CN105983413B - Preparation method of high-activity residual oil hydrogenation catalyst - Google Patents
Preparation method of high-activity residual oil hydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 230000000694 effects Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 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 36
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 30
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 3
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 3
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 3
- 150000003658 tungsten compounds Chemical class 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract 2
- 239000002893 slag Substances 0.000 claims description 18
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910000765 intermetallic Inorganic materials 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- -1 rare earth compound Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
A preparation method of a high-activity residual oil hydrogenation catalyst comprises the following steps: with Al2O3Mixing rare earth compound, active metal compound and deionized water or ammonia water as carrier to obtain metal dipping solution, and preparing the additive by saturated dipping methodThe method comprises the steps of hydrogenating a catalyst, drying the catalyst at 70-160 ℃ for 1-9 hours, roasting the catalyst in air at 280-650 ℃ for 1-7 hours, and finally obtaining a rare earth metal oxide and a catalyst with active metal oxides distributed on the surface of the catalyst at intervals, wherein the active metal compounds are at least one selected from the group consisting of molybdenum compounds, tungsten compounds, nickel compounds and cobalt compounds, and the active metal oxides are selected from MoO3、WO3At least one of the group consisting of CoO and NiO.
Description
Technical field
The present invention relates to a kind of preparation methods of high activity slag oil hydrogenation catalysts.Especially heavy, residuum hydrodesulfurization and
Hydrodenitrogeneration, carbon residue catalyst and preparation method thereof.
Background technique
The in short supply and in poor quality of global petroleum resources leads on Crude Oil Market the ratio of heavy crude and sour crude not
It is disconnected to improve；Increasingly strict with China's rapid development of economy and environmental regulation simultaneously, market also exists to clear gusoline demand
Rapidly increase.Therefore, light materialization of heavy oil and high quality are current vital tasks urgently to be solved.Residual hydrocracking technology is
A kind of effective means to solve the above problems.In existing residual hydrogenation technology, fixed bed residual hydrogenation technology is the most mature,
It is most widely used.In usual fixed bed residual hydrogenation reaction, when oil product passes through protective agent bed, metal remover bed, desulfurizing agent
After bed, most of metal and sulphur are effectively removed, but remaining impurity high stability, are in particular in current industrial application
Fixed bed residual hydrogenation equipment end reactor latter end transformation efficiency is low, and denitrogenation and de- carbon residue are not ideal enough, this is to catalyst grade
Activity and activity stability with middle end loading catalyst propose high request.
CN103480390A provides a kind of catalyst and its preparation method and application with hydrogenation catalyst effect, this is urged
Agent contains carrier and loads at least one group VIII metallic element on the carrier and at least one group VIB
Metallic element, the carrier are hydrated alumina forming matter, by containing rare earth member containing at least one hydrated alumina, at least one
The compound of element and the raw material of at least one cellulose ether are made.Catalyst according to the invention is in hydrocarbon ils (especially heavy hydrocarbon
Oil) hydrodemetallization reaction in show higher catalytic activity, better catalytic stability and longer service life.
CN1352227A discloses a kind of hydrotreating catalyst and preparation method thereof, especially heavy oil hydrodesulfurization and is catalyzed
Agent and preparation method thereof.The invention is using a kind of cheap and environmental-friendly Ti-contained aluminium hydroxide carrier.Pass through titaniferous hydrogen-oxygen
Change the materials such as aluminium and metallic salt kneading process, promote metal dispersion, all materials after kneading is at plastic, extrusion at
Catalyst is made through high-temperature activation in type.The shaping of catalyst of preparation is easy, and Acidity is suitable for, while having excellent plus hydrogen de-
Sulphur and preferable hydrodenitrogeneration and removal of ccr by hydrotreating activity.But it uses full kneading mode to prepare catalyst, active metal point
Divergence, specific surface area of catalyst and pore volume room for promotion are all little, and then the activity for influencing catalyst improves.
Rare earth is introduced into catalyst by the present invention using impregnation method, can improve the stable structure of carrier in catalyst
Property, guarantee that it keeps high specific surface area during the reaction, and the dispersion performance of Ni, Mo isoreactivity component can be improved, two sides
Face improves the activity and activity stability of catalyst.
