG C of roastings, 6 hours obtained silicon-containing alumina carriers
S1。
4) 100 grams of above-mentioned silicon-containing alumina carrier Ss 1 are weighed to be placed in a beaker, are impregnated with 100mL molybdenum-nickel-phosphor active metal
Liquid (is equivalent to containing MoO310 grams, NiO1.2 grams) dipping 5 hours, redundant solution is filtered, the material after dipping dries 6 in 120 DEG C
Hour, then roasted 5 hours at 500 DEG C.
5) catalyst after roasting that step 4) obtains is placed in sealing tube furnace, is passed through the mixing of ammonia and water vapour
Gas, wherein ammonia partial pressure is 30%, and the pressure for controlling mixed gas in tube furnace is 4MPa, the sealing heat treatment 8 at 125 DEG C
Hour.In 120 DEG C siliceous Hydrodemetalation catalyst C1, the catalysis is made in dry 5 hours in catalyst after sealing heat treatment
The property of agent is shown in Table 1.
Embodiment 2
It is prepared similarly to Example 1 containing siliceous Hydrodemetalation catalyst, unlike:
In step 1), the partial size of the first carbon black powder is 325 mesh, and additional amount is 12.5 grams, uses 3.8mL methyl orthosilicate
Ethanol solution (dosage is the 30% of the first carbon black powder saturated water adsorptive value, wherein being equivalent to containing 2 grams of silica) sprays the first carbon
Black powder.
In step 2), the partial size of the second carbon black powder is 1100 mesh, and additional amount is 7.5 grams, uses 7.5mL methyl orthosilicate
Ethanol solution (dosage is the second carbon black powder saturated water adsorptive value, wherein being equivalent to containing silica 1 gram) sprays the second carbon black powder.
In step 3), maturing temperature in a nitrogen atmosphere is 500 DEG C, and maturing temperature is 750 DEG C under air atmosphere.
In step 5), the pressure of mixed gas is 3MPa, and wherein ammonia partial pressure is 50%, and heat treatment temperature is 150 DEG C, place
Managing the time is 5 hours.
To which siliceous Hydrodemetalation catalyst C2 be made, the property of the catalyst is shown in Table 1.
Embodiment 3
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike:
In step 1), the partial size of the first carbon black powder is 540 mesh, and additional amount is 10 grams, uses the second of 4.5mL methyl orthosilicate
Alcoholic solution (dosage is the 45% of the first carbon black powder saturated water adsorptive value, wherein being equivalent to containing 6 grams of silica) sprays the first carbon black
Powder.
In step 2), the partial size of the second carbon black powder is 1800 mesh, and additional amount is 10 grams, uses the second of 10mL methyl orthosilicate
Alcoholic solution (dosage is the second carbon black powder saturated water adsorptive value, wherein being equivalent to containing 0.75 gram of silica) sprays the second carbon black powder.
In step 3), maturing temperature in a nitrogen atmosphere is 600 DEG C.Maturing temperature is 900 DEG C under air atmosphere.
In step 5), the pressure of mixed gas is 5MPa, and wherein ammonia partial pressure is 40%, and heat treatment temperature is 100 DEG C, place
Managing the time is 10 hours.
To which siliceous Hydrodemetalation catalyst C3 be made, the property of the catalyst is shown in Table 1.
Embodiment 4
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike: ethyl orthosilicate in step 1)
The dosage of ethanol solution is the first carbon black powder saturated water adsorptive value (amount of contained ethyl orthosilicate is constant).The siliceous plus de- gold of hydrogen is made
The property of metal catalyst C4, the catalyst are shown in Table 1.
Embodiment 5
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike: ethyl orthosilicate in step 2)
The dosage of ethanol solution is 50% (amount of contained ethyl orthosilicate is constant) of the second carbon black powder saturated water adsorptive value.It is made siliceous to add
Hydrogen catalyst for demetalation C5, the property of the catalyst are shown in Table 1.
Embodiment 6
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike: without step 5), it is made and contains
Silicon Hydrodemetalation catalyst C6, the property of the catalyst are shown in Table 1.
