CN106914250A - Catalyst for hydrotreatment of residual oil and preparation method thereof - Google Patents
Catalyst for hydrotreatment of residual oil and preparation method thereof Download PDFInfo
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- CN106914250A CN106914250A CN201510989775.0A CN201510989775A CN106914250A CN 106914250 A CN106914250 A CN 106914250A CN 201510989775 A CN201510989775 A CN 201510989775A CN 106914250 A CN106914250 A CN 106914250A
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- Prior art keywords
- catalyst
- center
- carrier
- residual oil
- metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000011148 porous material Substances 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010941 cobalt Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 239000010937 tungsten Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 21
- 239000013618 particulate matter Substances 0.000 claims description 17
- 239000007921 spray Substances 0.000 claims description 13
- 238000000746 purification Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 18
- 239000012535 impurity Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 31
- 238000009826 distribution Methods 0.000 description 19
- 239000003921 oil Substances 0.000 description 15
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 6
- 206010013786 Dry skin Diseases 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 238000002803 maceration Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UFMBFIIJKCBBHN-MEKJRKEKSA-N myelin peptide amide-16 Chemical compound C([C@@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](CO)C(=O)N[C@@H](C)C(N)=O)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CO)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](C)NC(=O)[C@H](C)NC(C)=O)C1=CC=C(O)C=C1 UFMBFIIJKCBBHN-MEKJRKEKSA-N 0.000 description 1
- 108010074682 myelin peptide amide-16 Proteins 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/66—Pore distribution
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- C10G2300/205—Metal content
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of catalyst for hydrotreatment of residual oil and preparation method thereof.Catalyst pore volume of the present invention is 0.2~1.2mL/g；Specific surface area is 40~200m2/g；Average pore diameter is in radially gradually to increase from center to outer surface along carrier granular, the average pore diameter of 50% part 3~10nm small compared with the average pore diameter of particle diameter 80% to surface portion from granular center to particle diameter；With aluminum oxide as carrier, the oxide of the cobalt and/or nickel of molybdenum and/or tungsten and 0.4-4% containing total catalyst weight 4-12% in catalyst；The method of the present invention is the aluminum oxide precursor that will be molded simultaneously preroast, and with concentration, gradually increased acid solution is processed；Predrying and washing process is carried out after the impregnated metal of carrier, most catalyst is obtained through dry and roasting afterwards.The present invention provides catalyst has de- impurity activity and stability high.
Description
Technical field
The present invention be on a kind of catalyst for hydrotreatment of residual oil and preparation method thereof, be in particular on
It is a kind of to be reduced at the residual hydrogenation of distribution characteristics with metal component gradient while having aperture gradient to increase
Reason catalyst and preparation method thereof.Catalyst of the present invention can be used for the hydrotreating of inferior heavy oil particularly residual oil
Process.
Background technology
Inferior heavy oil such as residual oil etc. contains the metal impurities such as Ni, V higher, it usually needs at hydrogenation
Reason is removed, by follow-up processing (such as catalytic cracking), to produce the oil such as vapour, the diesel oil of cleaning
Product and industrial chemicals.Research shows that metal impurities are primarily present in resin and asphalt in residual oil, this part
Molecular weight of material is big, complex structure, and diffusion is difficult, therefore it is required that catalyst have excellent pore passage structure and
Good active metal dispersing characteristic, to promote macromolecular reaction material to catalyst granules diffusion inside, instead
Should and deposit, so as to obtain de- impurity activity and stability high.
The pore structure of catalyst has important influence to its performance.Especially residual oil adds for mink cell focus hydrotreating
Hydrogen processing procedure is typical interior diffusion controlled process, it is necessary to catalyst has unobstructed duct.Duct is unobstructed
Be conducive to the diffusion and reaction of macromolecule hydrocarbon material in mink cell focus, so as to improve the reactivity of catalyst；
Metal deposit or reaction coking is avoided to cause catalyst aperture to block and cause rapid catalyst deactivation simultaneously, with
Improve the activity stability of catalyst and hold impurity ability.Therefore a unobstructed residual hydrocracking in duct is urged
Agent, by with good reactivity and activity stability.
