CN106140180A - 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 catalyst, including alumina support and the hydrogenation active metals of lamellar polycrystalline gama-alumina composition；Wherein the character of lamellar polycrystalline gama-alumina is as follows: grain size is 100-600nm, and thickness is 40-100nm, and lamellar polycrystalline gamma-alumina particle is made up of the gama-alumina crystal grain of 5-40nm.The preparation method of this catalyst is as follows: former for lamellar γ-polycrystal alumina powder adds binding agent, extrusion aid kneading, molding, is dried and roasting, obtain alumina support；Use conventional method supported active metals on the alumina support of gained.Heavy-oil hydrogenation catalyst of the present invention has the macroporous structure run through, higher porosity, the mesoporous distribution of concentration, and mass transfer diffusion is excellent, has broad application prospects in weight, residual hydrogenation catalytic reaction.
Description
Technical field
The present invention relates to a kind of heavy-oil hydrogenation catalyst and preparation method thereof.
Background technology
Along with heaviness day by day, the in poor quality of crude oil, oil refining enterprise faces substantial amounts of heavy, Residual cracking Utilizing question.Weight, residual oil molecule have the three dimensional structure of complexity, and sulfur-bearing condensed-nuclei aromatics side chain frequently forms sterically hindered, and the sulphur atom in obstruction five, hexatomic ring is adsorbed by catalyst active center.In catalytic hydrogenation, heavy oil macromolecules adsorption is also deposited on surface or the aperture of catalyst, makes reaction inside diffusional resistance increase, causes the apparent activity of catalyst to decline.Meanwhile, containing more coke precursor in weight, residual oil, they cause the active center of catalyst to be poisoned in generating coke under certain condition and being deposited on hole.Catalyst internal diffusion becomes to attach most importance to, the governing factor of residual oil catalytic hydrogenation, therefore heavy, the catalytic hydrogenation of residual oil needs macroporous catalyst, and there is bigger aperture and pore volume, in order to accommodate more carbon deposit, metal deposit etc., reduce the diffusional resistance that macromolecular reaction runs into.The large aperture of catalyst and pore volume mainly rely on the carrier of the big pore volume in corresponding large aperture.
The duct of catalyst derives from carrier, it is thus achieved that the catalyst of different ducts feature, is first to start with from catalyst carrier.Good macropore carrier is on pore-size distribution, in addition to should having the pore-size distribution of the 10-20nm more concentrated, also should have the appropriate big pore size distribution more than 50nm, to delay the blocking in macromole aperture in the catalyst and to accommodate more carbon deposit, metal deposit etc..Therefore, use big small-bore the catalyst made of carrier of Based on Dual-Aperture distribution deposited, there is superior performance.But, the aperture of the aluminium oxide being commonly used for preparing hydrotreating catalyst is less, it is impossible to meet the needs preparing heavy oil, residuum hydrogenating and metal-eliminating catalyst.Therefore the way of reaming must be used in preparation process to obtain macropore.Conventional expanding method is to add various types of expanding agent in intending the forming processes such as thin water aluminum oxide dry glue powder kneading, extrusion.The physics expanding agent used at present has the organic substances such as carbon black, carbon fiber, saccharide.
It, with carbon black as expanding agent, is become plastic extruded moulding with boehmite kneading by US4448896.During carrier calcination, expanding agent is oxidized, burning, progressively escapes with gaseous state thing, forms cavity in the carrier, thus constitutes bigger duct.But amount of carbon blacks used by this patent is relatively big, commonly reaches more than 20wt%, the relatively low ability of mechanical strength of resulting vehicle, pore size distribution more disperse.British patent EP237240 uses carbon fiber to be that expanding agent prepares macroporous aluminium oxide, but equally exists that expanding agent consumption is big and support strength is low waits deficiency.
CN96103297.9 is by adding physics expanding agent such as white carbon black and chemical enlargement agent such as phosphide in boehmite dry glue powder, and by kneading method molding, resulting vehicle can several bore dias be 10 ~ 20nm.Thus when the required catalyst requirement carrier of reaction has dual duct and higher mechanical strength to be had, this kind of carrier just receives a definite limitation.
The common issue that above-mentioned patent is faced also has, and carbon black, activated carbon fiber or other organic substance used need to be prepared by special technique.Such as, mainly there are channel carbon black, high abrasion carbon black and acetylene method carbon black in the source of carbon black powder.This expanding agent prepared through special process is used virtually to add macropore oxidation.
Additionally, for the design of industrial catalyst, also should have higher specific surface area, in order to the concentration making the active sites of catalyst is bigger.But specific surface area pore size may often be such that contradiction.In order to suppress the deposit deposition to aperture, need bigger hole to be diffused, but bigger hole generally means that relatively low specific surface area.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of heavy-oil hydrogenation catalyst and preparation method thereof.The catalyst of heavy-oil hydrogenation catalyst of the present invention, has the macroporous structure run through, higher porosity, the mesoporous distribution of concentration, and mass transfer diffusion is excellent, stronger for weight, residual hydrogenation catalytic desulfurization, denitrogenation and demetalization ability.
The heavy-oil hydrogenation catalyst of the present invention, including alumina support and the hydrogenation active metals of lamellar polycrystalline gama-alumina composition；Wherein the character of lamellar polycrystalline gama-alumina is as follows: grain size is 100-600nm, and thickness is 40-100nm, and lamellar polycrystalline gamma-alumina particle is made up of the gama-alumina crystal grain of 5-40nm.
Described heavy-oil hydrogenation catalyst, has the property that porosity is 70%-90%, and pore volume is 0.8-2.0cm3/ g, specific surface area is 200-400m2/ g, the mesoporous 5-50nm that is distributed as, distribution concentration degree is 70%-90%.
Described hydrogenation active metals is VIB or group VIII metal element, and vib metals is preferably molybdenum and/or tungsten, and the metal of group VIII is preferably cobalt and/or nickel.On the basis of the weight of catalyst, the content of group vib metal is calculated as 5.0wt%-25.0wt% with oxide, and the content of group VIII metal is calculated as 1.0-5.0% with oxide.
The preparation method of the heavy-oil hydrogenation catalyst of the present invention, including following content:
Former for lamellar γ-polycrystal alumina powder is added binding agent, extrusion aid kneading, molding, is dried and roasting, obtain alumina support；Use conventional method supported active metals on the alumina support of gained；
Wherein the preparation method of lamellar γ-polycrystal alumina, comprises the steps:
(1) inorganic aluminate, low-carbon alcohols and/or water, low-carbon (LC) epoxyalkane mix homogeneously, forms gel, then carries out aging by gel；
(2) gel low-carbon alcohols step (1) obtained is soaked, then dry, roasting；
(3) material that step (2) obtains immerses and carries out airtight hydrothermal treatment consists in ammonia, and solid-liquid separation is dried, obtains the former powder of lamellar γ-polycrystal alumina.
In step (1), described inorganic aluminate is water-soluble inorganic aluminium salt, one or more in aluminum chloride, aluminum nitrate and aluminum sulfate, preferably aluminum chloride；Low-carbon alcohols is C5Following alcohol, one or more in methanol, ethanol, normal propyl alcohol and isopropanol, more preferably ethanol and/or propanol；Low-carbon alcohols can mix with arbitrary proportion with water, and the preferably mass ratio of water/low-carbon alcohols is 0.5-2.0.
In step (1), the carbon number of described low-carbon (LC) epoxyalkane is 2-4, preferably oxirane and/or expoxy propane.
In step (1), each constituent content in step (1) mixture, in terms of percent mass: the total content of inorganic aluminate 10%-60%, preferably 20%-35%, water and/or low-carbon alcohols is 30%-70%, rest materials is low-carbon (LC) epoxyalkane.Low-carbon (LC) epoxyalkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxyalkane/Al3+For 2.5-9, preferably 3.5-7.0.
In step (1), described aging temperature is 20-90 DEG C, preferably 30-60 DEG C, and ageing time is 1-72 hour, preferably 12-60 hour.
In step (2), described low-carbon alcohols is C5One or more in following alcohol, preferably methanol, ethanol, normal propyl alcohol and isopropanol, preferably ethanol and/or propanol.
In step (2), described soaking conditions is: temperature 20-80 DEG C, preferably 30-60 DEG C, 1-72 hour time, preferably 12-60 hour.
In step (2), described baking temperature is not more than 200 DEG C, preferably not greater than 120 DEG C.
In step (3), described ammonia concn is 0.01-0.5mol/L, with molar amount, ammonia/Al3+Ratio 0.5-20, preferably 1.0-5.0；Handled material at least can be totally submerged by the volume of ammonia.
In step (3), described airtight hydrothermal condition is: hydrothermal treatment consists 1-12 hour at 130-180 DEG C.
In step (3), described baking temperature is not more than 200 DEG C, preferably not greater than 120 DEG C, degree of drying: material constant weight at this temperature.
The heavy-oil hydrogenation catalyst of the present invention, carrier is made up of lamellar polycrystalline gama-alumina, lamellar polycrystalline gama-alumina is that gama-alumina second particle has sheet-like morphology, gama-alumina second particle is made up of the least crystal grain of gama-alumina, form polycrystalline gama-alumina, therefore can keep the activity of the irregular alumina particle of conventional polysilicon.Meanwhile, the lamellar polycrystalline gama-alumina of the present invention, lack of alignment in carrier granular, formed continuously and bigger porosity, beneficially colloid, the mass transport process of asphalitine in heavy oil macromole especially residual oil.Meanwhile, tabular alumina crystal grain uniformity on pattern and size is of a relatively high, it is possible to significantly improves the centrality of the pore size distribution formed by offspring in carrier material, thus improves the catalytic performance of catalyst.The heavy-oil hydrogenation catalyst of the present invention is applied to weight, residual hydrogenation reaction, has the strongest hydrogenation catalyst desulfurization, denitrogenation and demetalization ability.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the lamellar gama-alumina of the embodiment of the present invention 1 preparation.
Fig. 2 is the transmission electron microscope photo of the lamellar gama-alumina of the embodiment of the present invention 1 preparation.
Fig. 3 is X-ray diffraction (XRD) spectrogram of the lamellar gama-alumina of the embodiment of the present invention 1 preparation.
Fig. 4 is the pore size distribution$ figure of the lamellar gama-alumina of the embodiment of the present invention 1 preparation.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.Porosity with mercury injection method test macroporous aluminium oxide.Specific surface area uses BET method to measure, and mesoporous distribution concentration degree uses integrating peak areas method to measure.Lamellar gama-alumina particle size is measured according to scanning electron microscope image.The little crystal grain of composition sheet-like particle, by transmission electron microscope observing, observes its size range.Crystal formation uses X-ray diffraction to characterize.
Lamellar γ-polycrystal alumina in alumina support of the present invention, concrete preparation method is as follows:
(1) inorganic aluminate, low-carbon alcohols and/or water, low-carbon (LC) epoxyalkane mix homogeneously, forms gel, then carries out aging by gel；
Described inorganic aluminate is water-soluble inorganic aluminium salt, one or more in aluminum chloride, aluminum nitrate and aluminum sulfate, preferably aluminum chloride；Low-carbon alcohols is C5Following alcohol, one or more in methanol, ethanol, normal propyl alcohol and isopropanol, more preferably ethanol and/or propanol；Low-carbon alcohols can mix with arbitrary proportion with water, and the preferably mass ratio of water/low-carbon alcohols is 0.5-2.0；The carbon number of described low-carbon (LC) epoxyalkane is 2-4, preferably oxirane and/or expoxy propane；Each constituent content in mixture, in terms of percent mass: the total content of inorganic aluminate 10%-60%, preferably 20%-35%, water and/or low-carbon alcohols is 30%-70%, rest materials is low-carbon (LC) epoxyalkane.Low-carbon (LC) epoxyalkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxyalkane/Al3+For 2.5-9, preferably 3.5-7.0；Described aging temperature is 20-90 DEG C, preferably 30-60 DEG C, and ageing time is 1-72 hour, preferably 12-60 hour；
(2) gel low-carbon alcohols step (1) obtained is soaked, then dry, roasting；
Described low-carbon alcohols is C5One or more in following alcohol, preferably methanol, ethanol, normal propyl alcohol and isopropanol, preferably ethanol and/or propanol；Described soaking conditions is: temperature 20-80 DEG C, preferably 30-60 DEG C, 1-72 hour time, preferably 12-60 hour；Described baking temperature is not more than 200 DEG C, preferably not greater than 120 DEG C.
(3) material that step (2) obtains immerses and carries out airtight hydrothermal treatment consists in ammonia, and solid-liquid separation is dried, obtains the former powder of lamellar γ-polycrystal alumina；
Described ammonia concn is 0.01-0.5mol/L, with molar amount, ammonia/Al3+Ratio 0.5-20, preferably 1.0-5.0；Handled material at least can be totally submerged by the volume of ammonia；Described airtight hydrothermal condition is: hydrothermal treatment consists 1-12 hour at 130-180 DEG C；In step (3), described baking temperature is not more than 200 DEG C, preferably not greater than 120 DEG C, degree of drying: material constant weight at this temperature.
The concrete preparation process of heavy-oil hydrogenation catalyst of the present invention is as follows:
Former for lamellar γ-polycrystal alumina powder is added binding agent, extrusion aid kneading, molding, is dried and roasting, obtain alumina support；Use conventional method supported active metals on the alumina support of gained；
Binding agent used is one or more in nitric acid, phosphoric acid, Alumina gel, Ludox and citric acid；Described extrusion aid is one or more in dried starch, sesbania powder and graphite；Wherein after molding, the shape of carrier includes but not limited to spherical, bar shaped, cylinder, Herba Trifolii Pratentis, Herba Galii Bungei, tooth ball and other abnormity；Described is shaped to conventional shaping method, such as extruded moulding etc..Described baking temperature is not more than 200 DEG C, preferably not greater than 120 DEG C, and drying time is 5-24 hour；Described roasting condition is: 400-750 DEG C of roasting 1-12 hour, preferably 500-650 DEG C roasting 3-6 hour；The former powder material of described carrier is dried, it is also possible to not roasting.
The load of catalyst activity metal of the present invention, carrying method conventional in prior art can be used, preferably infusion process, can be saturated leaching, excess leaching or complexation leaching, i.e. with the solution impregnated catalyst carrier containing required active component, carrier after dipping is dried 1～12 hour at 80 DEG C～130 DEG C, then 500 DEG C～800 DEG C of roastings 2～7 hours, prepares final catalyst.
Embodiment 1
By water, dehydrated alcohol, aluminum chloride mixing, adding expoxy propane mix homogeneously, by weight, content is respectively as follows: water 23%, ethanol 23%, aluminum chloride 20%, expoxy propane 34% to each component of mixture.After mix homogeneously, gained gel at 30 DEG C aging 60 hours, then with soak with ethanol gel after aging, soaks 60 hours at 30 DEG C.After remove liquid phase, at 120 DEG C be dried until no longer there is obvious loss of weight in product.Then roasting 6 hours at 500 DEG C, are cooled to room temperature, then be immersed in excess to major general in the ammonia of its 0.01M flooded completely (with molar amount, ammonia/Al3+Ratio is 5.0), the most airtight and be warmed up to 135 DEG C of hydrothermal treatment consists 12 hours.By product dried at 120 DEG C roasting 3 hours at 650 DEG C, understanding through scanning electron microscopic observation after cooling, product morphology shows as lamellar, its a size of 100-400nm, and thickness is 36nm.Being ground and after ultrasonic disperse by sample, understand with transmission electron microscope observing, sheet-like particle is made up of the less crystal grain of 8-30nm.Owing to simple grinding can not destroy single crystal grain with supersound process, therefore sheet-like particle is not large single crystal crystal grain.The XRD result of product shows, it is gama-alumina.Therefore, sheet-like particle is polycrystalline gama-alumina.Physical absorption test shows, it has the narrower mesoporous distribution of 8-20nm.
Embodiment 2
Under room temperature, by water, dehydrated alcohol, aluminum chloride mixing, adding expoxy propane mix homogeneously, by weight, content is respectively as follows: water 15%, ethanol 20%, aluminum chloride 35%, expoxy propane 30% to each component of mixture.After mix homogeneously, gained gel at 40 DEG C aging 48 hours, then with propanol soak aging after mixture, temperature is 40 DEG C, and the time is 48 hours, after remove liquid phase, be dried until product no longer occurs obvious loss of weight at 100 DEG C.Then roasting 6 hours at 600 DEG C, are cooled to room temperature, then be immersed in excess to major general in the ammonia of its 0.1M flooded completely (with molar amount, ammonia/Al3+Ratio is 2.0), the most airtight and be warmed up to 150 DEG C of hydrothermal treatment consists 5 hours.By product dried at 100 DEG C roasting 5 hours at 550 DEG C.After cooling, scanning electron microscopic observation understands, and product morphology is lamellar, its a size of 254nm, and thickness is 41nm.Being ground and after ultrasonic disperse by sample, understand with transmission electron microscope observing, sheet-like particle is made up of the little crystal grain of 10-25nm.The XRD result of product shows, it is gama-alumina.So, sheet-like particle is polycrystalline gama-alumina.Physical absorption test shows, it has the narrower mesoporous distribution of 10-21nm.
Embodiment 3
Under room temperature, by water, dehydrated alcohol, aluminum chloride mixing, adding expoxy propane mix homogeneously, by weight, content is respectively as follows: water 30%, ethanol 23%, aluminum chloride 25%, expoxy propane 22% to each component of mixture.After mix homogeneously, gained gel at 60 DEG C aging 12 hours, then with ethanol 60 DEG C soak aging after mixture 24 hours, remove liquid phase afterwards, be dried until product no longer occurs obvious loss of weight at 120 DEG C.Then roasting 5 hours at 550 DEG C, are cooled to room temperature, then be immersed in excess to major general in the ammonia of its 0.3M flooded completely (with molar amount, ammonia/Al3+Ratio is 3.0), the most airtight and be warmed up to 165 DEG C of hydrothermal treatment consists 9 hours.By product dried at 120 DEG C roasting 8 hours at 500 DEG C, after cooling, scanning electron microscopic observation understands, and product morphology is lamellar, a size of 542nm, and thickness is 89nm.Being ground and after ultrasonic disperse by sample, understand with transmission electron microscope observing, sheet-like particle is made up of the little crystal grain of 10-35nm.The XRD result of product shows, it is gama-alumina, and therefore sheet-like particle is polycrystalline gama-alumina.Physical absorption test shows, it has the narrower mesoporous distribution of 35-47nm.
Embodiment 4
Use lamellar polycrystalline gama-alumina prepared by the method for embodiment 1.It being mixed with a small amount of sesbania powder, in mass, sesbania powder content is 2.5%, and remaining is the lamellar former powder of polycrystalline gamma-aluminium oxide carrier, and gross weight is 100g.Salpeter solution with 2% 140 grams infiltrates above-mentioned mixed-powder, and then kneading extrusion becomes cylinder, and 120 DEG C are dried 3 hours, and then 550 DEG C of roastings obtain carrier in 5 hours.Preparation ammonium molybdate and the mixed aqueous solution of nickel nitrate, load on above-mentioned carrier with infusion process, and 120 DEG C are dried 2 hours, are then warmed up to 650 DEG C of roastings 4 hours, obtain oxidized catalyst.Character is as shown in table 1.
Prepared heavy-oil hydrogenation catalyst needs gradually to switch to raw oil after presulfurization, sulfuration before using.Heavy diesel feedstock property used: relative density 0.898, sulfur content 6312 μ g/g, nitrogen content 9104 μ g/g.Reaction condition: temperature 350 DEG C, pressure 6MPa, air speed 1.0h-1, volume hydrogen-oil ratio 470.After the hydrogenated reaction of raw oil, character is as follows: relative density 0.871, sulfur content 104 μ g/g, nitrogen content 79 μ g/g.
Embodiment 5
Use lamellar polycrystalline gama-alumina prepared by the method for embodiment 3.It being mixed with a small amount of sesbania powder, in mass, sesbania powder content is 2.5%, and remaining is the lamellar former powder of polycrystalline gamma-aluminium oxide carrier, and gross weight is 100g.Salpeter solution with 2% 140 grams infiltrates above-mentioned mixed-powder, and then kneading extrusion becomes cylinder, and 120 DEG C are dried 3 hours, and then 550 DEG C of roastings obtain carrier in 5 hours.Preparation ammonium molybdate and the mixed aqueous solution of nickel nitrate, load on above-mentioned carrier with infusion process, and 120 DEG C are dried 2 hours, are then warmed up to 700 DEG C of roastings 5 hours, obtain oxidized catalyst.Character is as shown in table 1.
Prepared heavy-oil hydrogenation catalyst needs gradually to switch to raw oil after presulfurization, sulfuration before using.Residual oil raw material character used: relative density 0.942, sulfur content 24217 μ g/g, nitrogen content 3047 μ g/g.Reaction condition: temperature 390 DEG C, pressure 15.4MPa, air speed 0.6h-1, volume hydrogen-oil ratio 1000.Catalyst hydrogenation performance is as shown in table 1.After the hydrogenated reaction of raw oil, character is as follows: relative density 0.869, sulfur content 2404 μ g/g, nitrogen content 751 μ g/g.
Comparative example 1
Macroporous aluminium oxide is prepared according to the method for CN 96103297.9 embodiment 1.According to the method supported active metals of the embodiment of the present invention 5, use identical condition, and carry out slag oil desulfurization reaction.After the hydrogenated reaction of raw oil, character is as follows: relative density 0.892, sulfur content 3576 μ g/g, nitrogen content 1069 μ g/g.
Table 1 catalyst property.
As it can be seen from table 1 the pore size distribution relatively concentrated of catalyst of the present invention and bigger porosity.
Claims (22)
1. a heavy-oil hydrogenation catalyst, it is characterised in that include alumina support and hydrogenation active metals that lamellar polycrystalline gama-alumina forms；Wherein the character of lamellar polycrystalline gama-alumina is as follows: grain size is 100-600nm, and thickness is 40-100nm, and lamellar polycrystalline gamma-alumina particle is made up of the gama-alumina crystal grain of 5-40nm.
2. according to the catalyst described in claim 1, it is characterised in that having the property that porosity is 70%-90%, pore volume is 0.8-2.0cm3/ g, specific surface area is 200-400m2/ g, the mesoporous 5-50nm that is distributed as, distribution concentration degree is 70%-90%.
3. according to the catalyst described in claim 1 or 2, it is characterised in that described hydrogenation active metals is VIB or group VIII metal element, vib metals is molybdenum and/or tungsten, and the metal of group VIII is cobalt and/or nickel；On the basis of the weight of catalyst, the content of group vib metal is calculated as 5.0wt%-25.0wt% with oxide, and the content of group VIII metal is calculated as 1.0-5.0% with oxide.
4. a preparation method for the heavy-oil hydrogenation catalyst described in claim 1 ~ 3 any claim, including following content: former for lamellar γ-polycrystal alumina powder adds binding agent, extrusion aid kneading, molding, is dried and roasting, obtain alumina support；Use conventional method supported active metals on the alumina support of gained；
The wherein preparation method of lamellar γ-polycrystal alumina, comprises the steps: (1) inorganic aluminate, low-carbon alcohols and/or water, low-carbon (LC) epoxyalkane mix homogeneously, forms gel, then carries out aging by gel；(2) gel low-carbon alcohols step (1) obtained is soaked, then dry, roasting；(3) material that step (2) obtains immerses and carries out airtight hydrothermal treatment consists in ammonia, and solid-liquid separation is dried, obtains the former powder of lamellar γ-polycrystal alumina.
