CN104368347B - A kind of hydrogenation activity guard catalyst and its preparation and application - Google Patents

Abstract

A kind of hydrogenation activity guard catalyst and its preparation and application; described hydrogenation activity guard catalyst contains carrier and load hydrogenation active metals component on this carrier; described hydrogenation active metals group is selected from the metal component of at least one VIII race and at least one metal component selected from VB race; described carrier is a kind of Bimodal-pore alumina support of alkaline including earth metal component; characterized 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 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 hydrogenation protecting catalyst that the present invention provides has preferable HDM activity simultaneously.

Description

A kind of hydrogenation activity guard catalyst and its preparation and application

Technical field

The present invention relates to a kind of hydrogenation activity guard catalyst and its preparation and application.

Background technology

With the aggravation of crude oil heaviness, in poor quality trend, crude oil difficulty of processing increases, light oil yield Reduce, and market is being continuously increased to the demand of high grade light-end products, environmental regulation also increasingly tends to tight Lattice.At present, the processing of heavy oil especially residual oil and making full use of just becomes the main words of global Oil Refining Industry concern Topic, and residual hydrogenation technology is a kind of widely used processing technique in processing of heavy oil technique, is well recognized as Economic and environment-friendly moldeed depth process technology.In residual oil contain the metal impurities such as substantial amounts of Ni, V, Fe, Ca and Solid impurity, if this partial impurities can not effectively be removed, can produce unfavorable shadow to downstream hydrogenation catalyst Ring it is easy to make downstream catalyst inactivate.Solving one of effective way of this problem is in hydrogenation catalyst Top filling has the protective agent of hydrogenation activity, and therefore exploitation metal removal activity is high, hold the strong guarantor of metal ability Shield agent is one of key technology that heavy-oil hydrogenation is processed.In prior art, disclosed with regard to hydrogenation activity protection The example of catalyst and preparation method thereof includes：

CN101890381A discloses a kind of hydrotreating guard catalyst for residual oil and its application.This catalyst pore volume Greatly, aperture is big, and porosity is high, reasonable pore distribution, and outer surface orifice is larger, and duct penetrability is good, More than 1000nm contains more than 36% in duct.

CN00124903.7 discloses a kind of hydrogenation protecting catalyst, and this catalyst contains a kind of alumina support With the molybdenum loading on the alumina support and/or tungsten and nickel and/or cobalt, wherein, total ammonia of described alumina support Integral heat of adsorption is not more than 25 joule/gram, the ammonia integration absorption that ammonia differential heat of adsorption is more than 100 kj/mol The percent that heat accounts for total ammonia integral heat of adsorption is not more than 10%.

Patent CN98111379.6 discloses a kind of hydrogenation protecting catalyst and preparation method thereof, and catalyst carries Body is ultra-large aperture, and aperture is 0.1-30 μm of bimodal hole, and catalyst pore volume is 0.1-0.8ml/g, compares table Face 0.1-20m²/ g, containing VI B race metallic element 6.65m%-20.0m% and/or VIII race metallic element 8.7m1%, - 26.13m%.Preparation method is to prepare alumina support using the granule method of piling up, then adopt containing molybdenum solution and Solution containing nickel equivalent impregnation, the catalyst after dipping is dried 2-5h at 100-120 DEG C, joins at 500-550 DEG C Put roast 2-5h.

Content of the invention

The technical problem to be solved in the present invention is to provide a kind of new hydrogenation activity guard catalyst, this hydrogenation to live The preparation method of property guard catalyst and application.

The present invention relates to herein below：

1. a kind of hydrogenation activity guard catalyst, containing carrier and load hydrogenation active metals on this carrier Component, the metal component that described hydrogenation active metals group is selected from least one VIII race is selected from at least one The metal component of VB race, described carrier is a kind of Bimodal-pore alumina support of alkaline including earth metal component, to press Hydrargyrum method characterizes, 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, the pore volume in a diameter of 100-300nm hole Account for the 15-45% of total pore volume.

2. the catalyst according to 1 it is characterised in that described carrier pore volume 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. the catalyst according to 1 it is characterised in that described alkaline earth metal component be selected from beryllium, magnesium, One or more of calcium, strontium and barium, are counted and on the basis of carrier by oxide, described alkaline earth metal component Content be 0.1-6 weight %.

4. the catalyst according to 3 is it is characterised in that described alkaline earth metal component is magnesium or calcium, with oxygen Compound meter on the basis of carrier, the content of described alkaline earth metal component is 0.3-4 weight %.

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

6. the hydrogenation activity guard catalyst according to 1 is it is characterised in that described metal component of group VIII Selected from cobalt and/or nickel, the metal component of Group VB is selected from vanadium and/or niobium, in terms of oxide and with catalyst On the basis of, the content of described VIII race's metal component is more than 0 to less than or equal to 0.8 weight %, the Vth B race gold The content belonging to component is more than 0 to less than or equal to 4 weight %.