In order to improve alumina support diffusion, the side for adding expanding agent to increase carrier aperture is generally used
Method, such as patent US4,066,574, US4,113,661 and US4,341,625 describe a kind of carrying alumina
The preparation method of body, i.e., first add aqueous solution of nitric acid in Alpha-alumina monohydrate, fully adds again after effect
Enter a certain amount of ammonia spirit, reach the purpose for expanding carrier aperture.Although the method can play reaming work
With, but carrier bore dia is in single distribution by particle exterior surface to center, and hole is easily caused during the course of the reaction
Mouth is blocked, and is unfavorable for substantially playing the effect of particle surfaces externally and internally.
Patent CN104646005 discloses a kind of method for preparing catalyst with step pore-size distribution feature,
Catalyst average pore size is in gradually to increase from granular center to outer surface, so as to reduce catalyst in course of reaction
There is the possibility that aperture blocks.Its method is that the alumina support after shaping and roasting is gradually increased with concentration
Acid solution carry out spraying treatment, by various concentrations acid solution to aluminium oxide structure dissolved destruction degree
Difference, make carrier aperture from the center to outer surface in gradually increasing.The method is by acid solution to roasting
Aluminum oxide afterwards is processed, and reaming effect is limited.
In addition, the active metal dispersing characteristic by optimizing catalyst, i.e., by the way of non-uniform Distribution,
Make the content of active metal in catalyst gradually reduces from granular center to outer surface, reduces catalyst external surface
The hydrogenation activity at place, so as to promote metal impurities in residual oil raw material more to catalyst particles during the course of the reaction
Intragranular portion deposits, it is to avoid catalyst occurs aperture and blocks, and improves catalyst with this and holds metal ability and activity gold
Category utilization ratio, and then improve catalyst service life, it is ensured that the long-term operation of device.
European patent EP 0204314 is provided at a kind of hydrogenation with the distribution of uneven active metal component
Reason catalyst, the catalyst employs a kind of substep, the method for multiple dipping and supports active metal component, i.e.,
First carrier is immersed in the solution A containing amount of activated metal component, after taking-up through washing, dry and
Roasting, then immerse in the B solution containing other active components, through washing, drying and be calcined after taking-up
To catalyst.Because the method needs multiple, step impregnation, washing and roasting, preparation process is excessively complicated.
Patent CN101927196 discloses the hydrogenation that a kind of active metal component solution reduces distribution in gradient
Catalyst, its preparation method is gradually to reduce GOLD FROM PLATING SOLUTION during active metal solution is sprayed to belong to component
Concentration successively sprays concentration different solutions from high to low.Although this method has feasibility in theory,
Operation difficulty is larger, is difficult to ensure that solution is uniformly sprayed on different carrier granulars when spraying, gained catalysis
The gradient distribution uniformity of metal component is poor between variable grain in agent；In addition different metal component is in carrier hole
Absorption and diffusion property in road have differences, and are easily caused the metal group of same catalyst particles intragranular different zones
Distribution ratio has differences, so as to influence its catalytic performance.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of while having aperture gradient increase and metal
Composition gradient reduces hydrogenation catalyst of distribution characteristics and preparation method thereof, catalyst prepared by the inventive method
Diffusion is excellent, has the advantages that reactivity is high, appearance impurity ability is strong, long service life, can conduct
Heavy oil hydrogenation catalyst particularly catalyst for hydrotreatment of residual oil is used.