Comparative example 1
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike: without the first carbon black powder and the
The dipping process of two carbon black powders, i.e., without step 1) and 2), by same amount of first carbon black powder, the second carbon black powder and step
1), 2) used in the ethanol solution of ethyl orthosilicate directly carry out step 3).Siliceous Hydrodemetalation catalyst is finally made
The property of DC1, the catalyst are shown in Table 1.
Comparative example 2
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike: the leaching without the first carbon black powder
Stain process, i.e., without step 1), by the ethanol solution of the ethyl orthosilicate in same amount of first carbon black powder and step 1), with
The second carbon black powder after the dipping that step 2) obtains directly carries out step 3).Siliceous Hydrodemetalation catalyst DC2 is finally made,
The property of the catalyst is shown in Table 1.
Comparative example 3
Siliceous Hydrodemetalation catalyst is prepared similarly to Example 1, unlike: the leaching without the second carbon black powder
Stain process, i.e., without step 2), by the ethanol solution of the ethyl orthosilicate in same amount of second carbon black powder and step 2), with
The first carbon black powder after the dipping that step 1) obtains directly carries out step 3).Siliceous Hydrodemetalation catalyst DC3 is finally made,
The property of the catalyst is shown in Table 1.
The property of 1 catalyst of table
*: pore size distribution refers to that the Kong Rong that diameter range inner hole is corresponded in carrier accounts for the percentage of total pore volume.
Test case
The following examples illustrate the catalyst of the method for the present invention preparation and the catalytic performance of comparative example catalyst.
Using feedstock oil shown in table 2 as raw material, siliceous hydrodemetallization is evaluated on 200 milliliters of hydrogenation reaction device and is urged
The catalytic performance of agent C1-6, DC1-3, catalyst are long 2~3 millimeters of strip, and loaded catalyst is 100 milliliters, reaction
Temperature is 375 DEG C, hydrogen partial pressure 13MPa, and liquid hourly space velocity (LHSV) is 1.0 hours-1, hydrogen to oil volume ratio 1000, reaction 200 hours after survey
The fixed content for generating each impurity in oil calculates metal phase to removal efficiency, and evaluation result is shown in Table 3.
The property of 2 feedstock oil of table
| Project | Content |
| S, wt% | 4.21 |
| Ni, μ g/g | 21.5 |
| V, μ g/g | 83.2 |
3 catalyst hydrogenation performance of table
| C1 | C2 | C3 | C4 | C5 | C6 | DC1 | DC2 | DC3 | |
| Metal removal rate, % | 86.2 | 88.7 | 85.1 | 83.1 | 82.8 | 81.5 | 53.7 | 55.9 | 58.4 |
It can be seen from the result of table 3 compared with comparative example, the Hydrodemetalation catalyst of the method for the present invention preparation has
Higher hydrodemetallization activity.
Activity rating is carried out to catalyst obtained by above-described embodiment and comparative example, the temperature rise situation for running 5000h is shown in
Table 4.
4 reaction temperature lift-off value of table
| Catalyst | Reaction temperature lift-off value after reaction 5000 hours, DEG C |
| C1 | 18 |
| C2 | 17 |
| C3 | 18 |
| C4 | 19 |
| C5 | 20 |
| C6 | 21 |
| DC1 | 27 |
| DC2 | 26 |
| DC3 | 25 |
Find out from the result of table 4, after reaction 5000 hours, using Hydrodemetalation catalyst provided by the invention, in order to
High demetallization per is kept, required reaction temperature increase rate is far smaller than comparative catalyst, this explanation is provided by the invention to add hydrogen
Catalyst for demetalation has higher activity stability.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (11)
1. a kind of preparation method of siliceous Hydrodemetalation catalyst, which is characterized in that this method comprises the following steps,
(1) the first siliceous solution is carried out first with the first physics expanding agent to contact, the second siliceous solution and the second physics is expanded
Hole agent carries out the second contact；
(2) by the first physics expanding agent after contact that step (1) obtains, the second physics expanding agent after contact and intend thin water aluminium
Stone obtains silicon-containing alumina carrier by mixing, molding, the first drying, the first roasting；
(3) the silicon-containing alumina carrier for obtaining hydrogenation active component maceration extract and step (2) carries out third contact, and will contact
Silicon-containing alumina carrier afterwards is dry through second, second roasts, and obtains siliceous Hydrodemetalation catalyst；
Wherein, the described first siliceous solution and the second siliceous solution contain esters of silicon acis,
The partial size of the first physics expanding agent is 100-540 mesh, and the partial size of the second physics expanding agent is 900-2000 mesh.