7. the hydrogenation activity guard catalyst according to 6 it is characterised in that in terms of oxide and be catalyzed On the basis of agent, the content of described VIII race's metal component is 0.1-0.6 weight %, the Vth B race metal component Content is 1.5-3.5 weight %.

8. the preparation method of the hydrogenation activity guard catalyst according to 1, has bimodal hole knot including preparation The alumina support of the alkaline including earth metal component of structure, the preparation method of described carrier is included containing the thin water aluminum of plan Hydrated alumina PA and PB of stone is mixed with a kind of modifier PC of the hydrated alumina containing boehmite And the compound of introducing alkaline including earth metal, molding, drying roasting in the mixture, wherein, described The Mixing ratio by weight of PA, PB and PC is 20-60：20-50：The κ value of 5-50, PC for 0 to less than etc. In 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.

9. the method according to 8 is it is characterised in that method according to 8 is it is characterised in that institute The Mixing ratio by weight stating PA, PB and PC is 30-50：35-50：10-30；The k value of described PC be 0 to Less than or equal to 0.6；The pore volume of the described hydrated alumina PA containing boehmite be 0.75-1 milliliter/ Gram, specific surface is 200-450 rice²/ gram, most probable bore dia 3-10nm；Described containing boehmite The pore volume of hydrated alumina PB is 0.9-1.4 ml/g, and specific surface is 100-350 rice²/ gram, most probable Bore dia is more than 10 to less than or equal to 30nm；Counted and on the basis of described carrier by oxide, described containing alkali It is 0.1-6 weight % that the introduction volume of the compound of earth metal makes the content of alkaline earth metal component in final carrier.

10. the method according to 9 is 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, most probable 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, most probable bore dia is more than 10 to less than or equal to 25nm；In terms of oxide And on the basis of described carrier, the introduction volume of the compound of described alkaline including earth metal makes alkaline earth gold in final carrier The content belonging to component is 0.3-4 weight %.

11. methods according to 10 it is characterised in that being counted and on the basis of described carrier by oxide, It is 0.5- that the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier 2.5 weight %.

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

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

14. methods according to 8 are it is characterised in that the condition of described drying 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. methods according to 14 are it is characterised in that the condition of described drying 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. methods according to 8 are it is characterised in that change the hydrated alumina containing boehmite Property one of method for PC be by the described hydrated alumina molding containing boehmite, drying, afterwards It is completely or partially ground, sieves, the condition of described drying includes：Temperature is 40-350 DEG C, when Between be 1-24 hour；The two of method are the article shaped roastings obtaining method one, and sintering temperature is more than 350 To less than or equal to 1400 DEG C, roasting time is 1-8 hour, afterwards it is completely or partially ground, is sieved Point；The three of method be the hydrated alumina containing boehmite is dodged dry, 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 One or more of two and the modifier that obtains with the three of method are mixed to get.

17. methods according to 16 are it is characterised in that the condition of drying in methods described 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. methods according to 8 or 16 are it is characterised in that described PC is containing boehmite The particulate matter of 80-300 mesh in the modifier of hydrated alumina.

19. methods according to 18 are 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. methods according to 8 are it is characterised in that include loading hydrogenation activity gold on the carrier Belong to component, the described method in supported on carriers hydrogenation active metals component is infusion process, add including preparing to contain The solution of the compound of hydrogen activity metal simultaneously uses this solution impregnating carrier, is dried afterwards, roasting or do not roast Burn, described hydrogenation active metals group is selected from the metal component of at least one VIIIth race and at least one VB The metal component of race, is counted and on the basis of catalyst by oxide, the described compound containing hydrogenation active metals Make the containing of metal component of the VIIIth race in final catalyst in the concentration of described solution and the consumption of described solution Amount is to less than or equal to 0.8 weight % more than 0, the content of the metal component of described Group VB be more than 0 to Less than or equal to 4 weight %；Described drying condition includes：Temperature is 100-250 DEG C, and the time is that 1-10 is little When；Described roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hour.

21. methods according to 20 it is characterised in that the metal component of described VIIIth race be selected from nickel and/ Or cobalt, the metal component of Group VB is selected from vanadium and/or niobium, counted and on the basis of catalyst by oxide, institute Stating the compound containing hydrogenation active metals makes final catalyst in the concentration of described solution and the consumption of described solution In the content of metal component of group VIII be 0.2-0.6 weight %, the content of the metal component of Group VB is 1.5-3.5 weight %；Described drying condition includes：Temperature is 100-140 DEG C.

