CN104368332B

CN104368332B - A kind of hydrotreating catalyst and preparation and application thereof

Info

Publication number: CN104368332B
Application number: CN201310352852.2A
Authority: CN
Inventors: 孙淑玲; 杨清河; 胡大为; 刘佳; 曾双亲; 戴立顺
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-08-14
Filing date: 2013-08-14
Publication date: 2016-12-28
Anticipated expiration: 2033-08-14
Also published as: CN104368332A

Abstract

A kind of hydrotreating catalyst and preparation thereof and application, this catalyst contains carrier and load hydrogenation active metals component on this carrier, described hydrogenation active metals component selected from the metal component of at least one group vib with at least one selected from the metal component of VB race, described carrier is a kind of halogen-containing Bimodal-pore alumina support, characterize with mercury injection method, the pore volume of described carrier is 0.6 1.4 mls/g, and specific surface area is 80 400 meters²/ gram, the pore volume in a diameter of 5 20nm holes accounts for the 30 60% of total pore volume, and the pore volume in a diameter of 100 300nm holes accounts for the 15 45% of total pore volume.Compared with prior art, the catalyst that the present invention provides has preferably hydrogenation depitching matter and demetalization performance when for residual hydrocracking.

Description

A kind of hydrotreating catalyst and preparation and application thereof

Technical field

The present invention relates to a kind of hydrogenation depitching matter catalyst and preparation and application thereof.

Background technology

Mink cell focus including residual oil is carried out deep processing and not only contributes to improve the utilization of crude oil Rate, alleviates the nervous trend of energy supply, can also reduce environmental pollution simultaneously, reach the cleaning of the energy Utilize.Compared with distillate, containing macromolecular reactions such as substantial amounts of asphalitine, colloids in mink cell focus Thing, and the heteroatomic compounds such as sulfur in mink cell focus, nitrogen, oxygen and the heavy metal such as nickel and vanadium and condensed ring Aromatic hydrocarbons is largely focused in asphalitine, and these impurity and heavy metal can be right in the follow-up course of processing Corresponding catalyst pollutes, thus the hydro-conversion of asphalitine is key during residual hydrogenation A step.And in the conversion and subtractive process of asphalitine, need the characteristic according to asphalitine, select Activity is high and the catalyst of the function admirable of good stability.

For the hydrogenation catalyst of depitching matter, catalyst performance is had highly important by its pore-size distribution Meaning.The molecular size of asphalitine is about tens of to hundreds of nanometer, if the spacing of catalyst active center is little In asphaltene molecules, then asphaltene molecules is difficult to be contacted with the active center of catalyst by diffusion, and main It is to adsorb in the outer surface of catalyst or aperture, along with the carrying out of reaction can only form coke because of thermal condensation, leads Cause catalysqt deactivation.Macroporous catalyst is conducive to the removing of asphalitine, but the aperture of catalyst is mutual with specific surface For the catalyst that negative correlation, i.e. average pore size are big, its specific surface area is the least.Therefore to take into account this property Matter, catalyst needs rational pore size distribution.

Existing Heavy oil hydrogenation catalyst be disadvantageous in that its S, N removal rate, heavy metal removing rate and Can not reach between asphaltene removal well to mate, such as, often remove the high catalyst of metal active S, N removal rate and asphaltene removal are the highest.The reason producing problems is the most complicated.First consist in former Material, in residual oil, the feature of each component is that molecular weight is big, and structure is complicated, saturation low (armaticity is high), S, N content are high.And beyond sulphur removal, the overwhelming majority of impurity again more to be present in asphalitine, therefore it is intended to remove this Class S, N, it is necessary to asphaltene molecules is carried out the conversion (including saturated, open loop and hydrogenolysis etc.) of appropriateness.Its Secondary it is catalyst.In prior art, having the catalyst being suitable for carrying out this type of reaction aperture is that protection is urged Agent and catalyst for demetalation, such as:

A kind of hydrodemetallisation catalyst with relatively low carbon deposition quantity and greater activity disclosed in CN1267537C Agent and preparation method thereof.

A kind of residuum hydrogenating and metal-eliminating catalyst disclosed in CN1796500A, this catalyst is had dual by one The carrier in hole and load molybdenum on this carrier and/or tungsten and cobalt and/or nickel metal component composition.Catalyst The preparation method of the carrier used includes the nitrogenous chemical combination beyond by the precursor of a kind of aluminium oxide and a kind of deacidification Thing mixing, molding roasting.

Catalyst for heavy oil fixed bed hydrogenating treatment and preparation method etc. disclosed in CN1233795C.

But, the asphaltene removal of these catalyst is the most relatively low.

Summary of the invention

The technical problem to be solved in the present invention be to provide a kind of new, there is preferable hydrogenation depitching matter performance Catalyst, the preparation method of this catalyst and application.

The present invention relates to herein below:

1. a hydrotreating catalyst, containing carrier and load hydrogenation active metals group on this carrier Point, described hydrogenation active metals component is selected from at least one selected from the metal component of at least one group vib The metal component of VB race, described carrier is a kind of halogen-containing Bimodal-pore alumina support, with mercury injection method table Levying, the pore volume of described carrier is 0.6-1.4 ml/g, and specific surface area is 80-400 rice²/ gram, a diameter of The pore volume in 5-20nm hole accounts for the 30-60% of total pore volume, and the pore volume in a diameter of 100-300nm hole accounts for total hole The 15-45% held.

2. according to the catalyst described in 1, it is characterised in that the pore volume of described carrier be 0.7-1.3 milliliter/ Gram, specific surface area is 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-of total pore volume 50%, the pore volume in a diameter of 100-300nm hole accounts for the 20-40% of total pore volume.