The present invention provides a kind of catalyst for hydrotreatment of residual oil, it is characterised in that
Pore volume is 0.2~1.2mL/g；
Specific surface area is 40~200m2/g；
Average pore diameter is in radially gradually to increase from center to outer surface along carrier granular, from granular center to grain
Average pore diameter 3~the 10nm small compared with the average pore diameter of particle diameter 80% to surface portion of the part of footpath 50%；
With aluminum oxide as carrier, molybdenum and/or tungsten containing total catalyst weight 4-12% in catalyst and
The cobalt of 0.4-4% and/or the oxide of nickel；
Metal component concentration is gradually decreased from granular center to outside table in catalyst granules；Outside catalyst granules
The ratio between surface and center weight metal are 0.05-0.60, are with the ratio between center weight metal at 0.66R
With the ratio between center weight metal it is 0.60-0.95 at 0.40-0.80,0.33R.R is with catalyst granules
The heart is the particle radius of the catalyst of initial point.
The present invention also provides a kind of preparation method of catalyst for hydrotreatment of residual oil, and it is at above-mentioned residual hydrogenation
The preparation method of catalyst is managed, is comprised the following steps：
1) aluminum oxide precursor and peptizing agent, the abundant kneading of water, be molded and dry；
2) particulate matter to 1) middle gained carries out preroast 1~4 hour at 200-450 DEG C；
3) particulate matter to 2) middle gained uniformly sprays acid or the acid solution that concentration is increased continuously, or spray
Concentration two or more sour or acid solution from low to high is drenched, 0.5~3 hour is stood at 20-100 DEG C；It is dry
It is dry and be calcined, obtain carrier；
4) metallic solution containing molybdenum and/or tungsten and nickel and/or cobalt is prepared, and resulting vehicle is impregnated with saturation
Mode carried metal；
5) predrying, hot blast temperature is carried out to the particulate matter of 4) middle gained using vibra fluidized bed drying equipment
At 40-100 DEG C, the final water content control of catalyst is in 20-60% for control；
6) resulting material in 5) is dipped in water purification, immerses time 1-60 minute, 20-80 DEG C of water purification temperature；
7) step 6) in material after washing at 80-150 DEG C through vibra fluidized bed drying, control water contains
Amount is less than 8%, is then calcined 2-6 hours at 400-650 DEG C, contains in catalyst and accounts for total catalyst weight
The molybdenum and/or tungsten of 4-12% and the cobalt of 0.4-4% and/or the oxide of nickel.
The preparation method of catalyst for hydrotreatment of residual oil of the present invention, wherein, step 3) described in acid
Or acid solution is preferably nitric acid or acetic acid and its solution.
The present invention can be so that details are as follows：
Hydrogenation catalyst of the invention, pore volume is 0.2~1.2mL/g, and specific surface area is 40~200m2/g；
Its average pore diameter is in radially gradually to increase from center to outer surface along carrier granular, from granular center to particle diameter
The average pore diameter of 50% part 3~10nm small compared with the average pore diameter of particle diameter 80% to surface portion；Catalysis
The oxide of the cobalt and/or nickel of molybdenum and/or tungsten and 0.4-4% containing total catalyst weight 4-12% in agent；Urge
Metal component concentration is gradually decreased from granular center to outer surface in catalyst particles；Catalyst granules outer surface with
The ratio between center weight metal is 0.05-0.60, with the ratio between center weight metal is 0.40-0.80 0.66R at,
With the ratio between center weight metal it is 0.60-0.95 at 0.33R.R is with catalyst granules center as initial point
Catalyst particle radius.
The main points of the method provided by the present invention include：1) aluminum oxide precursor and peptizing agent, water etc. fully kneading,
It is molded and dries；2) particulate matter to 1) middle gained carries out preroast 1~4 hour at 200-450 DEG C；
3) in 2) gained to particulate matter uniformly spray acid or the acid solution that concentration is increased continuously, or spray
Concentration two or more sour or acid solution from low to high is drenched, 0.5~3 hour is stood at 20-100 DEG C；It is dry
It is dry and be calcined, obtain final carrier；4) metallic solution containing molybdenum and/or tungsten and nickel and/or cobalt is prepared,
And to resulting vehicle by saturation impregnate in the way of carried metal；5) using vibra fluidized bed drying equipment to 4)
The particulate matter of middle gained carry out it is predrying, hot blast temperature control in 40-100 DEG C, the final water content control of catalyst
System is in 20-60%；4) resulting material in 5) is dipped in water purification, immerses time 1-60 minute, water purification temperature
20-80 DEG C of degree；6) material after washing, through vibra fluidized bed drying, controls water content at 80-150 DEG C
Less than 8%, then it is calcined 2-6 hours at 400-650 DEG C, total catalyst weight 4-12% is contained in catalyst
Molybdenum and/or tungsten and 0.4-4% cobalt and/or nickel oxide.
