CN106140180B - A kind of heavy-oil hydrogenation catalyst and preparation method thereof - Google Patents
A kind of heavy-oil hydrogenation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of heavy-oil hydrogenation catalysts, include the alumina support and hydrogenation active metals of sheet polycrystalline gamma-alumina composition；The property of wherein sheet polycrystalline gamma-alumina is as follows：Grain size is 100 600nm, and thickness is 40 100nm, and sheet polycrystalline gamma alumina particle is made of the gamma-alumina crystal grain of 5 40nm.The preparation method of the catalyst is as follows：Sheet γ polycrystal aluminas original powder is added in into binding agent, extrusion aid kneading, molding, drying and roasting, obtains alumina support；Using conventional method on the alumina support of gained supported active metals.Heavy-oil hydrogenation catalyst of the present invention has perforative macroporous structure, and higher porosity, the mesoporous distribution of concentration, mass transfer diffusion is excellent, has broad application prospects in weight, residual hydrogenation catalysis reaction.
Description
Technical field
The present invention relates to a kind of heavy-oil hydrogenation catalysts and preparation method thereof.
Background technology
With increasingly heaviness, the in poor quality of crude oil, oil refining enterprise faces a large amount of weight, Residual cracking Utilizing question.Weight,
Residual oil molecule has complicated three-dimensional structure, and sulfur-bearing condensed-nuclei aromatics side chain frequently forms steric hindrance, interferes in five, hexatomic ring
Sulphur atom is adsorbed by catalyst active center.In catalytic hydrogenation, heavy oil macromolecules adsorption and the table for being deposited on catalyst
Face or aperture increase reaction inside diffusional resistance, the apparent activity of catalyst are caused to decline.Meanwhile containing more in weight, residual oil
Coke precursor, they can generate coke and be deposited under certain condition causes the activated centre of catalyst to be poisoned in hole.
Diffused into catalyst attach most importance to, the governing factor of residual oil catalytic hydrogenation, therefore again, the catalytic hydrogenation of residual oil macropore is needed to urge
Agent, and with larger aperture and Kong Rong, to accommodate more carbon deposits, metal deposit etc., reduce macromolecular reaction and meet
The diffusional resistance arrived.The large aperture of catalyst and hole, which hold, mainly relies on the carrier that corresponding large aperture macropore holds.
The duct of catalyst derives from carrier, obtains the catalyst of different duct features, is entered from catalyst carrier first
Hand.Good macropore carrier is on pore-size distribution, in addition to the pore-size distribution that should have the 10-20nm more concentrated, should also have
Suitable big pore size distribution more than 50nm, to delay the macromolecular blocking in aperture and the more carbon deposits of receiving, gold in the catalyst
Belong to deposit etc..Therefore, catalyst made of the carrier being distributed using big small-bore and the Based on Dual-Aperture deposited, has superior property
Energy.However, the aperture for being commonly used for preparing the aluminium oxide of hydrotreating catalyst is smaller, it is impossible to which satisfaction prepares heavy oil, residual oil adds
The needs of hydrogen catalyst for demetalation.Therefore macropore must be obtained using the method for reaming in preparation process.Common reaming
Method is to add in various types of expanding agents in the forming processes such as thin water aluminum oxide dry glue powder kneading, extrusion are intended.It uses at present
Physics expanding agent have the organic substances such as carbon black, carbon fiber, carbohydrate.
US4448896 is using carbon black as expanding agent, by it with boehmite kneading into plastic and extruded moulding.In carrier
In roasting process, expanding agent is oxidized, burning, is gradually escaped with gaseous state object, forms cavity in the carrier, larger so as to form
Duct.But amount of carbon blacks used in the patent is larger, commonly reaches more than 20wt%, the relatively low ability of mechanical strength of resulting vehicle, hole point
Cloth more disperse.British patent EP237240 uses carbon fiber to prepare macroporous aluminium oxide for expanding agent, but equally exists expanding agent
The deficiencies such as dosage is big and support strength is low.
CN96103297.9 in boehmite dry glue powder by adding in physics expanding agent such as carbon black and chemical enlargement agent
Such as phosphide, be molded by kneading method, resulting vehicle can several bore dias be 10 ~ 20nm.Thus when catalyst requirement needed for reaction
When carrier has dual duct and to have higher mechanical strength, such carrier just receives certain restrictions.