2. preparation method according to claim 1, wherein this method further includes following steps,
(4) the siliceous Hydrodemetalation catalyst that step (3) obtains is sealed heat treatment and third is dried；
Preferably, the sealing heat treatment carries out under ammonia and water vapor mixture atmosphere；
Preferably, it is 3-5MPa that the condition of the sealing heat treatment, which includes: gas pressure, and wherein the partial pressure of ammonia is 30%-
50%, remaining is water vapour, and heat treatment temperature is 100-150 DEG C, and the processing time is 5-10 hours；
Preferably, it is 80-120 DEG C that the third drying condition, which includes: temperature, and the time is 6-10 hours.
3. preparation method according to claim 1, wherein the first physics expanding agent and the second physics expanding agent difference
Selected from one of carbon black powder, charcoal or sawdust or a variety of；
Preferably, the first physics expanding agent and the second physics expanding agent are carbon black powder；
Preferably, the weight ratio of the first physics expanding agent and the second physics expanding agent is 2-3:1, more preferably 2.5-3:1；
Preferably, the additional amount of the first physics expanding agent is the 10-15 weight % of aluminium oxide butt；
Preferably, the additional amount of the second physics expanding agent is the 5-10 weight % of aluminium oxide butt.
4. preparation method according to claim 1, wherein the solvent of the first siliceous solution and the second siliceous solution point
It Xuan Zi not one of ethyl alcohol, methanol and acetone or a variety of；
Preferably, the esters of silicon acis is positive silicic acid aliphatic alcohol ester and/or metasilicic acid aliphatic alcohol ester；
Preferably, the esters of silicon acis be one of methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester and butyl silicate or
It is a variety of.
5. preparation method described in any one of -4 according to claim 1, wherein in terms of silica, described first is siliceous
The amount ratio of solution and the second siliceous solution is 2-12:1；
Preferably, in terms of silica, total dosage of the first siliceous solution and the second siliceous solution is aluminium oxide butt
2.5-7 weight %.
6. preparation method described in any one of -4 according to claim 1, wherein the volume of the first siliceous solution is the
The 30-50% of the saturated water adsorptive value of one physics expanding agent；
Preferably, the volume of the described second siliceous solution is the saturated water adsorptive value of the second physics expanding agent.
7. preparation method according to claim 1, wherein be additionally added extrusion aid and/or peptization when mixing in step (2)
Agent.
8. preparation method according to claim 1, wherein the described first dry condition includes: that temperature is 100-130
DEG C, the time is 1-10 hours；
Preferably, first roasting includes: first to roast in a nitrogen atmosphere, is then roasted in air atmosphere；
Preferably, the maturing temperature under the nitrogen atmosphere is 400-600 DEG C, and calcining time is 4-6 hours, the air atmosphere
Under maturing temperature be 600-900 DEG C, calcining time be 4-8 hours.
9. preparation method described in any one of -4 according to claim 1, wherein the hydrogenation active component maceration extract contains
The metal of group VIB and group VIII；
Preferably, vib metals content is 7-15g/100mL in terms of oxide, the group VIII tenor in terms of oxide
For 0.8-3g/100mL.
10. the siliceous Hydrodemetalation catalyst of any one of claim 1-9 the method preparation.