Method for preparing catalyst of the present invention can as needed add P, Ti, Si, Zr in carrier forming process
Etc. the extrusion aid such as different auxiliary agents and sesbania powder, starch.
The shape of catalyst of the present invention can be changed according to different requirements.
Compared with prior art, catalyst of the present invention has aperture gradient increase and metal component ladder simultaneously
Degree reduces distribution characteristics, and catalyst reaction activity, appearance impurity ability and service life are more excellent.Before roasting
Aluminum oxide precursor carries out acid treatment, and reaming is better；To the catalyst elder generation low temperature after impregnating metal solution
Predrying to carry out washing process again, metal component distribution gradient is good, and operability is relatively strong, different catalysts
Intergranular metal gradient distribution uniformity preferably, same catalyst particles intragranular different parts metal proportioning homogeneity compared with
It is good.
The present invention makes the principle of carrier aperture distribution gradient be：Its saturation is pressed to the particulate matter after shaping and drying
Water absorption rate spray acid or acid solution.While spray, the concentration of acid or acid solution is continuously adjusted；Or
Person's spray concentration two or more sour or acid solution from low to high.Due to the effect of capillary pressure, make
Acid or acid solution successively enter particulate matter duct from low to high by its concentration, finally make molten in particulate matter duct
Liquid acid concentration is in increase tendency by granular center to outer surface.By acid or acid solution and aluminum oxide precursor
Between effect, expanded the bore dia in duct.Due to the difference of acid solutions, its reaming is caused
Effect is different, finally makes carrier duct from granular center to outer surface in gradually increase tendency, is formed open
" trumpet type " pore passage structure so that carrier pore volume increase, duct it is open.Due to being to not being calcined
Aluminum oxide precursor carry out acid treatment, reaming is better.
Catalyst is carried out predrying using vibra fluidized bed drying equipment in this method or dried, with drying
The advantage that uniform in effect, drying temperature are low, rate of drying is fast, with vibrated fluidized bed to the catalyst after dipping
First low temperature is predrying, then washes again and is dried with vibratory liquefaction, it is possible to reduce caused by metal component spreads
Distribution gradient reduction, while gradient distribution uniformity is preferable between particle.
Hydrogenation catalyst of the present invention, can urge as heavy oil hydrogenating treatment catalyst, particularly residual hydrocracking
Agent is used.
There is the alumina support prepared by the method provided by the present invention typical aperture gradient to increase and gold
Category composition gradient reduces distribution characteristics.For example, according to the catalyst of the method provided by the present invention preparation through 500 DEG C
Roasting 3 hours, pore volume is 0.67cm3/ g, specific surface area is 135m2/g；50% from granular center to particle diameter
Partial average pore diameter 6nm small compared with the average pore diameter of particle diameter 80% to surface portion；Catalyst contains and accounts for
Its gross weight 8.1%MoO3NiO with 1.0%；Catalyst granules outer surface and center weight metal it
At 0.32,0.66R with the ratio between center weight metal it is 0.55,0.33R places and center metal weight than being
The ratio between amount is 0.78.
Brief description of the drawings
Fig. 1：The catalyst aperture radial distribution schematic diagram of embodiment 1；
Fig. 2：The catalyst metal components distribution schematic diagram of embodiment 1.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed implementation method and process, but protection scope of the present invention be not limited to it is following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Embodiment 1
Weigh the macropore boehmite dry glue powder (contents on dry basis of Yantai Heng Hui Chemical Co., Ltd.s production
71.5wt%) 500g, 10.7 grams of sesbania powder；It is slow to add by 17.9 grams of acetic acids in 430g water purification
Enter in afore-mentioned materials, then kneading is extruded into a diameter of 1.6mm's into plastic on single-screw extruder
Cloverleaf pattern.120 DEG C of dryings 2.0 hours, are processed 3 hours at 300 DEG C.Take 100g treatment after
Grain thing, 64.0g deionized waters are uniformly sprayed with the speed of 30mL/ minutes to gained alumina support, are sprayed
With the speed of 4.0g/ minutes to being uniformly added into glacial acetic acid 16.0g in foregoing deionized water while water drenching.Spray
To particulate matter saturated water absorption, 50 DEG C stand 1.0 hours.In 120 DEG C of dryings 2.0 hours, 850 DEG C
Roasting 3.0 hours, obtains carrier.Prepare and contain (12.5g MoO3+ 1.6g NiO)/100mL stable metal leaching
Stain liquid, impregnates in the method that saturation impregnates to resulting vehicle；Dipping resulting material is in vibrated fluidized bed
Predrying, 70 DEG C of hot blast temperature is carried out, it is 50% to control catalyst water content；Catalyst after predrying
It is placed in the water purification that temperature is 40 DEG C, soaks 20 minutes；Catalyst after washing is done in vibrated fluidized bed
It is dry, 120 DEG C of hot blast temperature, water content is 6% after drying；500 DEG C of constant temperature 3 hours, must urge in roaster
Agent A.Catalyst physical property is shown in Table 1.
Embodiment 2
It is molded according to preceding method and is dried, is processed 4 hours at 200 DEG C.After taking 100g treatment
Particulate matter, by 48.0g concentration for the acetum of 5.0wt% is uniformly sprayed onto material, finally by 32.0g
Concentration is uniformly sprayed onto resulting material for the acetum of 15.0wt%, and 20 DEG C stand 3.0 hours.With reality
Apply the identical method of example 1 to dry and be calcined, obtain carrier.Prepare and contain (18.8g WO3+0.6g NiO)/100mL
Stable metal maceration extract, with saturation impregnate method resulting vehicle is impregnated；Dipping resulting material exists
Predrying, 40 DEG C of hot blast temperature is carried out in vibrated fluidized bed, it is 60% to control catalyst water content；Predry
Catalyst after dry is placed in the water purification that temperature is 80 DEG C, is soaked 1 minute；Catalyst after washing is in shaking
Fluidized bed middle drying, 150 DEG C of hot blast temperature, water content is 4% after drying；400 DEG C of constant temperature in roaster
6 hours, obtain catalyst B.Catalyst physical property is shown in Table 1.
Embodiment 3
It is molded according to preceding method and is dried, is processed 1 hour at 450 DEG C.After taking 100g treatment
Particulate matter, by 28.0g concentration for the nitric acid of 1.0wt% is sprayed onto resulting material, continues 28.0g concentration
It is finally the nitric acid of 10.0wt% by 24.0g concentration for the salpeter solution of 5.0wt% is uniformly sprayed onto material
Solution is uniformly sprayed onto material, and 100 DEG C stand 0.5 hour.Method same as Example 1 dry and
Roasting, obtains carrier.Prepare and contain (9.4g WO3+6.3g MoO3+1.6g NiO+1.6g Co2O3)/100mL
Stable metal maceration extract, with saturation impregnate method resulting vehicle is impregnated；Dipping resulting material exists
Predrying, 100 DEG C of hot blast temperature is carried out in vibrated fluidized bed, it is 20% to control catalyst water content；Predry
Catalyst after dry is placed in the water purification that temperature is 20 DEG C, is soaked 60 minutes；Catalyst after washing is in shaking
Fluidized bed middle drying, 80 DEG C of hot blast temperature, water content is 7% after drying；650 DEG C of constant temperature in roaster
2 hours, obtain catalyst C.Catalyst physical property is shown in Table 1.
Embodiment 4
It is molded according to preceding method and is dried, is processed 2 hours at 350 DEG C.After taking 100g treatment
Particulate matter, is the uniform spray of 1.0wt% acetums on resulting material by 56.0g concentration, then will
24.0g concentration is uniformly sprayed onto material for the salpeter solution of 5.0wt%, and 70 DEG C stand 2.0 hours.With reality
Apply the identical method of example 1 to dry and be calcined, obtain carrier.Prepare and contain (6.3g MO3+6.3g NiO)/100mL
Stable metal maceration extract, with saturation impregnate method resulting vehicle is impregnated；Dipping resulting material exists
Predrying, 80 DEG C of hot blast temperature is carried out in vibrated fluidized bed, it is 40% to control catalyst water content；Predry
Catalyst after dry is placed in the water purification that temperature is 60 DEG C, is soaked 15 minutes；Catalyst after washing is in shaking
Fluidized bed middle drying, 110 DEG C of hot blast temperature, water content is 5% after drying；500 DEG C of constant temperature in roaster
3 hours, obtain catalyst D.Catalyst physical property is shown in Table 1.
Comparative example 1-2 illustrates existing method and the catalyst prepared by existing method.
Comparative example 1
Carrier is obtained according to the method described by CN104646005 in this comparative example, conventional method gold-supported
Category.
It is molded according to preceding method and is dried, in 850 DEG C of constant temperature 3 hours, is obtained carrier.Take 100g
Carrier after roasting, 64.0g deionized waters is uniform to gained alumina support with the speed of 30mL/ minutes
Spray, with the speed of 4.0g/ minutes to being uniformly added into glacial acetic acid in foregoing deionized water while shower water
16.0g.After being sprayed to particulate matter saturated water absorption, 50 DEG C of closed processes 1.0 hours, water purification is washed 3 times.
In 200 DEG C of dryings 3.0 hours, carrier is obtained.Prepare and contain (10.0g MoO3+ 1.3g NiO)/100mL
Stable metal maceration extract, impregnates, 120 in air dry oven in the method that saturation impregnates to resulting vehicle
DEG C drying 3 hours, 500 DEG C of constant temperature 3 hours, obtains catalyst E in roaster.Catalyst physical property is shown in Table 1.
Comparative example 2
Carrier is conventionally obtained in this comparative example, and Metal Supported enters according to CN101927196 methods
OK.
It is molded according to preceding method and is dried, in 850 DEG C of constant temperature 3 hours, is obtained carrier.Successively
To contain (10.7g MoO3+ 1.3g NiO)/100mL metallic solution and contain (7.4g MoO3+0.9g NiO)
The metallic solution of/100mL is sprayed to carrier, until saturation.120 DEG C of dryings 3 in air dry oven
Hour, 500 DEG C of constant temperature 3 hours, obtains catalyst F in roaster.Catalyst physical property is shown in Table 1.
Embodiment 5
This example is the physicochemical property and Activity evaluation of each example catalyst of the above.
Using BET, the analysis method such as SEM-EDX, XRF is analyzed to catalyst physical property, as a result
It is shown in Table 1.
The catalyst physico-chemical property of table 1
| Catalyst | A | B | C | D | E | F |
| 135 | 132 | 135 | 136 | 130 | 137 | |
| Pore volume, mL/g | 0.67 | 0.64 | 0.69 | 0.68 | 0.60 | 0.56 |
| 8.1 | 12.0 | 10.2 | 4.0 | 8.0 | 7.9 | |
| 1.0 | 0.4 | 2.0 | 4.0 | 1.0 | 1.0 | |
| Average pore diameter, nm | ||||||
| Outer surface -80%R* | 24.8 | 25.4 | 28.8 | 22.2 | 19.2 | 16.4 |
| 50%R- centers | 18.8 | 18.3 | 20.4 | 18.1. | 17.8 | 16.4 |
| Metal component is distributed | ||||||
| Outer surface/center | 0.32 | 0.58 | 0.47 | 0.44 | 1.0 | 0.51 |
| 0.66R/ centers | 0.55 | 0.76 | 0.64 | 0.59 | 1.0 | 0.72 |
| 0.33R/ centers | 0.78 | 0.92 | 0.88 | 0.86 | 1.0 | 0.84 |
* R is the particle radius of the catalyst with catalyst granules center as initial point
The result of table 1 shows, compared with comparative example, catalyst prepared by the inventive method is provided simultaneously with hole
Footpath gradient increase feature and active metal gradient reduce distribution characteristics, and pore volume, aperture are bigger, and duct is more
For open, Metal Distribution gradient is more excellent.
Activity stability evaluation is carried out to the catalyst of table 1, appreciation condition is shown in Table 2, and evaluation result is shown in Table 3.
The evaluating catalyst condition of table 2
| Raw material oil nature | Middle East residual oil |
| 0.99 | |
| S, % | 4.1 |
| 103 | |
| Process conditions | |
| Reaction temperature, DEG C | 385 |
| Hydrogen dividing potential drop, MPa | 16 |
| 0.85 | |
| Hydrogen/oil ratio | 750 |
The evaluating catalyst result of table 3
Known by the evaluation result of table 3, catalyst of the present invention is steady with de- impurity activity and more excellent activity higher
It is qualitative.
Claims (3)
1. a kind of catalyst for hydrotreatment of residual oil, it is characterised in that
Pore volume is 0.2~1.2mL/g；
Specific surface area is 40~200m2/g；
Average pore diameter is in radially gradually to increase from center to outer surface along carrier granular, from granular center to grain
Average pore diameter 3~the 10nm small compared with the average pore diameter of particle diameter 80% to surface portion of the part of footpath 50%；
With aluminum oxide as carrier, molybdenum and/or tungsten containing total catalyst weight 4-12% in catalyst and
The cobalt of 0.4-4% and/or the oxide of nickel；
Metal component concentration is gradually decreased from granular center to outside table in catalyst granules；Outside catalyst granules
The ratio between surface and center weight metal are 0.05-0.60, are with the ratio between center weight metal at 0.66R
With the ratio between center weight metal it is 0.60-0.95 at 0.40-0.80,0.33R, R is with catalyst granules
The heart is the particle radius of the catalyst of initial point.
2. a kind of preparation method of catalyst for hydrotreatment of residual oil, it is that residual oil described in claim 1 adds
Hydrogen processes the preparation method of catalyst, comprises the following steps：
1) aluminum oxide precursor and peptizing agent, the abundant kneading of water, be molded and dry；
2) particulate matter to 1) middle gained carries out preroast 1~4 hour at 200-450 DEG C；
3) particulate matter to 2) middle gained uniformly sprays acid or the acid solution that concentration is increased continuously, or spray
Concentration two or more sour or acid solution from low to high is drenched, 0.5~3 hour is stood at 20-100 DEG C；It is dry
It is dry and be calcined, obtain carrier；
4) metallic solution containing molybdenum and/or tungsten and nickel and/or cobalt is prepared, and resulting vehicle is impregnated with saturation
Mode carried metal；
5) predrying, hot blast temperature is carried out to the particulate matter of 4) middle gained using vibra fluidized bed drying equipment
At 40-100 DEG C, the final water content control of catalyst is in 20-60% for control；
6) resulting material in 5) is dipped in water purification, immerses time 1-60 minute, 20-80 DEG C of water purification temperature；
7) step 6) in material after washing at 80-150 DEG C through vibra fluidized bed drying, control water contains
Amount is less than 8%, is then calcined 2-6 hours at 400-650 DEG C, contains in catalyst and accounts for total catalyst weight
The molybdenum and/or tungsten of 4-12% and the cobalt of 0.4-4% and/or the oxide of nickel.
3. the preparation method of catalyst for hydrotreatment of residual oil according to claim 2, it is characterised in that
Step 3) described in acid or acid solution be nitric acid or acetic acid and its solution.
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