In 22. claim 1-7, the hydrogenation activity guard catalyst described in any one is processed in hydrocarbon oil hydrogenation In application.

The catalyst providing according to the present invention, requires carrier therein can be made into depending on difference various easily operated Article shaped, for example spherical, cellular, nest like, tablet or bar shaped（Herba Trifolii Pratentis, butterfly, cylinder Deng）.Wherein, the method described PA, PB and PC being mixed is conventional method, for example, by powder body PA, PB and PC put in stirring-type batch mixer according to ingredient proportion and mix.Mix to described PA, PB and PC The method introducing the compound of alkaline including earth metal in compound is conventional method, for example, it may be directly will be required The compound of the alkaline including earth metal of amount is mixed in aforesaid PA, PB and PC mixed process.

In an embodiment specifically preparing carrier, draw in the mixture of described PA, PB and PC The method entering the compound of alkaline including earth metal is that the compound of alkaline including earth metal is configured to aqueous solution, by this water Solution be mixed into while described PA, PB and PC mix or described PA, PB and PC mixing after again This aqueous solution is mixed into, aftershaping, drying roasting.The compound of described alkaline including earth metal can be appointed One or more of water soluble compound of alkaline including earth metal of meaning.For example, the water solublity of alkaline-earth metal is no One or more of machine salt.

In the present invention, described molding can be carried out according to a conventional method, for example, in spin, tabletting and extruded moulding A kind of method or several method combination.In 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, it is dried afterwards and roasting.Described extrusion aid, the species of peptizer and use Amount is known to those skilled in the art, and for example common extrusion aid can be selected from sesbania powder, Methyl cellulose One or more of 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 of hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol be preferably Polyethylene Glycol, poly- third One or more of alcohol, polyvinyl alcohol, surfactant is preferably fat alcohol polyethylene ether, fatty alcohol acyl In amine and its derivant, the molecular weight propylene alcohol copolymer and maleic acid copolymer for 200-10000 one Plant or several.

Sour peptization index D I in the preparation of described carrier refers to the hydrated alumina containing boehmite by one After fixed acid aluminum ratio adds nitric acid, by the hydration oxygen containing boehmite for the 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 mensure of DI includes：(1) measure the calcination base of the hydrated alumina containing boehmite（Also referred to as dry Base）Content（Calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, after its burning Weight ratio before weight and burning, is expressed as a percentage）, it is calculated as a；(2) weighed thin containing intending with analytical balance The hydrated alumina W of diaspore₀Gram, W₀Amount meet with Al₂O₃The W of meter₁For 6 grams（W₁/a=W₀）, claim Remove W gram of ionized water, W=40.0-W₀, under stirring by weigh the hydrated alumina containing boehmite and Deionized water adds in beaker and mixes；(3) pipette 20mL with 20mL pipet, concentration be 0.74N dilute nitre Acid solution, this acid solution is added to step（2）Beaker in, the lower reaction of stirring 8 minutes；(4) will walk Suddenly（3）Reacted serosity is centrifuged in centrifuge, precipitate is inserted the crucible weighed In, afterwards, by it in 125 DEG C of dryings 4 hours, 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.

Enough to, on the premise of making final carrier meet application claims, the present invention is to described containing the thin water aluminum of plan Hydrated alumina PA and PB of stone does not specially require, and can be the plan thin water aluminum of any prior art preparation Stone or the mixture of boehmite and other hydrated aluminas, described others aqua oxidations Aluminum is selected from one or more of a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.

In a detailed embodiment, the described preferred pore volume of hydrated alumina PA containing boehmite For 0.75-1 ml/g, specific surface is 200-450 rice²/ gram, most probable bore dia 3-10nm, further Preferably pore volume is 0.80-0.95 ml/g, and specific surface is 200-400 rice²/ gram, most probable 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, most probable bore dia is 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, most probable bore dia 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, characterized with X diffraction, the described hydration containing boehmite Boehmite content in aluminium oxide PA and PB is not less than 50%, is 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, with respect 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, drying roasting, gained To carrier there is obvious bimodal pore distribution.Particularly by the granule of 80-300 mesh therein, preferably After the granule of 100-200 mesh and PA and PB mixed-forming, drying roasting, obtained carrier bimodal In each unimodal pore size distribution especially concentrate.Here, the granule of described 80-300 mesh, preferably 100-200 Purpose granule refers to described modifier through sieving（Include step that is broken or grinding if necessary）, it sieves thing （Siftage）Meet the granule of 80-300 mesh, the particulate matter of preferably 100-200 mesh accounts for the percent of total amount （By weight）Not less than 60%, further preferably it is not less than 70%.Here containing boehmite Hydrated alumina can be boehmite or boehmite and its prepared by any prior art The mixture of his hydrated alumina, described others hydrated alumina is selected from a water aluminium oxide, three water oxygens One or more of aluminum and amorphous hydrated aluminium oxide.In a preferred embodiment, described PC is PA And/or the modifier of PB.

