CN104437519B

CN104437519B - Residuum hydrotreatment catalyst, and preparation and application thereof

Info

Publication number: CN104437519B
Application number: CN201310432522.4A
Authority: CN
Inventors: 赵新强; 孙淑玲; 贾燕子; 刘学芬; 杨清河; 刘涛
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-09-22
Filing date: 2013-09-22
Publication date: 2017-02-08
Anticipated expiration: 2033-09-22
Also published as: CN104437519A

Abstract

The invention discloses a residuum hydrotreatment catalyst, and preparation and application thereof. The catalyst comprises an aluminium oxide carrier and a hydrogenation active metal composition. The hydrogenation active metal composition comprises at least one metal composition selected from group VIII and at least one metal composition selected from groups VI B. Based on the catalyst in terms of oxides, the content of the group VIII metal composition is larger than 3 wt% and less than or equal to 10 wt%, and the content of the group VI B metal composition is larger than 10 wt% and less than or equal to 40 wt%. The carrier has a double-peak pore structure, and characterized by mercury intrusion porosimetry, the carrier has the pore volume of 0.6-1.4 mL/g and the specific surface area of 80-400 m＜2＞/g, the pore volume of pores with the diameter of 5-20 nm accounts for 30-60% of the total pore volume, and the pore volume of pores with the diameter of 100-300 nm accounts for 15-45% of the total volume. Compared with the prior art, the provided catalyst has relatively good hydrogenation residual-carbon removal performance when being applied to residuum hydrotreatment.

Description

A kind of catalyst for hydrotreatment of residual oil and its preparation and application

Technical field

The present invention relates to a kind of heavy oil hydrogenating treatment catalyst and its preparation and application.

Background technology

With between worldwide crude oil heaviness, in poor quality and the petrochemicals diversification of demand, lighting Being becoming increasingly acute of contradiction, residual hydrogenation is increasingly important with the effect of catalytic cracking combined technique.The purpose master of residual hydrogenation technology If providing qualified raw material for catalytic cracking (RFCC).As RFCC charging, the performance of residual hydrogenation product, especially gold Genus, sulfur, nitrogen and carbon residue have material impact to catalytic cracking process.The carbon residue of wherein residual hydrogenation product is to catalytic cracking Impact more important, the carbon residue of heavy oil represents high boiling component green coke trend in process, the conversion of carbon residue Rate is one important indicator of Residue Hydrotreating Technology.It is generally desirable to be less than as the residual hydrogenation product carbon residue content of RFCC charging 6% [5].The high raw material of carbon residue, in the RFCC course of processing, coke and slurry oil yield are high, can largely effect on the operation of RFCC device Stability and product slates.Reduce residual hydrogenation equipment generate oil carbon residue be beneficial to lifted catalytically cracked material property, Improve product slates, be favorably improved residual hydrogenation and the economic benefit of catalytic cracking combined device.

While catalyst carrier is for the diffusion of reactant molecule and the deposition offer path of metal impurities and space Load for active component provides necessary dispersion and stayed surface.Differential responses require catalyst to have different diffusions With active specific surface.Residual oil, after protective agent and metal remover bed, contains in the raw material entering de- carbon residue desulfurizing agent bed The compounds such as substantial amounts of polycyclic aromatic hydrocarbon, when catalyst aperture is less, resistance to mass tranfer is larger.On the other hand, due to taking off carbon residue agent The deposition still containing a certain amount of metal, therefore carbon deposit and metal sulfide in the material touching is also possible to cause catalyst Aperture blocking, limited reactions thing molecule diffuse into catalyst duct interior contact to active center.Numerous studies show, Kong Jie Structure is improper to be to lead to one of key factor of catalyst for hydrotreatment of residual oil inactivation.Pore-size distribution has ten to catalyst performance Divide important meaning.Macroporous catalyst is conducive to the removing of the macromole carbon residue predecessor such as colloid, asphalitine, but the hole of catalyst Footpath is negatively correlated each other with specific surface, i.e. the big catalyst of average pore size, and its specific surface area is just little.Therefore in order to take into account this property Matter, catalyst needs rational pore size distribution.