Common issue that above-mentioned patent is faced is in addition, carbon black, activated carbon fiber or other organic substance needs used
It is prepared by special technique.For example, mainly there are channel carbon black, high abrasion carbon black and acetylene method carbon black in the source of carbon black powder.
Macropore is virtually increased using this expanding agent prepared through special process to aoxidize.
In addition, for the design of industrial catalyst, should also have higher specific surface area, to make the work of catalyst
The concentration of property position is larger.However specific surface area pore size is often contradiction.In order to which deposit is inhibited to make the deposition in aperture
With larger hole being needed to be diffused, however larger hole generally means that relatively low specific surface area.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of heavy-oil hydrogenation catalyst and preparation method thereof.Present invention weight
The catalyst of oil hydrogenation catalysts has perforative macroporous structure, higher porosity, the mesoporous distribution of concentration, mass transfer diffusion
It has excellent performance, it is stronger for weight, residual hydrogenation catalytic desulfurization, denitrogenation and demetalization ability.
The heavy-oil hydrogenation catalyst of the present invention, alumina support and plus hydrogen work including sheet polycrystalline gama-alumina composition
Property metal；The property of wherein sheet polycrystalline gama-alumina is as follows：Grain size is 100-600nm, thickness 40-100nm, piece
Shape polycrystalline gamma-alumina particle is made of the gama-alumina crystal grain of 5-40nm.
The heavy-oil hydrogenation catalyst has following property：Porosity is 70%-90%, Kong Rongwei 0.8-2.0cm3/ g,
Specific surface area is 200-400m2/ g, mesoporous to be distributed as 5-50nm, distribution concentration degree is 70%-90%.
The hydrogenation active metals are VIB or group VIII metal element, and vib metals are preferably molybdenum and/or tungsten, the
The metal of VIII group is preferably cobalt and/or nickel.On the basis of the weight of catalyst, the content of group vib metal is calculated as with oxide
5.0wt%-25.0wt%, the content of group VIII metal are calculated as 1.0-5.0% with oxide.
The preparation method of the heavy-oil hydrogenation catalyst of the present invention, including following content：
Sheet γ-polycrystal alumina original powder is added in into binding agent, extrusion aid kneading, molding, drying and roasting, is aoxidized
Alumina supporter；Using conventional method on the alumina support of gained supported active metals；
The wherein preparation method of sheet γ-polycrystal alumina, includes the following steps：
（1）Inorganic aluminate, low-carbon alcohols and/or water, low-carbon epoxyalkane are uniformly mixed, formed gel, then by gel into
Row aging；
（2）By step（1）Obtained gel is impregnated with low-carbon alcohols, then dry, roasting；
（3）Step（2）Obtained material, which is immersed in ammonium hydroxide, carries out closed hydro-thermal process, and separation of solid and liquid is dry, obtains sheet
γ-polycrystal alumina original powder.
Step（1）In, the inorganic aluminate is water-soluble inorganic aluminium salt, in aluminium chloride, aluminum nitrate and aluminum sulfate
One or more, preferably aluminium chloride；Low-carbon alcohols are C5Following alcohol, in methanol, ethyl alcohol, normal propyl alcohol and isopropanol
It is one or more, more preferably ethyl alcohol and/or propyl alcohol；Low-carbon alcohols can be mixed with water with arbitrary proportion, preferably water/low-carbon alcohols
Mass ratio be 0.5-2.0.
Step（1）In, the carbon number of the low-carbon epoxyalkane is 2-4, preferably ethylene oxide and/or propylene oxide.
Step（1）In, step（1）Each component content in mixture, in terms of quality percentage：Inorganic aluminate 10%-60%, preferably
For 20%-35%, the total content of water and/or low-carbon alcohols is 30%-70%, and rest materials are low-carbon epoxyalkane.Low-carbon epoxyalkane
Meet following relationships with inorganic aluminate：With molar amount, low-carbon epoxyalkane/Al3+For 2.5-9, preferably 3.5-7.0.
Step（1）In, the aging temperature is 20-90 DEG C, and preferably 30-60 DEG C, ageing time is 1-72 hours, preferably
12-60 hours.
Step（2）In, the low-carbon alcohols are C5In following alcohol, preferably methanol, ethyl alcohol, normal propyl alcohol and isopropanol
It is one or more, preferably ethyl alcohol and/or propyl alcohol.