11. application of the siliceous Hydrodemetalation catalyst described in any one of claim 10 in hydrodemetallization reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710595286.6A CN109277108B (en) | 2017-07-20 | 2017-07-20 | Silicon-containing hydrodemetallization catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710595286.6A CN109277108B (en) | 2017-07-20 | 2017-07-20 | Silicon-containing hydrodemetallization catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109277108A true CN109277108A (en) | 2019-01-29 |
| CN109277108B CN109277108B (en) | 2021-07-27 |
Family
ID=65184857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710595286.6A Active CN109277108B (en) | 2017-07-20 | 2017-07-20 | Silicon-containing hydrodemetallization catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109277108B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433040A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
| WO2023173812A1 (en) * | 2022-03-16 | 2023-09-21 | 中国石油天然气股份有限公司 | α-ALUMINA SUPPORT, α-ALUMINA-BASED CATALYST, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2186090C2 (en) * | 2000-05-18 | 2002-07-27 | Королева Наталья Владиславовна | Method for production of liquid hydrocarbons by hydrogenation and demetallization of heavy oil feedstock |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
| CN102861616A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of alumina supporter with concentrated hole distribution |
| CN103566926A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst with hydrogenating function as well as preparation method and application thereof |
| CN103769231A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of silicon-containing alumina carrier |
| CN106140187A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrodemetalation catalyst |
| CN106140181A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of siliceous Hydrodemetalation catalyst |
| CN106669707A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrogenation and metal removing catalyst preparation method |
-
2017
- 2017-07-20 CN CN201710595286.6A patent/CN109277108B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2186090C2 (en) * | 2000-05-18 | 2002-07-27 | Королева Наталья Владиславовна | Method for production of liquid hydrocarbons by hydrogenation and demetallization of heavy oil feedstock |
| CN102441437A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation methods for macroporous alumina carrier and hydrodemetallization catalyst |
| CN102861616A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of alumina supporter with concentrated hole distribution |
| CN103566926A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化工股份有限公司 | Catalyst with hydrogenating function as well as preparation method and application thereof |
| CN103769231A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of silicon-containing alumina carrier |
| CN106140187A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrodemetalation catalyst |
| CN106140181A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of siliceous Hydrodemetalation catalyst |
| CN106669707A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrogenation and metal removing catalyst preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433040A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
| CN114433040B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | High-activity hydrotreating catalyst and preparation method and application thereof |
| WO2023173812A1 (en) * | 2022-03-16 | 2023-09-21 | 中国石油天然气股份有限公司 | α-ALUMINA SUPPORT, α-ALUMINA-BASED CATALYST, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109277108B (en) | 2021-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103785400B (en) | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst | |
| CN106140181B (en) | A kind of preparation method of siliceous Hydrodemetalation catalyst | |
| CN106669707B (en) | The preparation method of Hydrodemetalation catalyst | |
| Wang et al. | Effect of promoters on the selective hydrogenolysis of glycerol over Pt/W-containing catalysts | |
| CN103785401B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN104549328A (en) | Method for preparing residual oil hydro-demetallization catalyst | |
| Liu et al. | Chemoselective hydrogenation of α, β-unsaturated aldehydes over Rh nanoclusters confined in a metal–organic framework | |
| CN107303484B (en) | A kind of preparation method and hydrotreating catalyst of siliceous macropore alumina supporter | |
| CN111375396B (en) | Hydrotreating catalyst carrier, catalyst and preparation method thereof | |
| CN109277108A (en) | Siliceous Hydrodemetalation catalyst and its preparation method and application | |
| CN109794257A (en) | Sulfur-resistant transformation catalyst and preparation method thereof | |
| CN109304183A (en) | Handle the hydrotreating catalyst and the preparation method and application thereof of inferior oil material | |
| CN101288851B (en) | SBA-15 loaded high dispersion nickel catalyst modified by hole wall carbon and its preparation method | |
| CN106311358B (en) | A kind of shell profile catalyst and preparation method thereof and a kind of Fischer-Tropsch synthesis method | |
| CN105983418B (en) | Containing TiO2Preparation method of macroporous residual oil hydrodemetallization catalyst | |
| CN109277095A (en) | Silicon-containing alumina carrier and its preparation method and application | |
| CN105618072B (en) | The preparation method of Hydrodemetalation catalyst | |
| CN109277102A (en) | Hydrodemetalation catalyst and its preparation method and application | |
| CN106140122B (en) | A kind of preparation method of boracic Hydrodemetalation catalyst | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN107303491B (en) | The preparation method of Hydrodemetalation catalyst | |
| CN105582947B (en) | A kind of preparation method of carbon containing residuum hydrogenating and metal-eliminating catalyst | |
| CN105833869B (en) | A kind of shell profile catalyst and preparation method thereof and a kind of Fischer-Tropsch synthesis method | |
| CN111821990B (en) | Residual oil hydrogenation protective agent carrier, catalyst and preparation method thereof | |
| CN106140183B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing zirconium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |