CN104368395B - A kind of hydrogenation depitching matter catalyst and preparation and application thereof - Google Patents

Abstract

A kind of hydrogenation depitching matter catalyst and preparation and application thereof, described catalyst contains the halogen-containing alumina support with structure of double peak holes, characterizes with mercury injection method, and 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 55% 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 hydrogenation depitching matter 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 Hydrodemetalation catalyst with relatively low carbon deposition quantity and greater activity disclosed in CN1267537C 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 hydrogenation depitching matter catalyst, containing the halogen-containing carrying alumina with structure of double peak holes Body, characterizes with mercury injection method, and 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 30-55% of total pore volume, a diameter of 100-300nm hole Pore volume account for the 15-45% of total pore volume.

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 is selected from fluorine and chlorine, in terms of element also On the basis of carrier, 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 hydrogenation active metals component in described catalyst Selected from least one metal component of group VIII and at least one vib metals component, in terms of oxide and with On the basis of catalyst, the content of described VIII race's metal component more than 0.8 to less than or equal to 3 weight %, the VIth The content of B race metal component is more than 3 to less than or equal to 10 weight %.

7. according to the catalyst described in 6, it is characterised in that described metal component of group VIII selected from cobalt and/or Nickel, vib metals component is selected from molybdenum and/or tungsten, counts and on the basis of catalyst by oxide, described The content of VIII race's metal component is 1-2 weight %, and the content of metal component of group VIB is 4-8 weight %.

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 in the mixture and contain The compound of halogen, 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 k 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 is 200-450 rice²/ gram, Can and bore dia 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.9- 1.4 mls/g, specific surface is 100-350 rice²/ gram, can and bore dia more than 10 to being less than or equal to 30nm；Described halogen is selected from fluorine and chlorine, counts and on the basis of carrier by element, described halogen-containing compound Introduction volume make 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 is 200-400 rice²/ gram, can and bore dia 5- 10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.95-1.3 ml/g, than Surface is 120-300 rice²/ gram, can and bore dia 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 halogen in final carrier The content of element is 0.3-4 weight %.

11. according to the catalyst 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 halogen 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 article shaped roastings method one obtained, and sintering temperature is more than 350 To less than or equal to 1400 DEG C, roasting time is 1-8 hour, it is completely or partially ground afterwards, sieves Point；The three of method are to dodge dry by the hydrated alumina containing boehmite, dodge dry temperature be more than 150 to Less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, method it Two and the modifier that obtains with the three of method in one or more be mixed to get.

17. according to the method described in 16, it is characterised in that the condition being dried in described method one includes: Temperature is 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500- 1200 DEG C, roasting time is 0.1-6 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, dodges dry Time is 0.1-0.5 hour.

18. according to the method described in 16, it is characterised in that described PC is the hydration containing boehmite The particulate matter of 80-300 mesh in the modifier of aluminium oxide.

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 be included in described supported on carriers hydrogenation activity gold Belonging to component, the described method in supported on carriers hydrogenation active metals component is infusion process, including preparation containing adding The solution of the compound of hydrogen activity metal also uses this solution impregnating carrier, is dried afterwards, roasting or do not roast Burn, described hydrogenation active metals component selected from the metal component of at least one group VIB and at least one the VIIIth The metal component of race, counts and on the basis of catalyst by oxide, the described compound containing hydrogenation active metals The metal component of group VIB in final catalyst is made in the concentration of described solution and the consumption of described solution Content is more than 3 to less than or equal to 10 weight %, and the content of the metal component of described VIIIth race is more than 0.8 to little In equal to 3 weight %；Described drying condition includes: temperature is 100-250 DEG C, and the time is 1-10 hour； Described roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour.

21. according to the method described in 20, it is characterised in that the metal component of described vib selected from molybdenum and / or tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, counts and on the basis of catalyst by oxide, institute State the compound containing hydrogenation active metals and make final catalyst in the concentration of described solution and the consumption of described solution In the content of metal component of vib be 4-8 weight %, the content of the metal component of the VIIIth race is 1-2 Weight %；Described drying condition includes: temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting bar Part includes: temperature is 360-450 DEG C, and the time is 2-6 hour.

Catalyst described in any one application in hydrocarbon oil hydrogenation processes in 22. claim 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 is 200-450 rice²/ gram, can and bore dia 3-10nm, further Preferably pore volume is 0.80-0.95 ml/g, and specific surface is 200-400 rice²/ gram, can and bore dia 5- 10nm；The described preferred pore volume of hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, than Surface is 100-350 rice²/ gram, can and bore dia more than 10 to less than or equal to 30nm, further preferably Pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, can and bore dia 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 can and 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 C, the mixed proportion of the modifier PC respectively obtaining aforementioned several method does not limit System.

The catalyst provided according to the present invention, hydrogenation active metals component therein is selected from least one the VIIIth race Metal component and at least one vib metals component, count and on the basis of catalyst by oxide, described The content of VIII race's metal component more than 0.8 to less than or equal to 3 weight %, preferably 1-2 weight %, the VIth The content of B race metal component more than 3 to less than or equal to 10 weight %, preferably 4-8 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.Described one containing the compound selected from VIII race's metal component in their soluble compound or Several, such as the one in the soluble complexes of cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt Or several, preferably cobalt nitrate, basic cobaltous carbonate；Nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride. With one or more in the soluble complexes of nickel, preferably nickel nitrate, basic nickel carbonate.

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 is 280 meters²/ gram, can and 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, and specific surface is 290 meters²/ gram, can and 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 is 280 meters²/ gram, can and 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 It it is 260 meters²/ gram, can and 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 is in 120 DEG C it is dried 4 hours, obtains dried strip, by dried strip shaping, sieve, by length less than the dried strip of 2mm Material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh sieve Point, obtain the modifier PC-A1 of PA-1.The k 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 is in 120 DEG C it is dried 4 hours, 800 DEG C of roastings 4 hours, obtains carrier, by carrier strip shaping, sieve, by length 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 k 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 k 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 k 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 is in 120 DEG C it is dried 4 hours, 1200 DEG C of roastings 4 hours, obtains carrier, by carrier strip shaping, sieve, by length 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-B1 of PB-1.The k 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 k 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 is in 120 DEG C it is dried 4 hours, obtains dried strip, by dried strip shaping, sieve, by length less than the dried strip of 2mm Material (commonly referred to as industrially drying bar waste material) is milled, and sieves, takes wherein 100～200 mesh sieve Point, obtain the modifier PC-B3 of PB-2.The k 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 k 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 k 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 k value of PC-B6 is shown in Table 1.

Table 1

Embodiment	Raw material	DI	k
				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

The preparation method containing halogen bimodal hole carrier that the embodiment 11-18 explanation present invention provides.Comparative example 1- The preparation method of 5 explanation conventional catalyst carrier.

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 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution containing ammonium fluoride 9.8g 1300 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 900 DEG C of roastings of this article shaped 3 hours, obtain carrier Z1.Carrier Z1's Character is 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 the product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, the aqueous solution of chloride containing ammonia 7.6g 1300 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 900 DEG C of roastings of this article shaped 3 hours, obtain carrier Z2.Carrier Z2's Character is 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 product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, aqueous solution containing ammonium fluoride 9.8g 1300 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 950 DEG C of roastings of this article shaped 3 hours, obtain carrier Z3.Carrier Z3's Character is listed in table 2.

Comparative example 1

Weigh 500 grams of PA-2,500 grams of PB-2, add after mixing and produce containing nitric acid Tianjin chemical reagent three factory Product) 10 milliliters, aqueous solution 1300 milliliters containing ammonium fluoride 9.8g, double screw banded extruder is extruded into external diameter 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 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 and produce containing nitric acid Tianjin chemical reagent three factory Product) 10 milliliters, aqueous solution 1300 milliliters containing ammonium fluoride 9.8g, double screw banded extruder is extruded into external diameter The butterfly bar of φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 950 DEG C Roasting 3 hours, obtains 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 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), aqueous solution containing ammonium fluoride 19.6g 1300 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 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier Z4.Carrier Z4 Character be listed in table 2.

Embodiment 15

Weigh 350 grams of PA-2,350 grams of PB-2, after the 300 grams of raw materials prepared with embodiment 10 mix, Add the product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, aqueous solution 1440 containing ammonium fluoride 19.6g in the least Rise, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.It is little that wet bar is dried 4 in 120 DEG C Time, obtain article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier Z5.The property of carrier Z5 Matter 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 the product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, the aqueous solution of chloride containing ammonia 15.2g 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 Z6.Carrier Z6's Character is 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 the product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, aqueous solution containing ammonium fluoride 39.2g 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 Z7.Carrier Z76 Character be 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 the product in nitric acid Tianjin chemical reagent three factory) 10 milliliters, aqueous solution containing ammonium fluoride 39.2g 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 roasting 3 hours, obtains carrier DZ3.The character of carrier DZ3 is listed in table 2.