The most in accordance with the method for claim 4, it is characterised in that the inorganic aluminate described in step (1) is water-soluble inorganic aluminium salt, one or more in aluminum chloride, aluminum nitrate and aluminum sulfate.
The most in accordance with the method for claim 4, it is characterised in that the alcohol that low-carbon alcohols is below C5 described in step (1), one or more in methanol, ethanol, normal propyl alcohol and isopropanol.
7. according to the method described in claim 4 or 6, it is characterised in that the low-carbon alcohols described in step (1) is ethanol and/or propanol.
The most in accordance with the method for claim 4, it is characterised in that the mass ratio of the water/low-carbon alcohols described in step (1) is 0.5-2.0.
The most in accordance with the method for claim 4, it is characterised in that the carbon number of the low-carbon (LC) epoxyalkane described in step (1) is 2-4.
The most in accordance with the method for claim 4, it is characterised in that the low-carbon (LC) epoxyalkane described in step (1) is oxirane and/or expoxy propane.
11. in accordance with the method for claim 4, it is characterised in that each constituent content in step (1) mixture, in terms of percent mass: the total content of inorganic aluminate 10%-60%, water and/or low-carbon alcohols is 30%-70%, and rest materials is low-carbon (LC) epoxyalkane.
12. in accordance with the method for claim 4, it is characterised in that step (1) low-carbon (LC) epoxyalkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxyalkane/Al3+For 2.5-9.
13. according to the method described in claim 4 or 12, it is characterised in that step (1) low-carbon (LC) epoxyalkane and inorganic aluminate meet following relation: with molar amount, low-carbon (LC) epoxyalkane/Al3+For 3.5-7.0.
14. in accordance with the method for claim 4, it is characterised in that the aging temperature described in step (1) is 20-90 DEG C, and ageing time is 1-72 hour.
15. in accordance with the method for claim 4, it is characterised in that the alcohol that low-carbon alcohols is below C5 described in step (2).
16. in accordance with the method for claim 4, it is characterised in that the low-carbon alcohols described in step (2) is one or more in methanol, ethanol, normal propyl alcohol and isopropanol.
17. in accordance with the method for claim 4, it is characterised in that the soaking conditions described in step (2) is: temperature 20-80 DEG C, 1-72 hour time.
18. in accordance with the method for claim 4, it is characterised in that the baking temperature described in step (2) is not more than 200 DEG C.
19. in accordance with the method for claim 4, it is characterised in that in step (3), and described ammonia concn is 0.01-0.5mol/L, with molar amount, ammonia/Al3+Ratio 0.5-20, preferably 1.0-5.0；Handled material at least can be totally submerged by the volume of ammonia.
20. according to the method described in claim 4 or 19, it is characterised in that the ammonia concn described in step (3) is 0.01-0.5mol/L, with molar amount, ammonia/Al3+Ratio is 1.0-5.0.
21. in accordance with the method for claim 4, it is characterised in that the airtight hydrothermal condition described in step (3) is: hydrothermal treatment consists 1-12 hour at 130-180 DEG C.
22. in accordance with the method for claim 4, it is characterised in that uses infusion process supported active metals component, and the carrier after dipping is dried 1～12 hour at 80 DEG C～130 DEG C, then 500 DEG C～800 DEG C of roastings 2～7 hours, prepares heavy-oil hydrogenation catalyst.
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| ES2004759A6 (en) * | 1987-07-17 | 1989-02-01 | Espanola Alumina Sa | Method for the obtention of an especial alumina from the powder produced in metallurgical alumina calcination |
| CN1101455C (en) * | 2000-05-26 | 2003-02-12 | 中国石油化工集团公司 | Hydrorefining catalyst for hydrocarbons and its preparing process |
| CN101323977A (en) * | 2008-07-10 | 2008-12-17 | 上海交通大学 | Preparation of big length to diameter ratio aluminum oxide nanowire |
| CN102311134B (en) * | 2010-07-07 | 2013-08-28 | 中国石油化工股份有限公司 | Spherical integral macroporous alumina and preparation method thereof |
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