Step（2）In, the soaking conditions are：20-80 DEG C of temperature, preferably 30-60 DEG C, it is time 1-72 hour, excellent
It is selected as 12-60 hours.
Step（2）In, the drying temperature is not more than 200 DEG C, preferably not greater than 120 DEG C.
Step（3）In, the ammonia concn is 0.01-0.5mol/L, with molar amount, ammonium hydroxide/Al3+Ratio 0.5-
20, preferably 1.0-5.0；Handled material can be at least totally submerged by the volume of ammonium hydroxide.
Step（3）In, the closed hydrothermal condition is：Hydro-thermal process 1-12 hours at 130-180 DEG C.
Step（3）In, the drying temperature is no more than 200 DEG C, preferably not greater than 120 DEG C, degree of drying：It is warm herein
The lower material constant weight of degree.
The heavy-oil hydrogenation catalyst of the present invention, carrier are made of sheet polycrystalline gama-alumina, sheet polycrystalline gama-alumina
There is sheet-like morphology for gama-alumina second particle, gama-alumina second particle is made of little crystal grain of gama-alumina, shape
Into polycrystalline gama-alumina, therefore the activity of the irregular alumina particle of conventional polysilicon can be kept.Meanwhile sheet of the invention
Polycrystalline gama-alumina, it is disorderly arranged in carrier granular, continuous and larger porosity is formed, it is outstanding to be conducive to heavy oil macromolecular
It is colloid in residual oil, the mass transport process of asphalitine.Meanwhile uniformity is relatively on pattern and size for tabular alumina crystal grain
Height can significantly improve the centrality of the pore size distribution formed in carrier material by offspring, so as to improve catalyst
Catalytic performance.The heavy-oil hydrogenation catalyst of the present invention is applied to weight, residual hydrogenation reaction, and there is very strong hydrogenation catalyst to take off
Sulphur, denitrogenation and demetalization ability.
Description of the drawings
Fig. 1 is the stereoscan photograph of sheet gama-alumina prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope photo of sheet gama-alumina prepared by the embodiment of the present invention 1.
Fig. 3 is the X-ray diffraction of sheet gama-alumina prepared by the embodiment of the present invention 1（XRD）Spectrogram.
Fig. 4 is the pore size distribution$ figure of sheet gama-alumina prepared by the embodiment of the present invention 1.
Specific embodiment
The present invention is described in further detail with reference to embodiment.With the hole of mercury injection method test macroporous aluminium oxide
Rate.Specific surface area is measured using BET method, and mesoporous distribution concentration degree is measured using integrating peak areas method.Sheet gama-alumina particle
Size is measured according to scanning electron microscope image.The little crystal grain of sheet-like particle is formed by transmission electron microscope observing, observes its size range.
Crystal form is characterized using X-ray diffraction.
Sheet γ-polycrystal alumina, specific preparation method are as follows in alumina support of the present invention：
（1）Inorganic aluminate, low-carbon alcohols and/or water, low-carbon epoxyalkane are uniformly mixed, formed gel, then by gel into
Row aging；
The inorganic aluminate be water-soluble inorganic aluminium salt, one kind or more in aluminium chloride, aluminum nitrate and aluminum sulfate
Kind, preferably aluminium chloride；Low-carbon alcohols are C5Following alcohol, one kind or more in methanol, ethyl alcohol, normal propyl alcohol and isopropanol
Kind, more preferably ethyl alcohol and/or propyl alcohol；Low-carbon alcohols can be mixed with water with arbitrary proportion, preferably the mass ratio of water/low-carbon alcohols
For 0.5-2.0；The carbon number of the low-carbon epoxyalkane is 2-4, preferably ethylene oxide and/or propylene oxide；In mixture
Each component content, in terms of quality percentage：The total content of inorganic aluminate 10%-60%, preferably 20%-35%, water and/or low-carbon alcohols is
30%-70%, rest materials are low-carbon epoxyalkane.Low-carbon epoxyalkane meets following relationships with inorganic aluminate：With molar amount,
Low-carbon epoxyalkane/Al3+For 2.5-9, preferably 3.5-7.0；The aging temperature be 20-90 DEG C, preferably 30-60 DEG C, always
It is 1-72 hours, preferably 12-60 hours to change the time；
（2）By step（1）Obtained gel is impregnated with low-carbon alcohols, then dry, roasting；
The low-carbon alcohols are C5One kind or more in following alcohol, preferably methanol, ethyl alcohol, normal propyl alcohol and isopropanol
Kind, preferably ethyl alcohol and/or propyl alcohol；The soaking conditions are：20-80 DEG C of temperature, preferably 30-60 DEG C, the time, 1-72 was small
When, preferably 12-60 hours；The drying temperature is not more than 200 DEG C, preferably not greater than 120 DEG C.
（3）Step（2）Obtained material, which is immersed in ammonium hydroxide, carries out closed hydro-thermal process, and separation of solid and liquid is dry, obtains sheet
γ-polycrystal alumina original powder；
The ammonia concn is 0.01-0.5mol/L, with molar amount, ammonium hydroxide/Al3+Ratio 0.5-20, preferably
1.0-5.0；Handled material can be at least totally submerged by the volume of ammonium hydroxide；The closed hydrothermal condition is：130-180
Hydro-thermal process 1-12 hours at DEG C；Step（3）In, the drying temperature is not more than 200 DEG C, preferably not greater than 120 DEG C, does
Dry degree：Material constant weight at this temperature.
The specific preparation process of heavy-oil hydrogenation catalyst of the present invention is as follows：
Sheet γ-polycrystal alumina original powder is added in into binding agent, extrusion aid kneading, molding, drying and roasting, is aoxidized
Alumina supporter；Using conventional method on the alumina support of gained supported active metals；
Binding agent used is one or more of nitric acid, phosphoric acid, Aluminum sol, Ludox and citric acid；Described helps
Crowded agent is one or more of dried starch, sesbania powder and graphite；After being wherein molded the shape of carrier include but not limited to it is spherical,
Bar shaped, cylinder, clover, bunge bedstraw herb, tooth ball and other abnormity；Described is shaped to conventional shaping method, such as extruded moulding
Deng.The drying temperature is not more than 200 DEG C, and preferably not greater than 120 DEG C, drying time is 5-24 hours；The roasting
Condition is：400-750 DEG C roasts 1-12 hours, and preferably 500-650 DEG C roasts 3-6 hours；The carrier original powder material drying
Afterwards, it can not also roast.
Carrying method conventional in the prior art, preferably infusion process can be used in the load of catalyst activity metal of the present invention,
Can be saturation leaching, excessive leaching or complexing leaching, i.e., with the solution impregnated catalyst carrier containing required active component, after dipping
Then carrier is roasted 2~7 hours at 500 DEG C~800 DEG C, final catalyst is made in 80 DEG C~130 DEG C dryings 1~12 hour.
Embodiment 1
By water, absolute ethyl alcohol, aluminium chloride mix, add propylene oxide and be uniformly mixed, mixture each component by weight,
Content is respectively：Water 23%, ethyl alcohol 23%, aluminium chloride 20%, propylene oxide 34%.After mixing, gained gel is old at 30 DEG C
Change 60 hours, then impregnate the gel after aging with ethyl alcohol, impregnated 60 hours at 30 DEG C.After remove liquid phase, at 120 DEG C
Drying is until apparent loss of weight no longer occurs for product.Then it is roasted 6 hours at 500 DEG C, is cooled to room temperature, then be immersed in excess
The 0.01M at least flooding it completely ammonium hydroxide in (with molar amount, ammonium hydroxide/Al3+Ratio be 5.0), it is then closed and rise
Temperature was to 135 DEG C of hydro-thermal process 12 hours.Product dried at 120 DEG C is roasted 3 hours at 650 DEG C, through scanning after cooling
Electronic Speculum is observed it is found that product morphology shows as sheet, size 100-400nm, thickness 36nm.By sample grinding and ultrasound
After dispersion, with transmission electron microscope observing it is found that sheet-like particle is made of the more little crystal grain of 8-30nm.At simply grinding and be ultrasonic
Reason can not possibly destroy single crystal grain, therefore sheet-like particle is not large single crystal crystal grain.The XRD of product the result shows that, be gamma oxidation
Aluminium.Therefore, sheet-like particle is polycrystalline gama-alumina.Physical absorption test shows its relatively narrow mesoporous point with 8-20nm
Cloth.