In the present invention, the Mixing ratio by weight of described PA, PB and PC refers to described PA, PB and PC parts per hundred parts Mixture in PA, PB and PC respectively shared by parts by weight ratio.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.

Be based on be 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, for example：In extrusion In molding, bar shaped article shaped is being dried, the tailing of integer process by-product（Traditionally referred to as it is dried useless Material）, this tailing is milled, sieves and obtain PC.

(2) obtained based on roasting, including by hydrated alumina PA and/or PB containing boehmite by normal During regular oxidation alumina supporter is prepared in rule method molding, the tailing of fired by-product（Traditionally it is referred to as roasting Waste material）, for example, in roller forming, the tailing of spheroidal particle by-product in roasting process, by this tailing Milled, sieve and obtain PC；Or directly by PA and/or PB dodge dry obtain, directly by PA and / or when 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 being obtained based on preceding method.When using mixed When conjunction method obtains C, the mixed proportion of the modifier PC that aforementioned several method is respectively obtained does not limit System.

The hydrogenation protecting catalyst providing according to the present invention, wherein, described hydrogenation active metals component preferably the VIII race's metal component is cobalt and/or nickel, and the metal component of Group VB is vanadium and/or niobium, in terms of oxide simultaneously On the basis of catalyst, the content of described metal component of group VIII is to less than or equal to 0.8 weight more than 0 %, preferably 0.1-0.7 weight %, more preferably 0.2-0.6 weight %, described Group VB metal The content of component is to less than or equal to 4 weight %, preferably 1-4 weight % more than 0, more preferably 1.5-3.5 weight %.

On the premise of being enough to described hydrogenation active metals component is carried on described carrier, the present invention couple Described carrying method is not particularly limited, and preferred method is infusion process, including the change prepared 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 excessive immersion stain, hole saturation infusion process.Described containing the metal selected from V B race Component composition is selected from one or more of soluble compound in them, for example, it is possible to be selected from such as five One or more of V 2 O, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada polyacid, preferably wherein Ammonium metavanadate, ammonium vanadate.Described is selected from their solubility containing the compound selected from VIII race's metal component One or more of compound, such as cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt is solvable One or more of property complex, preferably cobalt nitrate, basic cobaltous carbonate；Nickel nitrate, nickel acetate, alkali One or more of soluble complexes of formula nickelous carbonate, Nickel dichloride. and nickel, preferably nickel nitrate, alkali formula Nickelous carbonate.

The catalyst providing according to the present invention, can also contain any present invention that do not affect provides catalyst performance Or the addO-on therapy of the catalytic performance of catalyst of present invention offer can be provided.As the interpolation groups such as phosphorus can be contained Point, counted 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 also containing the addO-on therapy such as phosphorus in described catalyst, the introducing method of described addO-on therapy can be Arbitrary method, as being directly to mix the compound containing components such as described phosphorus with described boehmite Conjunction, molding roasting；Can be by the compound containing components such as described phosphorus and containing hydrogenation active metals group The compound dividing impregnates described carrier after being configured to mixed solution；Can also be 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, preferably first with the carrier described in solution impregnation containing described addO-on therapy compound simultaneously Roasting, afterwards again with the solution impregnation containing hydrogenation active metals component composition.Wherein, described roasting temperature Spend for 400-600 DEG C, preferably 420-500 DEG C, roasting time is 2-6 hour, and preferably 3-6 is little When.

According to hydrocarbon ils provided by the present invention（Including residual oil）Hydrotreating method, the hydrogenation to described hydrocarbon ils The reaction condition processing is not particularly limited, in a preferred embodiment, 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 be any enough to make described raw oil at hydrotreating reaction conditions Carry out in the catalytic reactor with described catalyst, for example, in described fixed bed reactors, moving bed Carry out in reactor or fluidized bed reactor.

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

The catalyst that the present invention provides be can be used alone it is also possible to be used with other catalyst combinations, this is urged Agent is particularly suitable for heavy oil particularly poor residuum and carries out hydrotreating, to be subsequent technique（As urged Change process）Qualified raw oil is provided.Compared with the Hydrogenation active protective agent providing with prior art, this The Hydrogenation active protective agent that invention provides has preferable hydrogenation while having GPF (General Protection False agent function and takes off gold Belong to activity.

Specific embodiment

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

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

The boehmite using below in an example includes：

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

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

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

PB-2：The dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces（Pore volume is 1.1 mls/g, specific surface For 260 meters²/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, gibbsite content is 5 weight %, balance of 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 and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters 1000 milliliters of aqueous solution, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C drying 4 hours, obtains dried strip, dried strip shaping is sieved, and length is less than the dried strip of 2mm Material（Commonly referred to as industrially drying bar waste material）Milled, sieved, taken wherein 100～200 mesh sieves 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 and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters 1000 milliliters of aqueous solution, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C drying 4 hours, 800 DEG C of roastings 4 hours, obtain carrier, carrier strip shaping is sieved, by length Carrier strip material less than 2mm（Commonly referred to as industrial carrier waste material）Milled, sieved, taken wherein 100～200 mesh sieves divide, and obtain final product 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 the PC-A1 that obtain embodiment 1 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 and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters 1440 milliliters of aqueous solution, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C drying 4 hours, 1200 DEG C of roastings 4 hours, obtain carrier, carrier strip shaping is sieved, by length Carrier strip material less than 2mm（Commonly referred to as industrial carrier waste material）Milled, sieved, taken wherein 100～200 mesh sieves divide, and obtain final product 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 and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters 1440 milliliters of aqueous solution, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C drying 4 hours, obtains dried strip, dried strip shaping is sieved, and length is less than the dried strip of 2mm Material（Commonly referred to as industrially drying bar waste material）Milled, sieved, taken wherein 100～200 mesh sieves 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 the PC-B1 that obtain embodiment 5 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 that obtain embodiment 1 and embodiment 7 obtain, 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 the PC-A3 that obtain embodiment 3 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

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

Embodiment 11

Weigh each 400 grams of PA-1 and PB-1,200 grams of raw material PC-A2 being obtained with embodiment 2 are mixed Afterwards, add and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters, the aqueous solution containing 12.91g magnesium nitrate 1300 milliliters, external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm are extruded on plunger type bar extruder. Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, and 900 DEG C of roastings of this article shaped 3 hours obtain Carrier Z1.The property of carrier Z1 is listed in table 2.

Embodiment 12

Weigh 300 grams of PA-2,200 grams of PB-2,500 grams of raw material PC-B2 being obtained with embodiment 6 are mixed Afterwards, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters, the aqueous solution containing 12.91g magnesium nitrate 1300 milliliters, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, obtain article shaped, 900 DEG C of roastings of this article shaped 3 hours obtain carrier Z2.Carrier Z2's Property is listed in table 2.

Embodiment 13

Weigh 500 grams of PA-2,300 grams of PB-2,200 grams of raw material PC-B4 being obtained with embodiment 8 are mixed Afterwards, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters, the aqueous solution containing 10.25g calcium nitrate 1300 milliliters, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, obtain article shaped, 950 DEG C of roastings of this article shaped 3 hours obtain carrier Z3.Carrier Z3's Property is listed in table 2.

Comparative example 1

Weigh 500 grams of PA-2,500 grams of PB-2, after mixing, add the chemical reagent of Tianjin containing nitric acid three factory to produce Product）10 milliliters, 1300 milliliters of the aqueous solution containing 12.91g magnesium nitrate, are extruded into outer on plunger type bar extruder The Raschig ring shape bar of footpath 2.5mm, internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains molding Thing, 900 DEG C of roastings of this article shaped 3 hours obtain carrier DZ1.The property of carrier DZ1 is listed in table 2.

Embodiment 14

Weigh 250 grams of PA-1,500 grams of PB-1,250 grams of raw material PC-B5 being obtained with embodiment 9 are mixed Afterwards, add and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters, the aqueous solution containing 26.19g magnesium nitrate 1300 milliliters, external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm are extruded on plunger type bar extruder. Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, and 1000 DEG C of roastings of this article shaped 3 hours obtain Carrier Z4.The property of carrier Z4 is listed in table 2.

Embodiment 15

Weigh 350 grams of PA-2,350 grams of PB-2,300 grams of raw material PC-B6 being obtained with embodiment 10 are mixed After conjunction, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters, the aqueous solution containing 26.19g magnesium nitrate 1440 milliliters, external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm are extruded on plunger type bar extruder. Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, and 1000 DEG C of roastings of this article shaped 3 hours obtain Carrier Z5.The property of carrier Z5 is listed in table 2.

Embodiment 16

Weigh 200 grams of PA-1,600 grams of PB-1,200 grams of raw material PC-B1 being obtained with embodiment 5 are mixed Afterwards, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters, the aqueous solution containing 26.19g magnesium nitrate 1440 milliliters, external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm are extruded on plunger type bar extruder. Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, and 850 DEG C of roastings of this article shaped 3 hours obtain Carrier Z6.The property of carrier Z6 is listed in table 2.