3. according to the catalyst described in 1, it is characterised in that described halogen one in fluorine and chlorine and Mixture, counts and on the basis of carrier by element, and the content of described halogen is 0.1-6 weight %.

4. according to the catalyst described in 3, it is characterised in that described halogen is fluorine, in terms of element and with carrier On the basis of, the content of described halogen is 0.3-4 weight %.

5. according to the catalyst described in 4, it is characterised in that count and on the basis of carrier by element, described halogen The content of element is 0.5-2.5 weight %.

6. according to the catalyst described in 1, it is characterised in that the metal component of described group vib selected from molybdenum and/or Tungsten, VB race metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, described VIB The content of race's metal component is 0.2-15 weight %, and the content of VB race metal component is 0.2-12 weight %.

7. according to the catalyst described in 6, it is characterised in that count and on the basis of catalyst by oxide, institute The content stating group vib metal component is 0.5-12 weight %, and the content of VB race metal component is 0.5-9 weight Amount %.

8. according to the preparation method of catalyst described in 1, including preparing the halogen-containing oxygen with structure of double peak holes Changing alumina supporter, the preparation method of described carrier includes hydrated alumina PA and PB containing boehmite Mix with the modifier PC of a kind of hydrated alumina containing boehmite and introduce Halogen in the mixture The compound of element, molding, dry and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is The κ value of 20-60:20-50:5-50, PC is 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For The sour peptization index of PC hydrated alumina before modified, DI₂Sour peptization index for described PC.

9. according to the method described in 8, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35-50:10-30；The κ value of described PC is 0 to less than or equal to 0.6；Described containing intending thin water The pore volume of the hydrated alumina PA of aluminum stone is 0.75-1 ml/g, and specific surface area is 200-450 rice²/ Gram, most probable bore dia 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, specific surface area is 100-350 rice²/ gram, most probable bore dia is more than 10 to being less than Equal to 30nm；Described halogen is selected from fluorine and chlorine, counts and on the basis of carrier by element, described halogen-containingization The introduction volume of compound makes the content of halogen in final carrier be 0.1-6 weight %.

10. according to the method described in 9, it is characterised in that the described hydrated alumina containing boehmite The pore volume of PA is 0.80-0.95 ml/g, and specific surface area is 200-400 rice²/ gram, most probable bore dia 5-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.95-1.3 ml/g, Specific surface area is 120-300 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 25nm；Described halogen Element is fluorine, counts and on the basis of carrier by element, and the introduction volume of described halogen-containing compound makes final carrier The content of middle halogen is 0.3-4 weight %.

11. it is according to the method described in 10, it is characterised in that count and on the basis of carrier by element, described The introduction volume of halogen-containing compound makes the content of alkaline components in final carrier be 0.5-2.5 weight %.

12. according to the method described in 8 or 9, it is characterised in that described PC is the granule of 80-300 mesh Thing.

13. according to the method described in 12, it is characterised in that described PC is the particulate matter of 100-200 mesh.

14. according to the method described in 8, it is characterised in that described dry condition includes: temperature is 40- 350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is to being less than or equal to more than 500 1200 DEG C, the time is 1-8 hour.

15. according to the method described in 14, it is characterised in that described dry condition includes: temperature is 100- 200 DEG C, the time is 2-12 hour, and the condition of described roasting includes: temperature is to being less than or equal to more than 800 1000 DEG C, roasting time is 2-6 hour.

16. according to the method described in 8, it is characterised in that changed by the hydrated alumina containing boehmite Property be that one of the method for PC is by described hydrated alumina molding containing boehmite, is dried, afterwards It being completely or partially ground, sieve, described dry condition includes: temperature is 40-350 DEG C, time Between be 1-24 hour；The two of method are the article shaped roastings one of method obtained, and sintering temperature is for being more than 350 to less than or equal to 1400 DEG C, and roasting time is 1-8 hour, it is completely or partially ground afterwards Mill, screening；The three of method are to dodge the hydrated alumina containing boehmite to do, and dodge dry temperature for being more than 150 to less than or equal to 1400 DEG C, and flash-off time is 0.05-1 hour；The four of method be by one of method, The two of method and the modifier that obtains of the three of method in several be mixed to get.

17. according to the method described in 16, it is characterised in that the condition bag being dried in one of described method Including: temperature is 100-200 DEG C, the time is 2-12 hour；It is 200-that temperature is done in sudden strain of a muscle in the three of method 1000 DEG C, flash-off time is 0.1-0.5 hour.

18. according to the method described in 8 or 16, it is characterised in that described PC is containing boehmite The particulate matter of 80-300 mesh in the modifier of hydrated alumina.

19. according to the method described in 18, it is characterised in that described PC is the hydration containing boehmite The particulate matter of 100-200 mesh in the modifier of aluminium oxide.

20. according to the method described in 8, it is characterised in that described method is included in described supported on carriers and adds Hydrogen activity metal component, the method for load hydrogenation active metals component is infusion process on the carrier, including Preparation contains the solution of the compound of hydrogenation active metals and uses this solution impregnating carrier, is dried afterwards, roasts Burning or not roasting, described hydrogenation active metals component is selected from the metal component and at least of at least one vib A kind of Group VB metal component, counts and on the basis of catalyst by oxide, the concentration of described impregnation liquid and Consumption makes the content of group vib metal component described in final catalyst be 0.2-15 weight %, VB race gold The content belonging to component is 0.2-12 weight %, and described drying condition is: temperature 80-200 DEG C, and the time, 1-8 was little Time, roasting condition is: temperature 400-600 DEG C, 2-8 hour time.

21. according to the method described in 20, it is characterised in that the metal component of described group vib selected from molybdenum and/or Tungsten, VB race metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, described dipping The concentration of liquid and consumption make the content of group vib metal component described in final catalyst be 0.5-12 weight The content of amount %, VB race metal component is 0.5-9 weight %, and described drying condition is: temperature 100- 150 DEG C, 2-6 hour time, roasting condition is: temperature 420-500 DEG C, 3-6 hour time.

22. according to the method described in 21, it is characterised in that count and on the basis of catalyst by oxide, institute Concentration and the consumption of stating impregnation liquid make the content of group vib metal component described in final catalyst be 5-12 weight The content of amount %, VB race metal component is 1-9 weight %.

23. catalyst described in any one application in hydrocarbon oil hydrogenation processes in 1-7.

Depending on difference, the catalyst provided according to the present invention, requires that carrier therein can be made into various easily operated Article shaped, the most spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder Deng).Wherein, the method described PA, PB and PC mixed is conventional method, such as, by powder body PA, PB and PC put in stirring-type batch mixer according to ingredient proportion and mix.Mixed to described PA, PB and PC The method introducing halogen-containing compound in compound is conventional method, for example, it may be directly by the desired amount of Halogen-containing compound is mixed in aforesaid PA, PB and PC mixed process.

In a concrete embodiment preparing carrier, draw in the mixture of described PA, PB and PC The method entering halogen-containing compound is halogen-containing compound to be configured to aqueous solution, by this aqueous solution in institute It is mixed into or again that this is water-soluble after described PA, PB and PC mix while stating PA, PB and PC mixing Liquid is mixed into, aftershaping, be dried and roasting.Described halogen-containing compound can be the most halogen-containing One or more in water soluble compound.Such as fluorochemical can be selected from Fluohydric acid., in ammonium fluoride One and mixture thereof.

In the present invention, described molding can be carried out according to a conventional method, such as, in spin, tabletting and extruded moulding A kind of method or the combination of several method.When molding, such as extruded moulding, suitable for ensureing described molding Profit is carried out, and can add water, extrusion aid and/or adhesive, with or without reaming in described mixture Agent, then extrusion molding, be dried and roasting afterwards.Described extrusion aid, the kind of peptizer and use Measuring known to those skilled in the art, the most common extrusion aid can be selected from sesbania powder, Methyl cellulose One or more in element, starch, polyvinyl alcohol, PVOH, described peptizer can be mineral acid and/ Or organic acid, described expanding agent can be in starch, synthetic cellulose, polymeric alcohol and surfactant One or more.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose Element, one or more in hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol be preferably Polyethylene Glycol, poly-third One or more in alcohol, polyvinyl alcohol, surfactant is preferably fat alcohol polyethylene ether, fatty alcohol acyl Amine and derivant thereof, molecular weight are in the propenyl copolymer of 200-10000 and maleic acid copolymer Plant or several.

Sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina containing boehmite is by one After fixed acid aluminum ratio adds nitric acid, by the hydration oxygen containing boehmite of peptization within certain response time Change aluminum with Al₂O₃The percent of meter, DI=(1-W₂/W₁) × 100%, W₁And W₂Respectively intend thin water aluminum anti-with acid With Al after Ying Qianhe and acid reaction₂O₃The weight of meter.

The mensuration of DI includes: the calcination base (1) measuring the hydrated alumina containing boehmite is (the most dry Base) (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours content, after it burns Weight weight ratio front with burning, is expressed as a percentage), it is calculated as a；(2) weigh containing intending thin with analytical balance The hydrated alumina W of diaspore₀Gram, W₀Amount meet with Al₂O₃The W of meter₁It is 6 grams of (W₁/ a=W₀), claim Remove ionized water W gram, W=40.0-W₀, under stirring by the hydrated alumina containing boehmite that weighs and Deionized water adds in beaker and mixes；With 20mL pipet pipette 20mL, concentration is dilute nitre of 0.74N Acid solution, joins in the beaker of step (2) by this acid solution, the lower reaction of stirring 8 minutes；(4) will step Suddenly (3) reacted serosity is centrifuged separating in centrifuge, and precipitate is inserted the crucible weighed In, afterwards, it is dried 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh To calcination sample size W₂Gram；(5) according to formula DI=(1-W₂/W₁) × 100% is calculated.

On the premise of being enough to make final carrier meet application claims, the present invention to described containing intend thin water aluminum Hydrated alumina PA and PB of stone does not specially require, and can be plan thin water aluminum prepared by any prior art Stone, it is also possible to be boehmite and the mixture of other hydrated alumina, other aqua oxidation described One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide of aluminum.

In a detailed description of the invention, the described preferred pore volume of hydrated alumina PA containing boehmite For 0.75-1 ml/g, specific surface area is 200-450 rice²/ gram, most probable bore dia 3-10nm, enters one Walking preferred pore volume and be 0.80-0.95 ml/g, specific surface area is 200-400 rice²/ gram, most probable hole is straight Footpath 5-10nm；The described preferred pore volume of hydrated alumina PB containing boehmite be 0.9-1.4 milliliter/ Gram, specific surface area is 100-350 rice²/ gram, most probable bore dia, enters to less than or equal to 30nm more than 10 The one preferred pore volume of step is 0.95-1.3 ml/g, and specific surface area is 120-300 rice²/ gram, most probable hole is straight Footpath is more than 10 to less than or equal to 25nm.

In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and most probable hole Footpath, is by the described hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, by BET nitrogen Absorption representation obtains.

In further preferred embodiment, characterize with X diffraction, the described hydration containing boehmite Boehmite content in aluminium oxide PA and PB is not less than 50%, more preferably not less than 60%.

Inventors of the present invention have surprisingly found that, the hydrated alumina containing boehmite is carried out heat treatment Obtain modifier PC, relative to the original hydrated alumina containing boehmite, the glue of modifier PC Molten index changes, after by this modifier and PA and PB mixed-forming, dry also roasting, and gained To carrier there is obvious bimodal pore distribution.Particularly at the granule by 80-300 mesh therein, preferably The granule of 100-200 mesh and PA and PB mixed-forming, it is dried and after roasting, obtained carrier bimodal In each unimodal pore size distribution concentrate especially.Here, the granule of described 80-300 mesh, preferably 100-200 Purpose granule refers to that described modifier (includes step that is broken or that grind) if desired through sieving, and it sieves thing (siftage) meets the granule of 80-300 mesh, and the particulate matter of preferably 100-200 mesh accounts for the percent of total amount (by weight) not less than 60%, further preferably not less than 70%.Here containing boehmite Hydrated alumina can be boehmite prepared by any prior art, it is also possible to be boehmite and its The mixture of his hydrated alumina, described other hydrated alumina selected from a water aluminium oxide, three water oxidation One or more in aluminum and amorphous hydrated aluminium oxide.In a preferred embodiment, described PC is PA And/or the modifier of PB.

In the present invention, described PA, PB refer to the most described PA, PB and PC with the Mixing ratio by weight of PC Mixture in the ratio of PA, PB and PC respectively shared parts by weight.Wherein, PA:PB:PC is preferably 20-60:20-50:5-50, more preferably 30-50:35-50:10-30.

In the present invention, described PC conveniently can be obtained by following method:

Hereinafter, the method illustrating to obtain PC with described PA and PB for initiation material.

(1) based on being dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite by During regular oxidation alumina supporter is prepared in conventional method molding, the tailing of drying by-product, such as: in extrusion In molding, bar shaped article shaped (is referred to as being dried giving up at tailing dry, integer process by-product traditionally Material), this tailing is milled, sieves and obtain PC.

(2) obtain based on roasting, including by hydrated alumina PA and/or PB containing boehmite by often During regular oxidation alumina supporter is prepared in rule method molding, the tailing of fired by-product (is referred to as roasting traditionally Waste material), such as, in roller forming, spheroidal particle is the tailing of by-product in roasting process, by this tailing Mill, sieve and obtain PC；Or directly PA and/or PB is dodged dry obtaining, directly by PA and / or time PB dodges dry, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.

(3) two or more be mixed to get in the modifier PC obtained based on preceding method.Mixed when using When conjunction method obtains PC, the mixed proportion of the modifier PC respectively obtaining aforementioned several method does not limit System.

According to the present invention provide catalyst, wherein, described group vib metal component be preferably molybdenum and/or Tungsten, more preferably molybdenum or tungsten, VB race metal component is preferably vanadium and/or niobium, more preferably Vanadium.Counting and on the basis of catalyst by oxide, the content of described vib metals component is preferably 0.2- 15 weight %, more preferably 0.5-12 weight %, more preferably 5-12 weight %；Group VB gold The content belonging to component is preferably 0.2-12 weight %, more preferably 0.5-9 weight %, more preferably 1- 9 weight %.

On the premise of being enough to be carried on described carrier described hydrogenation active metals component, the present invention couple Described carrying method is not particularly limited, and preferred method is infusion process, including the preparation change containing described metal The dipping solution of compound, afterwards with the carrier described in this solution impregnation.Described dipping method is routine side Method, for example, it may be excess immersion stain, hole saturation infusion process.Described contains the metal selected from VI B race One or more in component composition soluble compound in them, as molybdenum oxide, molybdate, One or more in paramolybdate, molybdenum oxide preferably wherein, ammonium molybdate, ammonium paramolybdate；Tungstates, One or more in metatungstate, ethyl metatungstate, ammonium metatungstate preferably wherein, ethyl metatungstic acid Ammonium.The described one in the soluble compound being selected from them containing the compound selected from VB race metal component Or several, as a example by the vanadium of VB race, can be selected from such as vanadic anhydride, ammonium vanadate, ammonium metavanadate, sulfur One or more in acid vanadium, vanada polyacid, ammonium metavanadate preferably wherein, ammonium vanadate.

The catalyst provided according to the present invention, it is also possible to provide catalyst performance containing any present invention that do not affects Maybe can improve the addO-on therapy of the catalytic performance of the catalyst that the present invention provides.As the interpolation groups such as phosphorus can be contained Point, to count and on the basis of catalyst by oxide, the content of described addO-on therapy is less than 10 weight %, It is preferably 0.1-4 weight %.

When in described catalyst possibly together with addO-on therapy such as phosphorus, the introducing method of described addO-on therapy can be Arbitrary method, can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix Conjunction, molding roasting；Can be by the compound containing components such as described phosphorus and containing hydrogenation active metals group The compound divided impregnates described carrier after being configured to mixed solution；Can also is that the chemical combination containing components such as phosphorus Thing impregnates described carrier roasting after individually preparing solution.When the addO-on therapy such as phosphorus and hydrogenation active metals difference When introducing described carrier, first with carrier described in the solution impregnation containing described addO-on therapy compound the most also Roasting, the most again by the solution impregnation containing hydrogenation active metals component composition.Wherein, described roasting temperature Degree is for 400-600 DEG C, and preferably 420-500 DEG C, roasting time is 2-6 hour, and preferably 3-6 is little Time.

According to hydrocarbon ils provided by the present invention (including residual oil) hydrotreating method, the hydrogenation to described hydrocarbon ils The reaction condition processed is not particularly limited, in a preferred embodiment, and described hydrotreating reaction condition For: reaction temperature 300-550 DEG C, further preferred 330-480 DEG C, hydrogen dividing potential drop 4-20 MPa, further Preferably 6-18 MPa, volume space velocity 0.1-3.0 hour^-1, further preferred 0.15-2 hour^-1, hydrogen oil body Long-pending ratio 200-2500, further preferred 300-2000.

The device of described hydrogenation reaction can make described raw oil at hydrotreating reaction conditions any being enough to Reactor catalytic with described catalyst is carried out, such as, at described fixed bed reactors, moving bed Reactor or fluidized bed reactor are carried out.

According to the conventional method in this area, described hydrotreating catalyst before the use, generally can be at hydrogen In the presence of gas, at a temperature of 140-370 DEG C, carry out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this Presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component it loaded is converted into Metal sulfide component.

The catalyst that the present invention provides can be used alone, it is also possible to being applied in combination with other catalyst, this is urged Agent is particularly suitable for heavy oil particularly poor residuum and carries out hydrotreating, in order to (such as urge for subsequent technique Change process) qualified raw oil is provided.Compared with prior art, the present invention provide catalyst with There is when residual hydrocracking preferably hydrogenation depitching matter and demetalization performance.

Detailed description of the invention

The present invention will be further described for the following examples, but should be therefore understands that be not the limit to the present invention Fixed.

Agents useful for same in example, except as expressly described, is chemically pure reagent.

The boehmite used below in an example includes:

(pore volume is 0.9 ml/g to the dry glue powder that PA-1: Chang Ling catalyst branch company produces, and specific surface area is 280 meters²/ gram, most probable bore dia 8.5nm.Butt is 73%, and wherein boehmite content is 68%, Gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 34.6).

(pore volume is 0.9 ml/g to the dry glue powder of PA-2: Zibo limited production of neat cyclopentadienyl catalyst, specific surface area It it is 290 meters²/ gram, most probable bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 33.2).

(pore volume is 1.2 mls/g to the dry glue powder that PB-1: Chang Ling catalyst branch company produces, and specific surface area is 280 meters²/ gram, most probable bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 15.8).

(pore volume is 1.1 mls/g to the dry glue powder that PB-2: Yantai Heng Hui Chemical Co., Ltd. produces, specific surface Amass is 260 meters²/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2).

Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.

Embodiment 1

Weigh 1000 grams of PA-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1000 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar in 120 DEG C are dried 4 hours, obtain dried strip, by dried strip shaping, sieve, by length doing less than 2mm Dry bar material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh Screening, obtains the modifier PC-A1 of PA-1.The κ value of PC-A1 is shown in Table 1.

Embodiment 2

Weigh 1000 grams of PA-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1000 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar in 120 DEG C are dried 4 hours, and 800 DEG C of roastings 4 hours obtain carrier, by carrier strip shaping, sieve, will be long The degree carrier strip material (commonly referred to as industry carrier waste material) less than 2mm is milled, and sieves, takes wherein 100～200 mesh sieves divide, and obtain the modifier PC-A2 of PA-1.The κ value of PC-A2 is shown in Table 1.

Embodiment 3

Weigh 1000 grams of PA-2, dodge dry 6 minutes in 400 DEG C, obtain the modifier PC-A3 of PA-2.PC- The κ value of A3 is shown in Table 1.

Embodiment 4

The each 200 grams of mixing of PC-A3 that PC-A1 embodiment 1 obtained and embodiment 3 obtain, obtain The modifier PC-A4 of PA-1 and PA-2.The κ value of PC-A4 is shown in Table 1.

Embodiment 5

Weigh 1000 grams of PB-1, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar in 120 DEG C are dried 4 hours, and 1200 DEG C of roastings 4 hours obtain carrier, by carrier strip shaping, sieve, will The length carrier strip material (commonly referred to as industry carrier waste material) less than 2mm is milled, and sieves, takes it In 100～200 mesh sieves divide, obtain the modifier PC-B1 of PB-1.The κ value of PC-B1 is shown in Table 1.

Embodiment 6

Weigh 1000 grams of PB-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier PC-B2 of PB-2. The κ value of PC-B2 is shown in Table 1.

Embodiment 7

Weigh 1000 grams of PB-2, add afterwards containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) Aqueous solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar in 120 DEG C are dried 4 hours, obtain dried strip, by dried strip shaping, sieve, by length doing less than 2mm Dry bar material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh Screening, obtains the modifier PC-B3 of PB-2.The κ value of PC-B3 is shown in Table 1.

Embodiment 8

The each 200 grams of mixing of PC-B2 that PC-B1 embodiment 5 obtained and embodiment 6 obtain, obtain The modifier PC-B4 of PB-1 and PB-2.The κ value of PC-B4 is shown in Table 1.

Embodiment 9

150 grams of PC-B3 mixing that 100 grams of PC-A1 embodiment 1 obtained and embodiment 7 obtain, Modifier PC-B5 to PA-1 and PB-2.The κ value of PC-B5 is shown in Table 1.

Embodiment 10

The each 150 grams of mixing of PC-B1 that PC-A3 embodiment 3 obtained and embodiment 5 obtain, obtain The modifier PC-B6 of PA-2 and PB-1.The κ value of PC-B6 is shown in Table 1.