Existing Heavy oil hydrogenation catalyst is disadvantageous in that its S, N removal rate, heavy metal removing rate and asphalitine take off Except good coupling can not be reached between rate, for example, the high catalyst of removing metal active often S, N removal rate and carbon residue removing Rate is not high.The reason produce problems is very complicated.First consist in raw material, in residual oil, the feature of each component is that molecular weight is big, Complex structure, saturation is low（Armaticity are high）, S, N content are high.In prior art, have and be suitable for carrying out such reaction aperture Catalyst is guard catalyst and catalyst for demetalation, for example：

A kind of Hydrodemetalation catalyst with relatively low carbon deposition quantity and greater activity disclosed in CN1267537C and its Preparation method.

A kind of residuum hydrogenating and metal-eliminating catalyst disclosed in CN1796500A, this catalyst is by a kind of load with double-hole Body and the molybdenum loading on this carrier and/or tungsten and cobalt and/or nickel metal component composition.The preparation side of the carrier that catalyst uses Method includes mixing a kind of precursor of aluminium oxide with the nitrogen-containing compound beyond a kind of deacidification, molding roasting.

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

But, the catalyst common problem that prior art provides is that carbon residue removal efficiency is low.

Content of the invention

The technical problem to be solved in the present invention be provide a kind of catalyst new, that there is preferable removal of ccr by hydrotreating performance, The preparation method of this catalyst and application.

Content according to the present invention includes：

1. a kind of catalyst for hydrotreatment of residual oil, containing alumina support and hydrogenation active metals component, wherein, described plus Hydrogen activity metal component is selected from least one metal component of group VIII and at least one vib metals component, in terms of oxide And on the basis of catalyst, the content of described VIII race's metal component is more than 3 to less than or equal to 10 weight %, group VIB metal group The content divided is more than 10 to less than or equal to 40 weight %, and described carrier has structure of double peak holes, is characterized with mercury injection method, described carrier Pore volume be 0.6-1.4 ml/g, specific surface area be 80-400 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for total pore volume 30-60%, the pore volume in a diameter of 100-300nm hole accounts 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 ml/g, specific surface Amass as 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, a diameter of 100-300nm hole Pore volume accounts for the 20-40% of total pore volume.

3. the catalyst according to 1 is it is characterised in that described metal component of group VIII is selected from cobalt and/or nickel, VIB Race's metal component is selected from molybdenum and/or tungsten, is counted and on the basis of catalyst by oxide, and the content of described VIII race's metal component is 3- 6 weight %, the content of metal component of group VIB is more than 11 to less than or equal to 30 weight %.

4. according to 1 catalyst preparation method, including prepare carrier and on this carrier load hydrogenation active metals Component, wherein, the preparation of described carrier includes hydrated alumina PA and PB containing boehmite is thin containing intending with a kind of Modifier PC mixing, molding, drying the roasting of the hydrated alumina of diaspore, wherein, the weight mixing of described PA, PB and PC Than for 20-60：20-50：The κ value of 5-50, PC for 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For PC hydration before modified The sour peptization index of aluminium oxide, DI₂Sour peptization index for described PC.

5. the method according to 4 is it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：35-50： 10-30.

6. the method according to 4 is it is characterised in that the k value of described PC is 0 to less than or equal to 0.6.

7. the method according to 4 or 5 is it is characterised in that the hole of the described hydrated alumina PA containing boehmite Hold for 0.75-1 ml/g, specific surface is 200-450 rice²/ gram, most probable bore dia 3-10nm；Described containing boehmite Hydrated alumina PB pore volume be 0.9-1.4 ml/g, specific surface be 100-350 rice²/ gram, most probable bore dia is more than 10 To less than or equal to 30nm.

8. the method according to 7 is it is characterised in that the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, specific surface is 200-400 rice²/ gram, most probable bore dia 5-10nm；Described containing boehmite Hydrated alumina PB pore volume be 0.95-1.3 ml/g, specific surface be 120-300 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 25nm.

9. the method according to 4,5 or 6 any one is it is characterised in that described PC is the particulate matter of 80-300 mesh.

10. the method according to 9 is it is characterised in that described PC is the particulate matter of 100-200 mesh.

11. methods according to 4 are it is characterised in that the condition of described drying includes：Temperature is 40-350 DEG C, the time For 1-24 hour, the condition of described roasting includes：Temperature is that the time is 1-8 hour more than 500 to less than or equal to 1200 DEG C.

12. methods according to 11 are it is characterised in that the condition of described drying includes：Temperature is 100-200 DEG C, when Between be 2-12 hour, the condition of described roasting includes：Temperature is that roasting time is that 2-6 is little more than 800 to less than or equal to 1000 DEG C When.

13. methods according to 4 are it is characterised in that be modified as PC's by the hydrated alumina containing boehmite One of method is by the described hydrated alumina molding containing boehmite, drying, is completely or partially ground it afterwards Mill, screening, the condition of described drying includes：Temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are to obtain method one The article shaped roasting arrived, sintering temperature is that roasting time is 1-8 hour, afterwards that it is complete more than 350 to less than or equal to 1400 DEG C Portion or part are ground, sieve；The three of method are to dodge the hydrated alumina containing boehmite to do, and it is big for dodging dry temperature In 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 two and with One or more of modifier that the three of method obtain is mixed to get.

14. methods according to 13 are it is characterised in that the condition of drying in methods described one includes：Temperature is 100-200 DEG C, the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 0.1-6 is little When；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.

15. methods according to 13 are it is characterised in that described PC is changing of the hydrated alumina containing boehmite The particulate matter of 80-300 mesh in property thing.

16. methods according to 15 are it is characterised in that described PC is changing of the hydrated alumina containing boehmite The particulate matter of 100-200 mesh in property thing.

17. methods according to 4 are it is characterised in that the described method in supported on carriers hydrogenation active metals component For infusion process, simultaneously use this solution impregnating carrier including the solution preparing the compound containing hydrogenation active metals, be dried afterwards, Roasting or not roasting, described hydrogenation active metals group is selected from the metal component and at least one VIIIth of at least one vib The metal component of race, is counted and on the basis of catalyst by oxide, and the described compound containing hydrogenation active metals is in described solution Concentration and the consumption of described solution make the content of the metal component of vib in final catalyst be more than 10 to being less than or equal to 40 weight %, the content of the metal component of described VIIIth race is more than 3 to less than or equal to 10 weight %；Described drying condition includes：Temperature Spend for 100-250 DEG C, the time is 1-10 hour；Described roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hour.

18. methods according to 17 it is characterised in that the metal component of described vib is selected from molybdenum and/or tungsten, the The metal component of VIII race is selected from cobalt and/or nickel, is counted and on the basis of catalyst by oxide, the described change containing hydrogenation active metals Compound makes the content of the metal component of the vib in final catalyst big in the concentration of described solution and the consumption of described solution In 11 to less than or equal to 30 weight %, the content of the metal component of the VIIIth race is 3-6 weight %；Described drying condition includes：Temperature For 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.

Application in residual hydrocracking for the catalyst described in any one in 19. claim 1-3.

The catalyst providing according to the present invention, requires carrier therein to can be made into various easily operated molding depending on difference Thing, for example spherical, cellular, nest like, tablet or bar shaped（Herba Trifolii Pratentis, butterfly, cylinder etc.）.Described molding can be routinely square Method is carried out, for example, the combination of one of spin, tabletting and extruded moulding method or several method.In molding, such as extrusion Molding, for ensure described molding be smoothed out, can add in described mixture water, extrusion aid and/or adhesive, contain or Without expanding agent, then extrusion molding, it is dried afterwards and roasting.Described extrusion aid, the species of peptizer and consumption are this Well known to skilled person, for example common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, gather One or more of ethanol, described peptizer can be mineral acid and/or organic acid, described expanding agent can be starch, One or more of synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein is preferably hydroxylmethyl cellulose One or more of element, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably poly- One or more of ethylene glycol, poly- propanol, polyvinyl alcohol, surfactant is preferably fat alcohol polyethylene ether, fatty alcohol acyl Amine and its derivant, molecular weight are one or more of propylene alcohol copolymer and maleic acid copolymer of 200-10000.

In the present invention, described acid peptization index D I refers to the hydrated alumina containing boehmite and containing the thin water of plan The hydrated alumina modifier of aluminum stone adds after nitric acid by necessarily sour aluminum ratio, by peptization containing plan within certain response time The hydrated alumina of boehmite is with Al₂O₃The percent of meter, DI=（1-W₂/W₁) × 100%, W₁And W₂It is respectively to contain and intend thin water Before the hydrated alumina of aluminum stone and acid reaction and with acid reaction after with Al₂O₃The weight of meter.