Comparative example 2

Weigh 400 grams of PA-1,600 grams of PB-1, after mixing, add the chemical reagent of Tianjin containing nitric acid three factory to produce Product）10 milliliters, 1300 milliliters of the aqueous solution containing 26.19g magnesium nitrate, are extruded into outer on plunger type bar extruder The Raschig ring shape bar of footpath 2.5mm, internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains molding Thing, 950 DEG C of roastings of this article shaped 3 hours obtain carrier DZ2.The property of carrier DZ2 is listed in table 2.

Embodiment 17

Weigh 200 grams of PA-1,600 grams of PB-1,200 grams of raw material PC-A4 being obtained with embodiment 4 are mixed Afterwards, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters, the aqueous solution water containing 52.93 magnesium nitrates 1440 milliliters of solution, is extruded into external diameter 2.5mm, the Raschig ring shape of internal diameter 1.0mm on plunger type bar extruder Bar.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, Obtain carrier Z7.The property of carrier Z7 is listed in table 2.

Embodiment 18

Weigh 200 grams of PA-1,600 grams of PB-1,200 grams of raw material PC-A2 being obtained with embodiment 2 are mixed Afterwards, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters, the aqueous solution containing 42.02 calcium nitrates 1440 milliliters, external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm are extruded on plunger type bar extruder. Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, and 850 DEG C of roastings of this article shaped 3 hours obtain Carrier Z8.The property of carrier Z8 is listed in table 2.

Comparative example 3

The method providing according to patent CN1782031A embodiment 7, is extruded into external diameter on plunger type bar extruder The Raschig ring shape bar of 2.5mm, internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, By 900 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ3.The property of carrier DZ3 is listed in table 2.

Comparative example 4

The method providing according to patent CN1120971A embodiment 1, is extruded into external diameter on plunger type bar extruder The Raschig ring shape bar of 2.5mm, internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, By 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ3.The property of carrier DZ3 is listed in table 2.

Comparative example 5

Weigh 200 grams of PA-1,800 grams of PB-2, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 Milliliter, 1300 milliliters of the aqueous solution containing 42.02 calcium oxide, are extruded into external diameter on plunger type bar extruder The Raschig ring shape bar of 2.5mm, internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, By 1000 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ5.The property of carrier DZ5 is listed in table 2.

Table 2

Can be seen by the result of table 2, compared with conventional method, by the method provided by the present invention prepare containing magnesium Or calcium alumina support has obvious structure of double peak holes.

Embodiment 19-24 illustrates catalyst that the present invention provides and preparation method thereof.

Embodiment 19

Take 200 grams of carrier Z1, contain V with 220 milliliters₂O₅28.6 g/l, NiO5 g/l of ammonium metavanadate Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen activity guard catalyst C1.The composition of C1 is listed in Table 3 below.

Embodiment 20

Take 200 grams of carrier Z2, contain V with 220 milliliters₂O₅28.6 g/l, CoO5 g/l of ammonium metavanadate Impregnate 1 hour with cobalt nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen activity guard catalyst C2.The composition of C2 is listed in Table 3 below.

Embodiment 21

Take 200 carrier Z3, contain V with 220 milliliters₂O₅25 g/l, NiO3 g/l of ammonium metavanadate and nitre Sour nickel mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation and lives Property guard catalyst C3.The composition of C3 is listed in Table 3 below.

Embodiment 22

Take 200 grams of carrier Z4, contain V with 220 milliliters₂O₅25 g/l, CoO3 g/l of ammonium metavanadate and Cobalt nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Active protection catalyst C4.The composition of C4 is listed in Table 3 below.

Embodiment 23

Take 200 grams of carrier Z5, contain V with 220 milliliters₂O₅19.0 g/l, NiO2 g/l of ammonium metavanadate Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen activity guard catalyst C5.The composition of C5 is listed in Table 3 below.

Embodiment 24

Take 200 grams of carrier Z8, contain V with 220 milliliters₂O₅19.0 g/l, NiO2 g/l of ammonium metavanadate Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen activity guard catalyst C6.The composition of C6 is listed in Table 3 below.

Contrast row 6

Take 200 grams of carrier DZ1, contain V with 220 milliliters₂O₅28.6 g/l, NiO5 g/l of metavanadic acid Ammonium and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrogenation activity guard catalyst DC1.The composition of DC1 is listed in Table 3 below.

Contrast row 7

Take 200 grams of carrier DZ2, contain WO with 220 milliliters₃28.6 g/l, NiO5 g/l of ammonium metatungstate Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen activity guard catalyst DC2.The composition of DC2 is listed in Table 3 below.

Comparative example 8

Take 200 grams of carrier DZ3, contain V with 220 milliliters₂O₅25 g/l, NiO3 g/l of ammonium metavanadate Impregnate 1 hour with nickel nitrate mixed solution, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, added Hydrogen activity guard catalyst DC3.The composition of DC3 is listed in Table 3 below.