Embodiment 2
At room temperature, by water, absolute ethyl alcohol, aluminium chloride mix, add propylene oxide and be uniformly mixed, mixture each component with
Weight meter, content are respectively：Water 15%, ethyl alcohol 20%, aluminium chloride 35%, propylene oxide 30%.Be uniformly mixed after, gained gel in
Then the mixture after aging is impregnated in aging 48 hours at 40 DEG C with propyl alcohol, temperature is 40 DEG C, and the time is 48 hours, after
Liquid phase is removed, drying is until apparent loss of weight no longer occurs for product at 100 DEG C.Then it roasts 6 hours, is cooled at 600 DEG C
Room temperature, then be immersed in the ammonium hydroxide of the excessive 0.1M at least flooding it completely (with molar amount, ammonium hydroxide/Al3+Ratio is
2.0) it is, then closed and be warming up to 150 DEG C of hydro-thermal process 5 hours.It is small that product dried at 100 DEG C is roasted at 550 DEG C to 5
When.After cooling, scanning electron microscopic observation it is found that product morphology be sheet, size 254nm, thickness 41nm.Sample is ground
And after ultrasonic disperse, with transmission electron microscope observing it is found that sheet-like particle is made of the little crystal grain of 10-25nm.The XRD result tables of product
It is bright, it is gama-alumina.So sheet-like particle is polycrystalline gama-alumina.Physical absorption test shows it with 10-21nm
Relatively narrow mesoporous distribution.
Embodiment 3
At room temperature, by water, absolute ethyl alcohol, aluminium chloride mix, add propylene oxide and be uniformly mixed, mixture each component with
Weight meter, content are respectively：Water 30%, ethyl alcohol 23%, aluminium chloride 25%, propylene oxide 22%.Be uniformly mixed after, gained gel in
Then the mixture 24 hours after agings is impregnated in aging 12 hours at 60 DEG C with 60 DEG C of ethyl alcohol, remove liquid phase later, at 120 DEG C
Drying is until apparent loss of weight no longer occurs for product.Then it is roasted 5 hours at 550 DEG C, is cooled to room temperature, then be immersed in excess
The 0.3M at least flooding it completely ammonium hydroxide in (with molar amount, ammonium hydroxide/Al3+Ratio be 3.0), it is then closed and heat up
To 165 DEG C of hydro-thermal process 9 hours.Product dried at 120 DEG C is roasted 8 hours at 500 DEG C, scanning electron microscope is seen after cooling
Examine it is found that product morphology be sheet, size 542nm, thickness 89nm.After sample grinding and ultrasonic disperse, with transmission electricity
Sem observation is it is found that sheet-like particle is made of the little crystal grain of 10-35nm.The XRD of product the result shows that, be gama-alumina, therefore
Sheet-like particle is polycrystalline gama-alumina.Physical absorption test shows its relatively narrow mesoporous distribution with 35-47nm.
Embodiment 4
The sheet polycrystalline gama-alumina prepared using the method for embodiment 1.It is mixed with a small amount of sesbania powder, with matter
Gauge, sesbania powder content are 2.5%, remaining is sheet polycrystalline gamma-aluminium oxide carrier original powder, total weight 100g.With 2% nitric acid
The above-mentioned mixed-powders of 140 grams of solution infiltration, then kneading extrusion is into cylinder, then 120 DEG C of drying 3 hours roast 5 for 550 DEG C
Hour obtains carrier.The mixed aqueous solution of ammonium molybdate and nickel nitrate is prepared, is loaded on above-mentioned carrier with infusion process, 120 DEG C dry
It dry 2 hours, is then warming up to 650 DEG C and roasts 4 hours, obtain oxidized catalyst.Property is as shown in table 1.
Prepared heavy-oil hydrogenation catalyst is using preceding needing, through presulfurization, feedstock oil to be gradually switched to after vulcanization.Weight used
Matter diesel raw material property：Relative density 0.898,6312 μ g/g of sulfur content, 9104 μ g/g of nitrogen content.Reaction condition：Temperature 350
DEG C, pressure 6MPa, air speed 1.0h-1, volume hydrogen-oil ratio 470.After the hydrogenated reaction of feedstock oil, property is as follows：Relative density
0.871,104 μ g/g of sulfur content, 79 μ g/g of nitrogen content.