Comparative example 5

Weigh 200 grams of PA-1,800 grams of PB-2, add the product in nitric acid Tianjin chemical reagent three factory) 10 Milliliter, aqueous solution 1300 milliliters containing ammonium fluoride 39.2g, be extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by this article shaped 1000 DEG C Roasting 3 hours, obtains 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 210 milliliters containing MoO₃67.9 grams per liters, the oxidation of CoO 11.3 grams per liter Molybdenum and basic cobaltous carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 are little Time, obtain catalyst C1.Molybdenum oxide and the content of cobalt oxide in catalyst C1 are listed in table 3.

Comparative example 6

Take 200 grams of carrier DZ1, with 180 milliliters containing MoO₃79.2 grams per liters, the oxidation of CoO 13.2 grams per liter Molybdenum and basic cobaltous carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 are little Time, obtain catalyst DC1.Molybdenum oxide and the content of cobalt oxide in catalyst DC1 are listed in table 3.

Embodiment 20

Take 200 carrier Z2, with 200 milliliters containing MoO₃53.1 grams per liters, the molybdenum oxide of NiO 10.6 grams per liter Impregnate 1 hour with basic nickel carbonate mixed solution, dry 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, Obtain catalyst C2.Molybdenum oxide and the content of nickel oxide in catalyst C2 are listed in table 3.

Comparative example 7

Take 200 carrier DZ3, with 180 milliliters containing MoO₃59.0 grams per liters, the molybdenum oxide of NiO 11.8 grams per liter Impregnate 1 hour with basic nickel carbonate mixed solution, dry 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, Obtain catalyst DC2.Molybdenum oxide and the content of nickel oxide in catalyst DC2 are listed in table 3.

Embodiment 21

Take 200 grams of carrier Z3, with 205 milliliters containing MoO₃78.5 grams per liters, the molybdic acid of NiO 15.7 grams per liter Ammonium and nickel nitrate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, To catalyst C3.Molybdenum oxide and the content of nickel oxide in catalyst C3 are listed in table 3.

Comparative example 8

Take 200 grams of carrier DZ4, with 180 milliliters containing MoO₃87.2 grams per liters, the oxidation of NiO 17.4 grams per liter Molybdenum and basic nickel carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 are little Time, obtain catalyst DC3.Molybdenum oxide and the content of nickel oxide in catalyst DC3 are listed in table 3.

Embodiment 22

Take 200 grams of carrier Z6, with 210 milliliters containing MoO₃67.9 grams per liters, the oxidation of NiO 11.3 grams per liter Molybdenum and basic nickel carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 are little Time, obtain catalyst C4.Molybdenum oxide and the content of nickel oxide in catalyst C4 are listed in table 3.

Embodiment 23

Take 200 grams of carrier Z8, with 200 milliliters containing MoO₃82.8 grams per liters, the oxidation of CoO 19.1 grams per liter Molybdenum and basic cobaltous carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 are little Time, obtain catalyst C5.Molybdenum oxide and the content of cobalt oxide in catalyst C5 are listed in table 3.

Comparative example 9

Take 200 grams of carrier DZ5, with 200 milliliters containing MoO₃82.8 grams per liters, the oxidation of CoO 19.1 grams per liter Molybdenum and basic cobaltous carbonate mixed solution impregnate 1 hour, dry 2 hours in 120 DEG C, and 420 DEG C of roastings 3 are little Time, obtain catalyst DC4.Molybdenum oxide and the content of cobalt oxide in catalyst DC4 are listed 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/T0509-92).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	85	77
Comparative example 10	DC1	64	70
				25	C2	89	71
Comparative example 11	DC2	62	63
				26	C3	90	75
Comparative example 12	DC3	75	70
				27	C4	91	76
28	C5	92	81
				Comparative example 13	DC4	80	76

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 (22)

1. a hydrogenation depitching matter catalyst, containing the halogen-containing aluminium oxide with structure of double peak holes Carrier, characterizes with mercury injection method, and 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 30-55% of total pore volume, a diameter of The pore volume in 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 hole body in a diameter of 5-20nm hole The long-pending 35-50% accounting for total pore volume, the pore volume in a diameter of 100-300nm hole accounts for the 20-of total pore volume 40%.

Catalyst the most according to claim 1, it is characterised in that described halogen selected from fluorine and Chlorine, 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, with unit Element is counted and on the basis of carrier, and the content of described halogen is 0.3-4 weight %.