Comparative example 9

Take 200 grams of carrier DZ4, contain MoO with 220 milliliters₃25 g/l, CoO3 g/l of ammonium molybdate and Cobalt nitrate mixed solution impregnates 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, is hydrogenated with Active protection catalyst DC4.The composition of DC4 is listed in Table 3 below.

Table 3

In catalyst, the content of each metal component is value of calculation.

Embodiment 25-30

Embodiment 25-30 illustrates the demetallization per of hydrogenation protecting catalyst and the desulfurization degree of present invention offer.

With the normal slag of Yi Chong as raw material（Raw material oil nature is shown in Table 4）, in 100 milliliters of small fixed reactors Upper evaluation protective agent.

Catalyst C1, C2, C3, C4, C5 and C6 are broken into the granule of diameter 2-3 millimeter, catalysis Agent loading amount is 100 milliliters.Reaction condition is：380 DEG C of reaction temperature, 14 MPas of hydrogen dividing potential drop, liquid hourly space velocity (LHSV) For 0.7 hour^-1, hydrogen to oil volume ratio is 1000, sample analysis after reacting 200 hours.Using inductive etc. The content of metal in oil before and after ionomer emission spectrum instrument (ICP-AES) mensure hydrotreating（Instrument is U.S. State's PE company PE-5300 type plasma quantometer, concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90）.Calculate metal removal rate according to the following formula：

Raw material oil nature is listed in table 4, and evaluation result is listed in Table 5 below.

Comparative example 10-13

Method according to embodiment 25-30 evaluates the demetalization of catalyst DC1, DC2, DC3 and DC4 Rate, the results are shown in Table 5.

Table 4

Raw oil title	The normal slag of Yi Chong
		Density（20℃）, kg/m3	0.966
Mean molecule quantity	452
		Ni, μ g/g	47.7
V, μ g/g	133
		Fe, μ g/g	8.4
Ca, μ g/g	29.5

Table 5 protective agent evaluation result

Can be seen that compared with existing catalyst by the data of table 5, the hydrogenation protecting agent that the present invention provides has Higher demetallization per.

Claims (21)

1. a kind of hydrogenation activity guard catalyst, containing carrier and load hydrogenation activity on this carrier Metal component, described hydrogenation active metals group be selected from the metal component of at least one VIII race with least A kind of metal component selected from VB race, described carrier is a kind of bimodal hole oxidation of alkaline including earth metal component Alumina supporter, is characterized 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 30-60% of total pore volume, a diameter of The pore volume in 100-300nm hole accounts for the 15-45% of total pore volume；Described metal component of group VIII be selected from cobalt and / or nickel, the metal component of Group VB is selected from vanadium and/or niobium, is counted with oxide and with catalyst as base Standard, the content of described VIII race's metal component is more than 0 to less than or equal to 0.8 weight %, the Vth B race metal The content of component is more than 0 to less than or equal to 4 weight %.

2. hydrogenation activity guard catalyst according to claim 1 is it is characterised in that described load The pore volume of body is 0.7-1.3 ml/g, and specific surface area is 100-300 rice²/ gram, a diameter of 5- The pore volume in 20nm hole accounts for the 35-50% of total pore volume, and the pore volume in a diameter of 100-300nm hole accounts for total hole The 20-40% holding.

3. hydrogenation activity guard catalyst according to claim 1 is it is characterised in that described alkali Earth metal group is selected from one or more of beryllium, magnesium, calcium, strontium and barium, in terms of oxide and to carry On the basis of body, the content of described alkaline earth metal component is 0.1-6 weight %.

4. hydrogenation activity guard catalyst according to claim 3 is it is characterised in that described alkali Earth metal group is divided into magnesium or calcium, is counted and on the basis of carrier by oxide, described alkaline earth metal component Content is 0.3-4 weight %.

5. hydrogenation activity guard catalyst according to claim 4 is it is characterised in that with element Count and on the basis of carrier, the content of described alkaline-earth metal is 0.5-2.5 weight %.

6. hydrogenation activity guard catalyst according to claim 1 is it is characterised in that with oxide Count and on the basis of catalyst, the content of described VIII race's metal component is 0.1-0.6 weight %, the Vth B The content of race's metal component is 1.5-3.5 weight %.

7. the preparation method of hydrogenation activity guard catalyst according to claim 1, including preparation There is the alumina support of the alkaline including earth metal component of structure of double peak holes, the preparation method bag of described carrier Include hydrated alumina PA and PB containing boehmite and a kind of hydration oxygen containing boehmite The modifier PC changing aluminum mixes and introduces in the mixture the compound of alkaline including earth metal, molding, does Dry and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-60：20-50：5- 50, PC κ value for 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For PC before modified The sour peptization index of hydrated alumina, DI₂Sour peptization index for described PC.