Summary of the invention
The purpose of the present invention is in the impregnation step by rare earth and active metal synchronize be introduced into catalyst, improve and urge
The structural stability of carrier in agent, makes it keep high specific surface area during the reaction；In addition, also improving in catalyst
The dispersion performance of active component, two aspect effects have achieved the purpose that improve catalyst activity and activity stability.It solves
Have in technology of preparing, residual oil hydrocatalyst desulfurization, denitrogenation, de- carbon residue activity improve the limited problem in space.
The present invention provides a kind of preparation method of high activity slag oil hydrogenation catalysts, comprising the following steps: with Al2O3To carry
Rare earth compound, active metallic compound and deionized water or ammonium hydroxide are mixed and made into metal impregnation solution, controlled molten by body
Liquid pH value is 3~10, prepares hydrogenation catalyst using the method for saturation dipping, then dry 1~9h at 70~160 DEG C, then
1~7h is roasted in 280~650 DEG C of air, finally obtains rare-earth oxide, reactive metal oxides in catalyst surface
On the catalyst that is spaced apart, the active metallic compound is selected from by molybdenum compound, tungsten compound, nickel compound, cobalt chemical combination
At least one of the group that object is constituted, the reactive metal oxides are selected from by MoO3、WO3, the group that is constituted of CoO and NiO
At least one of group.
The preparation method of high activity slag oil hydrogenation catalysts of the present invention, wherein rare earth compound preferably contains La
And/or the compound of Ce.
The preparation method of high activity slag oil hydrogenation catalysts of the present invention, wherein preferably activity in catalyst
Metal oxide accounts for the 1~14% of total catalyst weight.
The preparation method of high activity slag oil hydrogenation catalysts of the present invention, wherein with overall catalyst weight meter, activity
Metal oxide MoO3And/or WO3Preferably 3~11%.
The preparation method of high activity slag oil hydrogenation catalysts of the present invention, wherein with overall catalyst weight meter, activity
Metal oxide CoO and/or NiO are preferably 0.5~6%, and more preferably 0.8~4.5%.
The preparation method of high activity slag oil hydrogenation catalysts of the present invention, wherein with overall catalyst weight meter, catalysis
Rare-earth oxide La in agent2O3And/or Ce2O3Preferably 0.1~3%.
The preparation method of high activity slag oil hydrogenation catalysts of the present invention, wherein maturing temperature is 400~
560℃。
The preparation method of high activity slag oil hydrogenation catalysts provided by the invention, using aluminium oxide as carrier, from VI B and/
Or VIII the oxide of race be active component, preferably Mo and/or W or Ni and/or Co, by a small amount of rare earth oxide, preferably La and/or
Ce is introduced in solution impregnation steps, is distributed to the surfaces externally and internally of catalyst.Gained catalyst has high removing sulphur, nitrogen, residual
The impurity ability such as charcoal.
By hydrogenation catalyst prepared by the method for the present invention, have a characteristic that
1) using aluminium oxide as carrier；
2) 0.3~2.0ml/g of Kong Rongwei, preferably 0.45~1.4ml/g；
3) specific surface is 50~280m2/ g, preferably 110~260m2/g；
4) active metal component accounts for the 1~14% of total catalyst weight in catalyst, preferably 3~11% MoO3With/
Or WO3And/or 0.5~6% CoO and/or NiO, preferably 0.8~4.5% CoO and/or NiO；La in catalyst2O3With/
Or Ce2O3Account for the 0.1~3% of total catalyst weight.
Effect of the invention:
In catalyst preparation process, rare earth is introduced in solution impregnation steps, is distributed to the surfaces externally and internally of alumina catalyst support,
The anti-caking power for improving carrier slows down the decline of catalyst specific surface area in reaction；Meanwhile it can effectively prevent nickel molybdenum
Isoreactivity component enters aluminium oxide lattice, also, due to rare earth oxide be distributed in Mo and/or W or Ni and/or Co oxide it
Between, the interval of active component is increased, the dispersibility of active component is improved, and then improves the desulfurization of catalyst, nitrogen, carbon residue
Equal impurity ability, furthermore preparation process is simple, has wide practical use in mink cell focus field of hydrogenation.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Rare earth compound:
In the present invention, rare earth compound is not particularly limited, the usual rare earth compound is containing La's and/or Ce
Compound.
Reactive metal oxides:
In the present invention, reactive metal oxides content is not particularly limited, active metal aoxidizes in usual catalyst
Object accounts for the 1~14% of total catalyst weight, if reactive metal oxides account for total catalyst weight less than 1%, due to active group
Divide content less, causes catalyst activity very low；And it is more than 14% that reactive metal oxides, which account for total catalyst weight, causes activity
Component waste, and will appear more metal oxide blocking catalyst duct, activation plays are influenced, have no other beneficial to effect
Fruit.
MoO3And/or WO3Content:
In the present invention, to MoO3And/or WO3Content is not particularly limited, usual reactive metal oxides MoO3And/or
WO33~11% are accounted for, if reactive metal oxides MoO3And/or WO3Content causes catalyst activity very low less than 3%；And it lives
Property metal oxide MoO3And/or WO3It greater than 11%, causes to waste, and will appear more metal oxide blocking catalyst hole
Road influences activation plays, has no other beneficial effects.
The content of reactive metal oxides CoO and/or NiO:
In the present invention, the content of reactive metal oxides CoO and/or NiO are not particularly limited, usually with catalyst
Total weight, reactive metal oxides CoO and/or NiO account for 0.5~6%, if reactive metal oxides CoO and/or NiO are accounted for
Total catalyst weight is less than 0.5%, since active component content is less, causes catalyst activity very low；And active metal aoxidizes
It is more than 6% that object CoO and/or NiO, which account for total catalyst weight, causes active component to waste, and will appear more metal oxide
Blocking catalyst duct, influences activation plays, has no other beneficial effects.
Rare Earths in Catalyst metal oxide La2O3And/or Ce2O3Content:
In the present invention, to rare-earth oxide La2O3And/or Ce2O3Content is not particularly limited, usually with catalysis
Agent total weight, Rare Earths in Catalyst metal oxide La2O3And/or Ce2O30.1~3% is accounted for, if rare-earth oxide
La2O3And/or Ce2O3Content causes active metal dispersion degree relatively low less than 0.1%；And rare-earth oxide La2O3And/or
Ce2O3It greater than 3%, causes to waste, and is easy to influence the dipping of active metal, influence catalyst activity, have no other beneficial to effect
Fruit.
Maturing temperature:
In the present invention, maturing temperature is not particularly limited, the usual maturing temperature is 400~560 DEG C, if roasting
Temperature is burnt less than 400 DEG C, since maturing temperature is too low, causes metal active constituent activation bad, influences catalyst activity, and is roasted
It burns temperature and is greater than 560 DEG C, since maturing temperature is excessively high, causes metal active component dispersion on catalyst to reduce, influence to be catalyzed
Agent activity, has no other beneficial effects.
Embodiment 1
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component for Mo, Ni
Catalyst.150g carrier is weighed, sprays 150mL ammonium molybdate containing 15.13g (containing MoO382m%), 7.21g nickel nitrate (contains NiO
25.2m%), 2.75g lanthanum nitrate (contains La2O3Mixed liquor 36m%), wherein the pH of mixed liquor is 6, is homogenized in spraying equipment
After 15 minutes, 2h is dried at 110 DEG C, roasts 2h in 550 DEG C of air atmospheres, catalyst is made, is denoted as C1, contains in catalyst
7.51% MoO3, 1.1% NiO, 0.6% La2O3。
Embodiment 2
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component for Mo, Ni
Catalyst.150g carrier is weighed, sprays 150mL ammonium molybdate containing 21.52g (containing MoO382m%), 21.01g nickel nitrate (contains NiO
25.2m%), 9.80g lanthanum nitrate (contains La2O3(wherein the mixed liquor joined 2mL concentration in configuration and is mixed liquor 36m%)
10% ammonium hydroxide, so that pH value of solution is 9), after being homogenized 15 minutes in spraying equipment, 3h, 450 DEG C of air to be dried at 100 DEG C
4h is roasted in atmosphere, catalyst is made, and is denoted as C2,10% MoO is contained in catalyst3, 3% NiO, 2% La2O3。
Embodiment 3
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component for Mo, W, Co
Catalyst.150g carrier is weighed, sprays 150mL ammonium molybdate containing 10.63g (containing MoO382m%), 10.63g ammonium metatungstate (contains
WO382m%), 20.76g cobalt nitrate (25.2m% containing CoO), 4.83g cerous nitrate (contain Ce2O3Mixed liquor 36.1m%), wherein
The pH of mixed liquor is 7, after being homogenized 15 minutes in spraying equipment, the dry 3h at 100 DEG C, is roasted in 650 DEG C of air atmospheres
Catalyst is made in 1.5h, is denoted as C3,5% MoO is contained in catalyst3, 5% WO3, 3% CoO, 1% Ce2O3。
Embodiment 4
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component urging for W, Co
Agent.150g carrier is weighed, sprays 150mL ammonium metatungstate containing 9.85g (containing WO382m%), 12.8g cobalt nitrate (contains CoO