Embodiment 5
The sheet polycrystalline gama-alumina prepared using the method for embodiment 3.It is mixed with a small amount of sesbania powder, with matter
Gauge, sesbania powder content are 2.5%, remaining is sheet polycrystalline gamma-aluminium oxide carrier original powder, total weight 100g.With 2% nitric acid
The above-mentioned mixed-powders of 140 grams of solution infiltration, then kneading extrusion is into cylinder, then 120 DEG C of drying 3 hours roast 5 for 550 DEG C
Hour obtains carrier.The mixed aqueous solution of ammonium molybdate and nickel nitrate is prepared, is loaded on above-mentioned carrier with infusion process, 120 DEG C dry
It dry 2 hours, is then warming up to 700 DEG C and roasts 5 hours, obtain oxidized catalyst.Property is as shown in table 1.
Prepared heavy-oil hydrogenation catalyst is using preceding needing, through presulfurization, feedstock oil to be gradually switched to after vulcanization.Slag used
Oily feedstock property：Relative density 0.942,24217 μ g/g of sulfur content, 3047 μ g/g of nitrogen content.Reaction condition：390 DEG C of temperature, pressure
Power 15.4MPa, air speed 0.6h-1, volume hydrogen-oil ratio 1000.Catalyst hydrogenation performance is as shown in table 1.The hydrogenated reaction of feedstock oil
Afterwards, property is as follows：Relative density 0.869,2404 μ g/g of sulfur content, 751 μ g/g of nitrogen content.
Comparative example 1
Method according to 96103297.9 embodiments 1 of CN prepares macroporous aluminium oxide.According to the method for the embodiment of the present invention 5
Supported active metals using identical condition, and carry out slag oil desulfurization reaction.After the hydrogenated reaction of feedstock oil, property is as follows：Phase
To density 0.892,3576 μ g/g of sulfur content, 1069 μ g/g of nitrogen content.
1 catalyst property of table.
As it can be seen from table 1 pore size distribution of the catalyst of the present invention compared with concentration and larger porosity.
Claims (17)
1. a kind of heavy-oil hydrogenation catalyst, which is characterized in that including sheet polycrystalline gama-alumina composition alumina support and plus
Hydrogen activity metal；The property of wherein sheet polycrystalline gama-alumina is as follows：Grain size is 100-600nm, thickness 40-
100nm, sheet polycrystalline gamma-alumina particle are made of the gama-alumina crystal grain of 5-40nm；
The preparation method of the heavy-oil hydrogenation catalyst, including following content：Sheet γ-polycrystal alumina original powder is added in viscous
Agent, extrusion aid kneading, molding, drying and roasting are tied, obtains alumina support；Using conventional method gained carrying alumina
Supported active metals on body；
The wherein preparation method of sheet γ-polycrystal alumina, includes the following steps：（1）It is inorganic aluminate, low-carbon alcohols and/or water, low
Carbon epoxyalkane is uniformly mixed, and forms gel, gel then is carried out aging；（2）By step（1）Obtained gel low-carbon alcohols
It impregnates, then dry, roasting；（3）Step（2）Obtained material, which is immersed in ammonium hydroxide, carries out closed hydro-thermal process, and separation of solid and liquid is done
It is dry, obtain sheet γ-polycrystal alumina original powder；Step（1）Each component content in mixture, in terms of quality percentage：Inorganic aluminate
The total content of 10%-60%, water and/or low-carbon alcohols is 30%-70%, and rest materials are low-carbon epoxyalkane；Step（1）Described is old
It is 20-90 DEG C to change temperature, and ageing time is 1-72 hours；Step（2）The soaking conditions are：20-80 DEG C of temperature, time 1-
72 hours；Step（2）The drying temperature is not more than 200 DEG C；Step（3）The closed hydrothermal condition is：130-180℃
Lower hydro-thermal process 1-12 hours.
2. catalyst described in accordance with the claim 1, which is characterized in that there is following property：Porosity is 70%-90%, Kong Rong
For 0.8-2.0cm3/ g, specific surface area 200-400m2/ g, mesoporous to be distributed as 5-50nm, distribution concentration degree is 70%-90%.