8. preparation method according to claim 7 is it is characterised in that side according to 8 Method is 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 for 0 to less than or equal to 0.6；The described aqua oxidation containing boehmite The pore volume of aluminum PA is 0.75-1 ml/g, and specific surface area is 200-450 rice²/ gram, most probable hole is straight Footpath 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite be 0.9-1.4 milliliter/ Gram, specific surface area is 100-350 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 30nm； Counted and on the basis of described carrier by oxide, the introduction volume of the compound of described alkaline including earth metal makes In whole carrier, the content of alkaline earth metal component is 0.1-6 weight %.

9. preparation method according to claim 8 it is characterised in that described containing intend thin water aluminum The pore volume of the hydrated alumina PA of stone 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 For 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；Counted and on the basis of described carrier by oxide, the change of described alkaline including earth metal It is 0.3-4 weight % that the introduction volume of compound makes the content of alkaline earth metal component in final carrier.

10. preparation method according to claim 9 is it is characterised in that in terms of oxide and with institute On the basis of stating carrier, the introduction volume of the compound of described alkaline including earth metal makes alkaline-earth metal in final carrier The content of component is 0.5-2.5 weight %.

11. preparation methoies according to claim 7 or 8 are it is characterised in that described PC is 80- The particulate matter of 300 mesh.

12. preparation methoies according to claim 11 are it is characterised in that described PC is 100- The particulate matter of 200 mesh.

13. preparation methoies according to claim 7 are it is characterised in that the condition bag of described drying Include：Temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting includes：Temperature is big In 500 to less than or equal to 1200 DEG C, the time is 1-8 hour.

14. preparation methoies according to claim 13 are it is characterised in that the condition of described drying Including：Temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting includes：Temperature It is that roasting time is 2-6 hour more than 800 to less than or equal to 1000 DEG C.

15. preparation methoies according to claim 7 will be it is characterised in that boehmite will be contained Hydrated alumina to be modified as one of method of PC be by the described hydrated alumina containing boehmite It is completely or partially ground, sieves by molding, drying afterwards, the condition bag of described drying Include：Temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are the one-tenth obtaining one of method Type thing roasting, sintering temperature is that roasting time is that 1-8 is little more than 350 to less than or equal to 1400 DEG C When, afterwards it is completely or partially ground, sieves；The three of method are will to contain boehmite Hydrated alumina dodge dry, dodging dry temperature is to less than or equal to 1400 DEG C more than 150, and flash-off time is 0.05-1 hour；The four of method are by one of method, the two of method and the modification that obtains with the three of method Several in thing are mixed to get.

16. preparation methoies according to claim 15 are it is characterised in that in one of methods described The condition of drying include：Temperature is 100-200 DEG C, and the time is 2-12 hour；In the three of method Dodge dry temperature and be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.

17. preparation methoies according to claim 7 or 15 it is characterised in that described PC be containing There is the particulate matter of 80-300 mesh in the modifier of hydrated alumina of boehmite.

18. preparation methoies according to claim 17 are it is characterised in that described PC is containing plan The particulate matter of 100-200 mesh in the modifier of the hydrated alumina of boehmite.

19. preparation methoies according to claim 7 are it is characterised in that include on the carrier Load hydrogenation active metals component, the described method in supported on carriers hydrogenation active metals component is leaching Stain method, the solution including the compound prepared containing hydrogenation active metals simultaneously uses this solution impregnating carrier, it After be dried, roasting or not roasting, described hydrogenation active metals group is selected from least one VIIIth race Metal component and at least one Group VB metal component, counted with oxide and with catalyst as base Standard, the described compound containing hydrogenation active metals makes in the concentration of described solution and the consumption of described solution The content of the metal component of the VIIIth race in final catalyst is to less than or equal to 0.8 weight % more than 0, The content of the metal component of described Group VB is to less than or equal to 4 weight % more than 0；Described dried strip Part includes：Temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes：Temperature For 360-500 DEG C, the time is 1-10 hour.

20. preparation methoies according to claim 19 are it is characterised in that the gold of described VIIIth race Genus group is selected from nickel and/or cobalt, and the metal component of Group VB is selected from vanadium and/or niobium, in terms of oxide simultaneously On the basis of catalyst, the described compound containing hydrogenation active metals is in the concentration of described solution and described It is 0.2-0.6 weight % that the consumption of solution makes the content of the metal component of group VIII in final catalyst, the The content of the metal component of VB race is 1.5-3.5 weight %；Described drying condition includes：Temperature is 100-140℃.

In 21. claim 1-6, the hydrogenation activity guard catalyst described in any one is at hydrocarbon oil hydrogenation Application in reason.