25.2m%), 0.90g lanthanum nitrate (contains La2O3Mixed liquor 36m%), wherein the pH of mixed liquor is 10, is homogenized in spraying equipment
After 15 minutes, 3h is dried at 160 DEG C, roasts 6h in 280 DEG C of air atmospheres, catalyst is made, is denoted as C4, contains in catalyst
5% WO3, 2% CoO, 0.2% La2O3。
Embodiment 5
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component for Mo, Ni
Catalyst.150g carrier is weighed, sprays 150mL ammonium molybdate containing 6.1g (containing MoO382m%), 39.7g nickel nitrate (contains NiO
25.2m%), 4.62g cerous nitrate (contains Ce2O3Mixed liquor 36.1m%), wherein the pH of mixed liquor is 8, in spraying equipment
After changing 15 minutes, 3h is dried at 80 DEG C, roasts 5h in 400 DEG C of air atmospheres, catalyst is made, is denoted as C1, contains in catalyst
3% MoO3, 6% NiO, 1% Ce2O3。
Embodiment 6
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component for Mo, Ni
Catalyst.150g carrier is weighed, sprays 150mL ammonium metatungstate containing 24.24g (containing WO382m%), 21.51g nickel nitrate (contains NiO
25.2m%), 10.04g lanthanum nitrate (contains La2O336m%), 5.0g cerous nitrate (contains Ce2O3Mixed liquor 36.1m%), wherein mixing
The pH for closing liquid is 9, after being homogenized 15 minutes in spraying equipment, the dry 9h at 70 DEG C, roasts 2h in 550 DEG C of air atmospheres, makes
Catalyst is obtained, C1 is denoted as, 11% WO is contained in catalyst3, 3% NiO, 2% La2O3, 1% Ce2O3。
Comparative example 1
Using aluminium oxide as carrier, water absorption rate 1.0mL/g.Use saturation dipping method preparation active component for Mo, Ni
Catalyst.150g carrier is weighed, sprays 150mL ammonium molybdate containing 21.02g (containing MoO382m%), 20.52g nickel nitrate (contains NiO
Ammonia spirit 25.2m%) after being homogenized 15 minutes in spraying equipment, 3h is dried at 100 DEG C, is roasted in 450 DEG C of air atmospheres
4h is burnt, catalyst is made, D1 is denoted as, 10% MoO is contained in catalyst3, 3% NiO.
Comparative example 2
Referring to the catalyst that CN1352227A embodiment 1 is prepared, it is denoted as D2, contains 7.51MoO in catalyst3, 1.1%
NiO, 0.89% P2O5。
Comparative example 3
The catalyst that CN103480390A embodiment 1 is prepared is denoted as D3, contains 7.51MoO in catalyst3, 1.1%
NiO, 0.89% P2O5。
The physico-chemical property of catalyst and its contrast medium provided by the present invention, is shown in Table 1.
Catalyst property obtained by 1 embodiment of the present invention of table and comparative example
Embodiment 7
Hydrogenation of the present embodiment to illustrate catalyst provided by the present invention, and compared with contrast medium.In 100mL
It is evaluated on small fixed hydrogenation plant.Evaluation raw material oil nature is shown in Table 2.
2 test raw material oil main character of table
| Density (20 DEG C), kg/m3 | 968.2 |
| (Ni+V),μg/g | 110 |
| Sulphur, % | 4.50 |
| Nitrogen, μ g/g | 1900 |
| Carbon residue, % | 18.8 |
Evaluation condition is as shown in table 3.
Table 3 evaluates process conditions
| Pressure, MPa | 15 |
| Hydrogen-oil ratio (volume) | 1000 |
| Reaction temperature, DEG C | 385 |
| Liquid hourly space velocity (LHSV), h- 1 | 0.4 |
De- percentage of admixture when opposite desulfurization degree, denitrification percent, de- carbon yield are with C1 catalyst runs 500h makees benchmark for 1.0
Compare and obtains.Catalyst activity and stability contrast the results are shown in Table 4.As can be seen from Table 4, as the duration of runs extends, C1 is urged
The opposite desulfurization degree of agent, takes off carbon yield obviously higher than D2 catalyst, the opposite desulfurization degree of C2 catalyst, denitrogenation at denitrification percent
Rate, de- carbon yield are obviously higher than D1 catalyst；The opposite desulfurization degree of C1 catalyst, denitrification percent, de- carbon yield and activity stabilized
Property obviously higher than D3 catalyst, this is because C1 specific surface area of catalyst is much larger than D3 catalyst, the dispersion of active component
Property be higher than D3 catalyst, active utilization rate is high.Show that high desulfurization, nitrogen and carbon residue are living using catalyst prepared by the present invention
Property and good activity stability.