Table 1

Embodiment	Raw material	DI	κ
				1	PC-A1	10.0	0.29
2	PC-A2	0.9	0.02
				3	PC-A3	3.6	0.11
4	PC-A4	6.7	0.20
				5	PC-B1	0	0
6	PC-B2	2.1	0.12
				7	PC-B3	5.3	0.31
8	PC-B4	1.0	0.06
				9	PC-B5	7.0	0.29
10	PC-B6	1.6	0.07

Bimodal hole carrier that the embodiment 11-18 explanation present invention provides and preparation method thereof.Comparative example 1-5 is said Bright conventional catalyst carrier and preparation method thereof.

Embodiment 11

Weighing each 400 grams of PA-1 and PB-1, the 200 grams of raw material PC-A2 prepared with embodiment 2 mix After, add the ammonium fluoride containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), fluorine-containing 3.52 grams water-soluble Liquid 1300 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C Dry 4 hours, obtain article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtain carrier Z1.Carrier Z1 Character be listed in table 2.

Embodiment 12

Weighing 300 grams of PA-2,200 grams of PB-2, the 500 grams of raw material PC-B2 prepared with embodiment 6 mix After, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), the ammonium chloride solution of chloride 3.52 grams Liquid 1300 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C Dry 4 hours, obtain article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtain carrier Z2.Carrier Z2 Character be listed in table 2.

Embodiment 13

Weighing 500 grams of PA-2,300 grams of PB-2, the 200 grams of raw material PC-B4 prepared with embodiment 8 mix After, add the ammonium fluoride containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), fluorine-containing 3.52 grams water-soluble Liquid 1300 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C Dry 4 hours, obtain article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtain carrier Z3.Carrier Z3 Character be listed in table 2.

Comparative example 1

Weigh 500 grams of PA-2,500 grams of PB-2, add after mixing containing nitric acid (Tianjin chemical reagent three factory product Product) 10 milliliters, the ammonium fluoride aqueous solution 1300 milliliters of fluorine-containing 3.52 grams, double screw banded extruder is extruded into The butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtain carrier DZ1.The character of carrier DZ1 is listed in table 2.

Comparative example 2

Weigh 400 grams of PA-1,600 grams of PB-1, add after mixing containing nitric acid (Tianjin chemical reagent three factory product Product) 10 milliliters, the ammonium fluoride aqueous solution 1300 milliliters of fluorine-containing 3.52 grams, double screw banded extruder is extruded into The butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 950 DEG C of roastings 3 hours, obtain carrier DZ2.The character of carrier DZ2 is listed in table 2.

Embodiment 14

Weighing 250 grams of PA-1,500 grams of PB-1, the 250 grams of raw material PC-B5 prepared with embodiment 9 mix After, add the ammonium fluoride containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), fluorine-containing 7.07 grams water-soluble Liquid 1300 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C Dry 4 hours, obtain article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier Z4.Carrier The character of Z4 is listed in table 2.

Embodiment 15

Weighing 350 grams of PA-2,350 grams of PB-2, the 300 grams of raw material PC-B6 prepared with embodiment 10 mix After conjunction, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), the ammonium fluoride water of fluorine-containing 7.07 grams Solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C It is dried 4 hours, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier Z5.Carry The character of body Z5 is listed in table 2.

Embodiment 16

Weighing 200 grams of PA-1,600 grams of PB-1, the 200 grams of raw material PC-B1 prepared with embodiment 5 mix After, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), the ammonium chloride solution of chloride 7.07 grams Liquid 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is done in 120 DEG C Dry 4 hours, obtain article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtain carrier Z6.Carrier Z6 Character be listed in table 2.

Embodiment 17

Weighing 200 grams of PA-1,600 grams of PB-1, the 200 grams of raw material PC-A4 prepared with embodiment 4 mix After, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), the ammonium fluoride water of fluorine-containing 14.29 grams Solution 1440 milliliters, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C It is dried 4 hours, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtain carrier Z7.Carrier The character of Z76 is listed in table 2.

Embodiment 18

Weighing 200 grams of PA-1,600 grams of PB-1, the 200 grams of raw material PC-A2 prepared with embodiment 2 mix After, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), the ammonium fluoride of fluorine-containing 14.29 grams 1440 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried in 120 DEG C 4 hours, obtain article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtain carrier Z8.Carrier Z8's Character is listed in table 2.

Comparative example 3

The method provided according to patent CN1782031A embodiment 7, is extruded into external diameter on plunger type bar extruder The butterfly bar of φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 900 DEG C Roasting 3 hours, obtains carrier DZ3.The character of carrier DZ3 is listed in table 2.

Comparative example 4

The method provided according to patent CN1120971A embodiment 1, is extruded into external diameter on plunger type bar extruder The butterfly bar of φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtain carrier DZ4.The character of carrier DZ4 is listed in table 2.

Comparative example 5

Weigh 200 grams of PA-1,800 grams of PB-2, add containing nitric acid (Tianjin chemical reagent three factory product) 10 Milliliter, the ammonium fluoride 1300 milliliters of fluorine-containing 14.29 grams, be extruded into external diameter φ 1.4mm on double screw banded extruder Butterfly bar.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by the 1000 DEG C of roastings 3 of this article shaped Hour, obtain carrier DZ5.The character of carrier DZ5 is listed in table 2.

Table 2

By the result of table 2 it will be seen that compared with conventional method, provider's method of the present invention the oxidation prepared Alumina supporter has obvious structure of double peak holes.

Catalyst that the embodiment 19-23 explanation present invention provides and preparation method thereof.

Wherein, in catalyst, the content of active metal component uses Xray fluorescence spectrometer to measure (all instrument Device is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometer, and concrete grammar is shown in oil Chemical analysis method RIPP133-90).

Embodiment 19

Take 200 grams of carrier Z1, with 220 milliliters containing MoO₃80 grams per liters, V₂O₅The ammonium heptamolybdate of 16 grams per liters Impregnate 1 hour with ammonium metavanadate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain The composition of Hydrodemetalation catalyst C1, C1 is shown in Table 3.

Comparative example 6

Take 200 grams of DZ1, with 220 milliliters containing MoO₃80 grams per liters, the ammonium heptamolybdate of NiO16 grams per liter and Nickel nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, is hydrogenated with The composition of catalyst for demetalation DC1, DC1 is shown in Table 3.

Embodiment 20

Take 200 grams of carrier Z2, with 220 milliliters containing MoO₃80 grams per liters, V₂O₅The ammonium heptamolybdate of 16 grams per liters Impregnate 1 hour with ammonium metavanadate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain The composition of Hydrodemetalation catalyst C2, C2 is shown in Table 3.

Comparative example 7

Take 200 grams of carrier DZ3, with 220 milliliters containing WO₃80 grams per liters, V₂O₅The ammonium heptamolybdate of 16 grams per liters Impregnate 1 hour with ammonium metavanadate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain The composition of Hydrodemetalation catalyst DC2, DC2 is shown in Table 3.

Embodiment 21

Take 200 grams of carrier Z3, with 220 milliliters containing MoO₃80 grams per liters, V₂O₅The ammonium heptamolybdate of 16 grams per liters Impregnate 1 hour with ammonium metavanadate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain The composition of Hydrodemetalation catalyst C3, C3 is shown in Table 3.

Comparative example 8

Take 200 grams of carrier DZ4, with 220 milliliters containing WO₃60 grams per liters, V₂O₅The ammonium heptamolybdate of 60 grams per liters Impregnate 1 hour with ammonium metavanadate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain The composition of Hydrodemetalation catalyst DC3, DC3 is shown in Table 3.

Embodiment 22

Take 200 grams of Z6, with 220 milliliters containing MoO₃90 grams per liters, V₂O₅The ammonium heptamolybdate of 20 grams per liters and Ammonium metavanadate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is added Hydrogen catalyst for demetalation C6.The composition of Hydrodemetalation catalyst C6 is shown in Table 2.

Embodiment 23

Take 200 grams of Z8, with 220 milliliters containing WO₃60 grams per liters, V₂O₅The ammonium tungstate of 60 grams per liters and inclined vanadium Acid ammonium mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation de- Metallic catalyst C8.The composition of Hydrodemetalation catalyst C8 is shown in Table 2.

Comparative example 9

Take 200 grams of carrier DZ5, with 500 milliliters containing MoO₃90 grams per liters, V₂O₅The ammonium heptamolybdate of 20 grams per liters Impregnate 1 hour with ammonium metavanadate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain The composition of Hydrodemetalation catalyst DC4, DC43 is shown in Table 3.

Table 3

Embodiment 24-28

The residuum hydrogenating and metal-eliminating performance of the catalyst that the embodiment 24-28 explanation present invention provides.

The granule that catalyst C1, C2, C3, C4 and C5 are broken into diameter 2-3 millimeter respectively loads anti- Answer device.Reaction condition is: reaction temperature 380 DEG C, hydrogen dividing potential drop 14 MPas, uses inductively coupled plasma Emission spectrometer (ICP-AES) measures before and after hydrotreating the content of nickel and vanadium in oil, and (instrument is the U.S. PE company PE-5300 type plasma quantometer, concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124- 90).Before and after using asphalt compound mensuration method to analyze hydrotreating, oil studies on asphaltene mass fraction is (concrete Method sees SH/T 0509-92).Calculating asphalitine and metal removal rate according to the following formula:

Raw oil be nickel content be 29.3ppm, content of vanadium be 83ppm, sulfur content be 4.7%, nitrogen content be 0.3%, carbon residue is the normal slag of Kuwait of 15.1%.

The activity data of each catalyst is shown in Table 4.

Comparative example 10-13

Method according to embodiment 24-28 evaluates the demetallization per of catalyst DC1, DC2, DC3 and DC4 With depitching matter rate, the results are shown in Table 4.

Table 4

Embodiment	Catalyst is numbered	Depitching matter rate/%	Demetallization per/%
				24	C1	88	76
Comparative example 10	DC1	64	70
				25	C2	90	68
Comparative example 11	DC2	62	65
				26	C3	87	73
Comparative example 12	DC3	68	73
				27	C4	88	76
28	C5	87	81
				Comparative example 13	DC4	75	73

By table 4 result it will be seen that provided catalyst by the present invention in poor residuum hydroprocessing processes Depitching matter and metal removal activity to be substantially better than existing catalyst, illustrate that this technological invention catalyst is more suitable for Processed in poor residuum.

Claims

1. a hydrotreating catalyst, containing carrier and load hydrogenation active metals component on this carrier, described hydrogenation active metals component selected from the metal component of at least one group vib with at least one selected from the metal component of VB race, described carrier is a kind of halogen-containing Bimodal-pore alumina support, characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4 ml/g, and specific surface area is 80-400 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 30-60% of total pore volume, and the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.

Catalyst the most according to claim 1, it is characterised in that the pore volume of described carrier is 0.7-1.3 ml/g, specific surface area is 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, and the pore volume in a diameter of 100-300nm hole accounts for the 20-40% of total pore volume.