Catalyst the most according to claim 4, it is characterised in that in terms of element and with carrier be Benchmark, the content of described halogen is 0.5-2.5 weight %.

Catalyst the most according to claim 1, it is characterised in that the hydrogenation in described catalyst Active metal component is selected from least one metal component of group VIII and at least one vib metals group Point, count and on the basis of catalyst by oxide, the content of described VIII race's metal component more than 0.8 to Less than or equal to 3 weight %, the content of metal component of group VIB is more than 3 to less than or equal to 10 weights Amount %.

Catalyst the most according to claim 6, it is characterised in that described metal component of group VIII Selected from cobalt and/or nickel, vib metals component is selected from molybdenum and/or tungsten, in terms of oxide and with catalysis On the basis of agent, the content of described VIII race's metal component is 1-2 weight %, containing of metal component of group VIB Amount is 4-8 weight %.

The most according to claim 1, the preparation method of catalyst, has structure of double peak holes including preparation Halogen-containing alumina support, the preparation method of described carrier includes the water containing boehmite Close aluminium oxide PA and PB to mix also with the modifier PC of a kind of hydrated alumina containing boehmite Introduce halogen-containing compound, molding in the mixture, be dried and roasting, wherein, described PA, The Mixing ratio by weight of PB and PC be the κ value of 20-60:20-50:5-50, PC be 0 to being less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For the sour peptization index of PC hydrated alumina before modified, DI₂For The sour peptization index of described PC.

Method the most according to claim 8, it is characterised in that the weight of described PA, PB and PC Amount mixing ratio 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, specific surface area For 200-450 rice²/ gram, most probable bore dia 3-10nm；The described hydration oxygen containing boehmite The pore volume changing aluminum PB 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, in terms of element and with carrier On the basis of, 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 described containing boehmite The pore volume of hydrated alumina 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 more than 10 to Less than or equal to 25nm；Described halogen is fluorine, counts and on the basis of carrier by element, described halogen-containing The introduction volume of 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 in terms of element and with carrier be Benchmark, the introduction volume of described halogen-containing compound makes the content of halogen 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 80-300 Purpose particulate matter.

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

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

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

16. methods according to claim 8, it is characterised in that by the water containing boehmite Closing one of alumina modified method for PC is to be become by the described hydrated alumina containing boehmite Type, be 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 one of method obtained Roasting, sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, it After it be completely or partially ground, sieve；The three of method are by the hydration containing boehmite Aluminium oxide dodges dry, and dodging dry temperature is that flash-off time is 0.05-1 more than 150 to less than or equal to 1400 DEG C Hour；The four of method are by one of method, the two of method and the modifier that obtains with the three of method Several it is mixed to get.

17. methods according to claim 16, it is characterised in that doing in one of described method Dry condition 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 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 for containing intending 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 for containing intending thin water The particulate matter of 100-200 mesh in the modifier of the hydrated alumina of aluminum stone.

20. methods according to claim 8, it is characterised in that be included in described supported on carriers Hydrogenation active metals component, the described method in supported on carriers hydrogenation active metals component is dipping Method, contains the solution of the compound of hydrogenation active metals and uses this solution impregnating carrier, afterwards including preparation Be dried, roasting or not roasting, described hydrogenation active metals component is selected from least one group VIB Metal component and the metal component of at least one the VIIIth race, count and on the basis of catalyst by oxide, The described compound containing hydrogenation active metals makes finally in the concentration of described solution and the consumption of described solution The content of the metal component of the group VIB in catalyst more than 3 to less than or equal to 10 weight %, described the The content of the metal component of VIII race is more than 0.8 to less than or equal to 3 weight %；Described drying condition includes: Temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes: temperature is 360- 500 DEG C, the time is 1-10 hour.

21. methods according to claim 20, it is characterised in that the metal of described vib Component be selected from molybdenum and/or tungsten, the metal component of the VIIIth race be selected from cobalt and/or nickel, in terms of oxide and with On the basis of catalyst, the described compound containing hydrogenation active metals is in the concentration of described solution and described molten The consumption of liquid makes the content of the metal component of the vib in final catalyst be 4-8 weight %, and the VIIIth The content of the metal component of race is 1-2 weight %；Described drying condition includes: temperature is 100- 140 DEG C, the time is 1-6 hour；Described roasting condition includes: temperature is 360-450 DEG C, and the time is 2-6 hour.

Catalyst described in any one application in hydrocarbon oil hydrogenation processes in 22. claim 1-7.