4 catalyst activity of table and stability contrast
Claims (8)
1. a kind of preparation method of high activity slag oil hydrogenation catalysts, comprising the following steps: with Al2O3For carrier, by rare earth chemical combination
Object, active metallic compound and deionized water or ammonium hydroxide are mixed and made into metal impregnation solution, control metal impregnation solution ph
It is 3~10, hydrogenation catalyst is prepared using the method for saturation dipping, then dry 1~9h at 70~160 DEG C, then 280~
1~7h is roasted in 650 DEG C of air, finally obtains rare-earth oxide, reactive metal oxides are spaced on catalyst surface
The catalyst of distribution, the active metallic compound are selected from by molybdenum compound, tungsten compound, nickel compound, cobalt compound institute structure
At at least one of group, the reactive metal oxides are selected from by MoO3、WO3, in the group that is constituted of CoO and NiO
It is at least one.
2. the preparation method of high activity slag oil hydrogenation catalysts according to claim 1, it is characterised in that: the rare earth
Conjunction object is the compound containing La and/or Ce.
3. the preparation method of high activity slag oil hydrogenation catalysts according to claim 1 or 2, it is characterised in that: catalyst
Middle reactive metal oxides account for the 1~14% of total catalyst weight.
4. the preparation method of high activity slag oil hydrogenation catalysts according to claim 3, it is characterised in that: total with catalyst
Poidometer, reactive metal oxides MoO3And/or WO3Account for 3~11%.
5. the preparation method of high activity slag oil hydrogenation catalysts according to claim 1 or 2, it is characterised in that: with catalysis
Agent total weight, reactive metal oxides CoO and/or NiO account for 0.5~6%.
6. the preparation method of high activity slag oil hydrogenation catalysts according to claim 5, it is characterised in that: total with catalyst
Poidometer, reactive metal oxides CoO and/or NiO account for 0.8~4.5%.
7. the preparation method of high activity slag oil hydrogenation catalysts described according to claim 1 or 2 or 4 or 6, it is characterised in that:
With overall catalyst weight meter, Rare Earths in Catalyst metal oxide La2O3And/or Ce2O3Account for 0.1~3%.
8. the preparation method of high activity slag oil hydrogenation catalysts described according to claim 1 or 2 or 4 or 6, it is characterised in that:
The maturing temperature is 400~560 DEG C.
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| CN101423775A (en) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | Selective nickel hydrogenation catalyst and preparation method thereof |
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| CN102284300A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Inferior diesel oil hydrotreating catalyst and preparation method thereof |
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| US3531396A (en) * | 1968-06-25 | 1970-09-29 | Texaco Inc | Hydrocracking in the presence of hydrogen containing a minor amount of carbon monoxide |
| CN1102448C (en) * | 1999-09-29 | 2003-03-05 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
| JP2003200054A (en) * | 2001-11-05 | 2003-07-15 | Catalysts & Chem Ind Co Ltd | Hydrogenation treatment catalyst for hydrocarbon oil and method for manufacturing the same |
| CN101722006A (en) * | 2009-11-24 | 2010-06-09 | 山东齐鲁科力化工研究院有限公司 | Dual-functional hydrogenation catalyst |
| CN104096584B (en) * | 2013-04-03 | 2016-11-09 | 中国石油天然气股份有限公司 | Residual oil hydrogenation catalyst and preparation method thereof |
| CN104107694A (en) * | 2013-04-17 | 2014-10-22 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst, preparation method and application thereof |
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| CN101423775A (en) * | 2007-11-01 | 2009-05-06 | 中国石油天然气股份有限公司 | Selective nickel hydrogenation catalyst and preparation method thereof |
| CN101927196A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient decreasing distribution and preparation method thereof |
| CN102284300A (en) * | 2010-06-21 | 2011-12-21 | 中国石油天然气股份有限公司 | Inferior diesel oil hydrotreating catalyst and preparation method thereof |
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