Catalyst the most according to claim 1, it is characterised in that described halogen is selected from the one in fluorine and chlorine and mixture thereof, counts and on the basis of carrier by element, and the content of described halogen is 0.1-6 weight %.

Catalyst the most according to claim 3, it is characterised in that described halogen is fluorine, counts and on the basis of carrier by element, the content of described halogen is 0.3-4 weight %.

Catalyst the most according to claim 4, it is characterised in that count and on the basis of carrier by element, the content of described halogen is 0.5-2.5 weight %.

Catalyst the most according to claim 1, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, count and on the basis of catalyst by oxide, the content of described group vib metal component is 0.2-15 weight %, and the content of VB race metal component is 0.2-12 weight %.

Catalyst the most according to claim 6, it is characterised in that count and on the basis of catalyst by oxide, the content of described group vib metal component is 0.5-12 weight %, and the content of VB race metal component is 0.5-9 weight %.

The preparation method of catalyst the most according to claim 1, including preparing the halogen-containing alumina support with structure of double peak holes, the preparation method of described carrier includes the modifier PC of hydrated alumina PA and PB containing boehmite with a kind of hydrated alumina containing boehmite being mixed and being introduced in the mixture halogen-containing compound, molding, be dried and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-60:20-50:5-50, the κ value of PC is 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For the sour peptization index of PC hydrated alumina before modified, DI₂Sour peptization index for described PC.

Method the most according to claim 8, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35-50:10-30；The κ value of described PC is 0 to less than or equal to 0.6；The pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface area is 200-450 rice²/ gram, most probable bore dia 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface area is 100-350 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 30nm；Described halogen is selected from fluorine and chlorine, counts and on the basis of carrier by element, and the introduction volume of described halogen-containing compound makes the content of halogen in final carrier be 0.1-6 weight %.

Method the most according to claim 9, it is characterised in that the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, and specific surface area is 200-400 rice²/ gram, most probable bore dia 5-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.95-1.3 ml/g, and specific surface area is 120-300 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 25nm；Described halogen is fluorine, counts and on the basis of carrier by element, and the introduction volume of described halogen-containing compound makes the content of halogen in final carrier be 0.3-4 weight %.

11. methods according to claim 10, it is characterised in that count and on the basis of carrier by element, the introduction volume of described halogen-containing compound makes the content of alkaline components in final carrier be 0.5-2.5 weight %.

12. methods according to claim 8 or claim 9, it is characterised in that described PC is the particulate matter of 80-300 mesh.

13. methods according to claim 12, it is characterised in that described PC is the particulate matter of 100-200 mesh.

14. methods according to claim 8, it is characterised in that described dry condition includes: temperature is 40-350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500.

15. methods according to claim 14, it is characterised in that described dry condition includes: temperature is 100-200 DEG C, the time is 2-12 hour, and the condition of described roasting includes: temperature is that roasting time is 2-6 hour to less than or equal to 1000 DEG C more than 800.

16. methods according to claim 8, it is characterized in that, one of hydrated alumina method being modified as PC containing boehmite is by described hydrated alumina molding containing boehmite, is dried, afterwards it is completely or partially ground, sieves, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are the article shaped roastings one of method obtained, and sintering temperature is that roasting time is 1-8 hour, it is completely or partially ground afterwards, sieves more than 350 to less than or equal to 1400 DEG C；The three of method are to dodge the hydrated alumina containing boehmite to do, and dodging dry temperature is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C；The four of method are several in three modifiers obtained of one of method, the two of method and method to be mixed to get.

17. methods according to claim 16, it is characterised in that the condition being dried in one of described method includes: temperature is 100-200 DEG C, and the time is 2-12 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.

Method described in 18. according to Claim 8 or 16, it is characterised in that described PC is containing the particulate matter of 80-300 mesh in the modifier of the hydrated alumina of boehmite.

19. methods according to claim 18, it is characterised in that described PC is containing the particulate matter of 100-200 mesh in the modifier of the hydrated alumina of boehmite.

null20. methods according to claim 8，It is characterized in that，Described method is included in described supported on carriers hydrogenation active metals component，The method of load hydrogenation active metals component is infusion process on the carrier，Contain the solution of the compound of hydrogenation active metals including preparation and use this solution impregnating carrier，It is dried afterwards、Roasting or not roasting，Described hydrogenation active metals component is selected from metal component and at least one Group VB metal component of at least one vib，Count and on the basis of catalyst by oxide，The concentration of described impregnation liquid and consumption make the content of group vib metal component described in final catalyst be 0.2-15 weight %，The content of VB race metal component is 0.2-12 weight %，Described drying condition is: temperature 80-200 DEG C，1-8 hour time，Roasting condition is: temperature 400-600 DEG C，2-8 hour time.

21. methods according to claim 20, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, count and on the basis of catalyst by oxide, the concentration of described impregnation liquid and consumption make the content of group vib metal component described in final catalyst be 0.5-12 weight %, the content of VB race metal component is 0.5-9 weight %, described drying condition is: temperature 100-150 DEG C, 2-6 hour time, roasting condition is: temperature 420-500 DEG C, 3-6 hour time.

22. methods according to claim 21, it is characterized in that, counting and on the basis of catalyst by oxide, the concentration of described impregnation liquid and consumption make the content of group vib metal component described in final catalyst be 5-12 weight %, and the content of VB race metal component is 1-9 weight %.

Catalyst described in any one application in hydrocarbon oil hydrogenation processes in 23. claim 1-7.