The mensure of DI includes：(1) measure the calcination base of the hydrated alumina containing boehmite（Also referred to as butt）Content （Calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, its burning after weight with burn before weight ratio, with Percent represents）, it is calculated as a；(2) the hydrated alumina W containing boehmite is weighed with analytical balance₀Gram, W₀Amount meet with Al₂O₃The W of meter₁For 6 grams（W₁/a=W₀）, weigh W gram of deionized water, W=40.0-W₀, will weigh containing the thin water aluminum of plan under stirring The hydrated alumina of stone and deionized water add mixing in beaker；(3) pipette 20mL with 20mL pipet, concentration is the dilute of 0.74N Salpeter solution, this acid solution is added to step（2）Beaker in, the lower reaction of stirring 8 minutes；(4) by step（3）Reacted Serosity is centrifuged in centrifuge, precipitate is inserted in the crucible weighed, afterwards, it is little in 125 DEG C of dryings 4 When, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain 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 the described water containing boehmite Close aluminium oxide PA and PB not specially require, can be boehmite or the thin water of plan of any prior art preparation Aluminum stone and the mixture of other hydrated aluminas, described others hydrated aluminas are selected from a water aluminium oxide, gibbsite One or more of and amorphous hydrated aluminium oxide.

In a detailed embodiment, the described preferred pore volume of hydrated alumina PA containing boehmite is 0.75-1 Ml/g, specific surface is 200-450 rice²/ gram, most probable bore dia 3-10nm, further preferred pore volume is 0.80-0.95 milli Rise/gram, specific surface is 200-400 rice²/ gram, most probable bore dia 5-10nm；The described hydrated alumina containing boehmite The preferred pore volume of 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 being less than or equal to 30nm, further preferred 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 pore size, are by institute State the hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, characterized by BET N2 adsorption and obtain.

In further preferred embodiment, characterized with X diffraction, the described hydrated alumina PA containing boehmite It is not less than 50% with the boehmite content in PB, be more preferably not less than 60%.

Inventors of the present invention have surprisingly found that, the hydrated alumina containing boehmite is carried out being thermally treated resulting in changing Property thing PC, with respect to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, will After this modifier and PA and PB mixed-forming, drying roasting, obtained carrier has obvious bimodal pore distribution.Especially It is after by the granule of 80-300 mesh therein, the preferably 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 The granule of 100-200 mesh refers to described modifier through sieving（Include step that is broken or grinding if necessary）, it sieves thing（Under sieve Thing）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 the hydrated alumina containing boehmite can be any prior art preparation Boehmite or the mixture of boehmite and other hydrated aluminas, described others hydrated aluminas Selected from one or more of a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment, Described PC is the modifier of PA and/or PB.

In the present invention, the Mixing ratio by weight of described PA, PB and PC refers to parts per hundred parts in the mixture of described PA, PB and PC The ratio of parts by weight shared by PA, PB and PC difference.Wherein, PA：PB：PC is preferably 20-60：20-50：5-50, further preferably For 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) it is based on and be dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method During regular oxidation alumina supporter is prepared in molding, the tailing of drying by-product, for example：In extruded moulding, bar shaped article shaped exists The dry, tailing of integer process by-product（Waste material is traditionally referred to as dried）, this tailing is milled, sieves and obtain PC.

(2) obtained based on roasting, become according to a conventional method including by hydrated alumina PA and/or PB containing boehmite During regular oxidation alumina supporter prepared by type, the tailing of fired by-product（Traditionally it is referred to as roasting waste material）, for example, become in spin In type, the tailing of spheroidal particle by-product in roasting process, this tailing is milled, sieves and obtain PC；Or directly will PA and/or PB dodge dry obtains, directly will PA and/or PB dodge dry when, flash-off time is preferably 0.05-1 hour, further preferably For 0.1-0.5 hour.

(3) two or more be mixed to get in the modifier PC being obtained based on preceding method.When being obtained using mixed method When obtaining C, the mixed proportion of the modifier PC that aforementioned several method is respectively obtained does not limit.

The catalyst providing according to the present invention, wherein, the preferred VIII race's metal component of described hydrogenation active metals component is Cobalt and/or nickel, VI B race metal component is molybdenum and/or tungsten, is counted and on the basis of catalyst by oxide, described VIII race's metal group Point content preferably greater than 3 to less than or equal to 10 weight %, more preferably 3-6 weight %, described VI B race metal component , to less than or equal to 40 weight %, further preferably greater than 11 to less than or equal to 30 weight % for content preferably greater than 10.

Enough to, on the premise of described hydrogenation active metals component is carried on described carrier, the present invention is to described negative Support method is not particularly limited, and preferred method is infusion process, including the dipping solution of the compound prepared containing described metal, it Afterwards with the carrier described in this solution impregnation.Described dipping method is conventional method, for example, it may be excessive immersion stain, hole are satisfied With method infusion process.One of described soluble compound being selected from containing the metal component compound selected from VI B race in them Or several, such as one or more of molybdenum oxide, molybdate, paramolybdate, molybdenum oxide preferably wherein, ammonium molybdate, para-molybdic acid Ammonium；One or more of tungstates, metatungstate, ethyl metatungstate, ammonium metatungstate preferably wherein, ethyl metatungstic acid Ammonium.Described is selected from one or more of their soluble compound, such as nitre containing the compound selected from VIII race's metal component One or more of soluble complexes of sour cobalt, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt, preferably cobalt nitrate, alkali Formula cobalt carbonate；One or more of soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride. and nickel, preferably For nickel nitrate, basic nickel carbonate.

The catalyst providing according to the present invention, can also contain any present invention that do not affect provides catalyst performance or can change The addO-on therapy of the catalytic performance of catalyst that rare book invention provides.As the addO-on therapy such as phosphorus can be contained, in terms of oxide simultaneously On the basis of catalyst, the content of described addO-on therapy is less than 10 weight %, 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 can be the compound containing components such as described phosphorus is directly mixed with described boehmite, molding roasting；Permissible It is that the compound containing components such as described phosphorus and the compound containing hydrogenation active metals component are configured to leaching after mixed solution Carrier described in stain；Can also be individually to prepare the compound containing components such as phosphorus and after solution, impregnate described carrier roasting.When When the addO-on therapy such as phosphorus and hydrogenation active metals introduce described carrier respectively, preferably first with containing described addO-on therapy compound Carrier roasting described in solution impregnation, afterwards again with the solution impregnation containing hydrogenation active metals component composition.Wherein, institute State sintering temperature and be 400-600 DEG C, preferably 420-500 DEG C, roasting time is 2-6 hour, preferably 3-6 hour.

According to process for hydrogenating residual oil provided by the present invention, the reaction condition of the hydrotreating of described hydrocarbon ils is not had Especially limit, in a preferred embodiment, described hydrotreating reaction condition is：Reaction temperature 300-550 DEG C, excellent further Select 330-480 DEG C, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hour^-1, further preferably 0.15-2 hour^-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.

The device of described hydrogenation reaction can any enough to make described raw oil at hydrotreating reaction conditions with institute State in the catalytic reactor of catalyst and carry out, for example, in described fixed bed reactors, moving-burden bed reactor or ebullated bed are anti- Answer in device and carry out.

According to the conventional method in this area, described hydrotreating catalyst before the use, generally can exist in hydrogen Under, 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, 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 catalyst is special It is not suitable for heavy oil particularly poor residuum and carries out hydrotreating, to be subsequent technique（As catalytic cracking process）There is provided and close The raw oil of lattice.Compared with prior art, the catalyst that the present invention provides has more preferable adding when for residual hydrocracking Hydrogen takes off carbon residue performance.

Specific embodiment

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

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%, and gibbsite content is 5 weight %, surplus For 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%, and 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%, and gibbsite content is 5 weight %, remaining Measure as 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, and specific surface is 260 Rice²/ gram, most probable bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weights Amount %, balance of amorphous alumina, DI value 17.2）.

Embodiment 1-8 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 of aqueous solution 1000 Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar, in 120 DEG C of dryings 4 hours, obtains dried strip, By dried strip shaping, sieve, length is less than the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled, Sieve, take wherein 100～200 mesh sieves to divide, 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 of aqueous solution 1000 Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, 800 DEG C of roastings 4 Hour, obtain carrier, carrier strip shaping is sieved, length is less than the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up Material）Milled, sieved, take wherein 100～200 mesh sieves to divide, 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.The k value of PC-A3 is shown in Table 1.

Embodiment 4

Each 200 grams of the PC-A3 that the PC-A1 that obtain embodiment 1 and embodiment 3 obtain uniformly mixes, and obtains PA-1 and PA- 2 modifier PC-A4.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 of aqueous solution 1440 Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is in 120 DEG C of dryings 4 hours, 1200 DEG C of roastings 4 Hour, obtain carrier, carrier strip shaping is sieved, length is less than the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up Material）Milled, sieved, take wherein 100～200 mesh sieves to divide, 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 of aqueous solution 1440 Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar, in 120 DEG C of dryings 4 hours, obtains dried strip, By dried strip shaping, sieve, length is less than the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled, Sieve, take wherein 100～200 mesh sieves to divide, obtain the modifier PC-B3 of PB-2.The k value of PC-B3 is shown in Table 1.

Embodiment 8

Each 200 grams of the PC-B2 that the PC-B1 that obtain embodiment 5 and embodiment 6 obtain uniformly mixes, and obtains PB-1 and PB- 2 modifier PC-B4.The k value of PC-B4 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

Embodiment 9-16 illustrates the preparation method of the bimodal hole carrier that the present invention provides.Comparative example 1-5 illustrates Conventional catalytic The preparation method of agent carrier.

Embodiment 9

Weigh each 400 grams of PA-1 and PB-1, after 200 grams of raw material PC-A2 being obtained with embodiment 2 are uniformly mixed, addition contains Nitric acid（Tianjin chemical reagent three factory's product）1300 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.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 are carried Body Z1.The property of carrier Z1 is listed in table 2.

Embodiment 10

Weigh 300 grams of PA-2,200 grams of PB-2, after 500 grams of raw material PC-B2 being obtained with embodiment 6 are uniformly mixed, add The chemical reagent of Tianjin containing nitric acid three factory's product）1300 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.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 are carried Body Z2.The property of carrier Z2 is listed in table 2.

Embodiment 11

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

Comparative example 1

Weigh 500 grams of PA-2,500 grams of PB-2, after uniformly mixing, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 millis 1300 milliliters of the aqueous solution rising, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is little in 120 DEG C of dryings 4 When, obtain article shaped, 900 DEG C of roastings of this article shaped 3 hours obtain carrier DZ1.The property of carrier DZ1 is listed in table 2.

Comparative example 2

Weigh 400 grams of PA-1,600 grams of PB-1, after uniformly mixing, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 millis 1300 milliliters of the aqueous solution rising, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is little in 120 DEG C of dryings 4 When, obtain article shaped, 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 12

Weigh 250 grams of PA-1,500 grams of PB-1, with embodiment 1 be obtained 100 grams of raw material PC-A1 and embodiment 7 be obtained After 150 grams of raw material PC-B3 uniformly mix, add and contain nitric acid（Tianjin chemical reagent three factory's product）10 milliliters of aqueous solution 1300 milli Rise, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, will 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 13

Weigh 350 grams of PA-2,350 grams of PB-2, with embodiment 3 be obtained 150 grams of raw material PC-A3 and embodiment 5 be obtained After 150 grams of raw material PC-B1 uniformly mix, add the chemical reagent of Tianjin containing nitric acid three factory's product）10 milliliters of aqueous solution 1440 milli Rise, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, will 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 14

Weigh 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-B1 being obtained with embodiment 5 are uniformly mixed, add The chemical reagent of Tianjin containing nitric acid three factory's product）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.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 are carried Body Z6.The property of carrier Z6 is listed in table 2.

Embodiment 15

Weigh 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-A4 being obtained with embodiment 4 are uniformly mixed, add The chemical reagent of Tianjin containing nitric acid three factory's product）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.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 are carried Body Z7.The property of carrier Z76 is listed in table 2.

Embodiment 16

Weigh 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-A2 being obtained with embodiment 2 are uniformly mixed, add The chemical reagent of Tianjin containing nitric acid three factory's product）1440 milliliters of 10 milliliters of aqueous solution, is extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.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 are carried Body 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 φ 1.4mm's on plunger type bar extruder Butterfly bar.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 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 φ 1.4mm's on plunger type bar extruder Butterfly bar.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 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 milliliters of aqueous solution 1300 milliliters, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar, in 120 DEG C of dryings 4 hours, is become Type thing, 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, compared with conventional method, being had by alumina support prepared by the method provided by the present invention by the result of table 2 There is obvious structure of double peak holes.

Embodiment 17-20 illustrates catalyst that the present invention provides and preparation method thereof.

Wherein, in catalyst, the content of active metal component adopts Xray fluorescence spectrometer to measure（All appts are Japan Liue electrical machinery Industrial Co., Ltd 3271 type Xray fluorescence spectrometer, concrete grammar is shown in Petrochemical Engineering Analysis method RIPP133- 90）.

Embodiment 17

Take 200 grams of carrier Z1, contain MoO with 210 milliliters₃174.8 g/l, CoO42.2 g/l of molybdenum oxide and alkali formula carbon Sour cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst C1.In catalyst C1 Molybdenum oxide and the content of cobalt oxide be listed in table 3.

Comparative example 6

Take 200 grams of carrier DZ1, contain MoO with 180 milliliters₃203.9 g/l, CoO49.2 g/l of molybdenum oxide and alkali formula carbon Sour cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst DC1.Catalyst DC1 In molybdenum oxide and the content of cobalt oxide be listed in table 3.

Embodiment 18

Take 200 carrier Z2, contain MoO with 200 milliliters₃124.3 g/l, NiO29.6 g/l of molybdenum oxide and basic carbonate Nickel mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst C2.In catalyst C2 The content of molybdenum oxide and nickel oxide is listed in table 3.

Comparative example 7

Take 200 carrier DZ3, contain MoO with 180 milliliters₃138.1 g/l, NiO32.9 g/l of molybdenum oxide and basic carbonate Nickel mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst DC2.In catalyst DC2 Molybdenum oxide and the content of nickel oxide be listed in table 3.

Embodiment 19

Take 200 grams of carrier Z3, contain MoO with 205 milliliters₃179.1 g/l, NiO43.2 g/l of ammonium molybdate and nickel nitrate Mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, and 420 DEG C of roastings 3 hours obtain catalyst C3.Oxygen in catalyst C3 Change molybdenum and the content of nickel oxide is listed in table 3.

Comparative example 8

Take 200 grams of carrier DZ4, contain MoO with 180 milliliters₃203.9 g/l, NiO49.2 g/l of molybdenum oxide and alkali formula carbon Sour nickel mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst DC3.Catalyst DC3 In molybdenum oxide and the content of nickel oxide be listed in table 3.

Embodiment 20

Take 200 grams of carrier Z8, contain MoO with 200 milliliters₃209.1 g/l, CoO52.3 g/l of molybdenum oxide and alkali formula carbon Sour cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst C4.In catalyst C5 Molybdenum oxide and the content of cobalt oxide be listed in table 3.

Comparative example 9

Take 200 grams of carrier DZ5, contain MoO with 200 milliliters₃209.1 g/l, CoO52.3 g/l of molybdenum oxide and alkali formula carbon Sour cobalt mixed solution impregnates 1 hour, dries 2 hours in 120 DEG C, 420 DEG C of roastings 3 hours, obtains catalyst DC4.Catalyst DC4 In molybdenum oxide and the content of cobalt oxide be listed in table 3.

Table 3

Embodiment 21-24

Embodiment 21-24 illustrates that the residual hydrogenation of the catalyst that the present invention provides takes off carbon residue desulfurization performance.

The granule respectively catalyst C1, C2, C3 and C4 being broken into diameter 2-3 millimeter loads reactor.Reaction condition is： 380 DEG C of reaction temperature, 14 MPas of hydrogen dividing potential drop, raw oil：Raw oil for nickel content be 15.6ppm, content of vanadium be 38.2ppm, sulfur The husky light VRDS in Maoming that content is 3.3%, nitrogen content is 0.24%, carbon residue is 10.7%.

Product analyses：Carbon residue content in oil after being processed using oil product Conradson method mensure（Instrument is U.S. The micro carbon residue analyzer of ALCOR company of state MCRT-160 type, concrete grammar is shown in GB/T17144）.Measure containing of sulfur using coulometry Amount（Concrete grammar is shown in Petrochemical Engineering Analysis method RIPP62-90）.

Calculate total removal efficiency of impurity according to the following formula respectively：

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

Comparative example 10-13

Method according to embodiment 21-24 evaluates de- carbon yield and the desulfurization degree of catalyst DC1, DC2, DC3 and DC4, knot Fruit is shown in Table 4.