3. according to the catalyst described in claims 1 or 2, which is characterized in that the hydrogenation active metals are VIB or VIII group
Metallic element, vib metals are molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；Using the weight of catalyst as base
Standard, the content of group vib metal are calculated as 5.0wt%-25.0wt% with oxide, and the content of group VIII metal is calculated as 1.0- with oxide
5.0%。
4. a kind of preparation method of the heavy-oil hydrogenation catalyst described in claim 1 ~ 3 any claim, including following content：
Sheet γ-polycrystal alumina original powder is added in into binding agent, extrusion aid kneading, molding, drying and roasting, obtains alumina support；
Using conventional method on the alumina support of gained supported active metals；
The wherein preparation method of sheet γ-polycrystal alumina, includes the following steps：（1）It is inorganic aluminate, low-carbon alcohols and/or water, low
Carbon epoxyalkane is uniformly mixed, and forms gel, gel then is carried out aging；（2）By step（1）Obtained gel low-carbon alcohols
It impregnates, then dry, roasting；（3）Step（2）Obtained material, which is immersed in ammonium hydroxide, carries out closed hydro-thermal process, and separation of solid and liquid is done
It is dry, obtain sheet γ-polycrystal alumina original powder；Step（1）Each component content in mixture, in terms of quality percentage：Inorganic aluminate
The total content of 10%-60%, water and/or low-carbon alcohols is 30%-70%, and rest materials are low-carbon epoxyalkane；Step（1）Described is old
It is 20-90 DEG C to change temperature, and ageing time is 1-72 hours；Step（2）The soaking conditions are：20-80 DEG C of temperature, time 1-
72 hours；Step（2）The drying temperature is not more than 200 DEG C；Step（3）The closed hydrothermal condition is：130-180℃
Lower hydro-thermal process 1-12 hours.
5. according to the method for claim 4, which is characterized in that step（1）The inorganic aluminate is water-soluble inorganic aluminium
Salt, it is one or more in aluminium chloride, aluminum nitrate and aluminum sulfate.
6. according to the method for claim 4, which is characterized in that step（1）The low-carbon alcohols are the alcohol of below C5, are selected from
It is one or more in methanol, ethyl alcohol, normal propyl alcohol and isopropanol.
7. according to the method described in claim 4 or 6, which is characterized in that step（1）The low-carbon alcohols are ethyl alcohol and/or third
Alcohol.
8. according to the method for claim 4, which is characterized in that step（1）The mass ratio of the water/low-carbon alcohols is 0.5-
2.0。
9. according to the method for claim 4, which is characterized in that step（1）Described in the carbon number of low-carbon epoxyalkane be
2-4。
10. according to the method for claim 4, which is characterized in that step（1）Described in low-carbon epoxyalkane be epoxy second
Alkane and/or propylene oxide.
11. according to the method for claim 4, which is characterized in that step（1）Under low-carbon epoxyalkane meets with inorganic aluminate
State relationship：With molar amount, low-carbon epoxyalkane/Al3+For 2.5-9.
12. according to the method described in claim 4 or 11, which is characterized in that step（1）Low-carbon epoxyalkane is expired with inorganic aluminate
Foot states relationship：With molar amount, low-carbon epoxyalkane/Al3+For 3.5-7.0.
13. according to the method for claim 4, which is characterized in that step（2）The low-carbon alcohols are the alcohol of below C5.
14. according to the method for claim 4, which is characterized in that step（2）The low-carbon alcohols are methanol, ethyl alcohol, positive third
It is one or more in alcohol and isopropanol.
15. according to the method for claim 4, which is characterized in that step（3）In, the ammonia concn is 0.01-
0.5mol/L, with molar amount, ammonium hydroxide/Al3+Ratio 0.5-20；The volume of ammonium hydroxide at least can soak handled material completely
Not yet.
16. according to the method described in claim 4 or 15, which is characterized in that step（3）The ammonia concn is 0.01-
0.5mol/L, with molar amount, ammonium hydroxide/Al3+Ratio is 1.0-5.0.
17. according to the method for claim 4, which is characterized in that using infusion process supported active metals component, after dipping
Then carrier is roasted 2~7 hours, obtained heavy-oil hydrogenation is urged at 500 DEG C~800 DEG C in 80 DEG C~130 DEG C dryings 1~12 hour
Agent.
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| CN110467206B (en) * | 2018-05-11 | 2021-10-08 | 中国石油化工股份有限公司 | Macroporous alumina and preparation method thereof |
| CN110935429B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Macroporous alumina and preparation method thereof |
| CN110935432B (en) * | 2018-09-25 | 2022-09-09 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide composite oxide and preparation method thereof |
| CN112708928B (en) | 2019-10-25 | 2021-10-08 | 中国石油化工股份有限公司 | Alumina crystal grain and preparation method thereof |
| CN116037218A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Boron modified alumina carrier, hydrogenation carbon residue removal catalyst and preparation method thereof |
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