Table 4

Embodiment	Catalyst is numbered	De- carbon yield/%	Desulfurization degree/%
				21	C1	48.4	82.0
Comparative example 10	DC1	43.9	81.8
				22	C2	50.2	79.8
Comparative example 11	DC2	44.7	78.6
				23	C3	51.9	81.1
Comparative example 12	DC3	45.3	78.9
				24	C4	49.4	83.0
Comparative example 13	DC4	46.0	83.0

Can be seen by table 4 result, the de- carbon residue activity of catalyst is provided by the present invention during residual hydrocracking Existing catalyst to be substantially better than with desulphurizing activated, illustrate this technology invention catalyst more suitable for the processing of poor residuum at Reason.

Claims

1. a kind of catalyst for hydrotreatment of residual oil, containing alumina support and hydrogenation active metals component, wherein, described hydrogenation is lived Property metal component be 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 is more than 3 to less than or equal to 10 weight %, metal component of group VIB Content is more than 10 to less than or equal to 40 weight %, and described carrier has structure of double peak holes, is characterized with mercury injection method, the hole of described carrier Hold for 0.6-1.4 ml/g, specific surface area is 80-400 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 30- of total pore volume 60%, the pore volume in a diameter of 100-300nm hole accounts for the 15-45% of total pore volume.

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

3. catalyst according to claim 1 is it is characterised in that described metal component of group VIII is selected from cobalt and/or nickel, and the Group vib metal component is selected from molybdenum and/or tungsten, is counted and on the basis of catalyst by oxide, the content of described VIII race's metal component For 3-6 weight %, the content of metal component of group VIB is more than 11 to less than or equal to 30 weight %.

4. the preparation method of catalyst according to claim 1, including preparing carrier and load hydrogenation activity on this carrier Metal component, wherein, the preparation of described carrier is included by the hydrated alumina PA containing boehmite with containing the thin water aluminum of plan The hydrated alumina PB of stone is mixed with a kind of modifier PC of the hydrated alumina containing boehmite, molding, drying roasting Burn, wherein, the pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 Rice²/ gram, most probable bore dia 3-10nm；The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 milli Rise/gram, specific surface is 100-350 rice²/ gram, most probable bore dia is more than 10 to less than or equal to 30nm；Described PA, PB and PC's Mixing ratio by weight is 20-60：20-50：The κ value of 5-50, PC for 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁Change for PC The sour peptization index of the hydrated alumina before property, DI₂Sour peptization index for described PC.

5. method according to claim 4 is it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50：35- 50：10-30.

6. method according to claim 4 it is characterised in that described PC κ value for 0 to less than or equal to 0.6.

7. the method according to claim 4 or 5 is it is characterised in that the described hydrated alumina PA containing boehmite Pore volume be 0.80-0.95 ml/g, specific surface be 200-400 rice²/ gram, most probable bore dia 5-10nm；Described containing plan The pore volume of the hydrated alumina PB of boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, most probable hole With diameter greater than 10 to less than or equal to 25nm.

8. the method according to claim 4,5 or 6 any one is it is characterised in that described PC is the granule of 80-300 mesh Thing.

9. method according to claim 8 is it is characterised in that described PC is the particulate matter of 100-200 mesh.

10. method according to claim 4 is it is characterised in that the condition of described drying includes：Temperature is 40-350 DEG C, Time is 1-24 hour, and the condition of described roasting includes：Temperature is that the time is that 1-8 is little more than 500 to less than or equal to 1200 DEG C When.

11. methods according to claim 10 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 less than or equal to 1000 DEG C more than 800, and roasting time is 2-6 hour.

12. methods according to claim 4 are it is characterised in that be modified as the hydrated alumina containing boehmite One of method of PC is by the described hydrated alumina molding containing boehmite, drying, completely or partially enters it afterwards Row grinds, screening, and the condition of described drying includes：Temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are by method One of the article shaped roasting that obtains, sintering temperature is that roasting time is 1-8 hour, afterwards more than 350 to less than or equal to 1400 DEG C It is completely or partially ground, sieves；The three of method are that the hydrated alumina containing boehmite dodges dry, the dry temperature of sudden strain of a muscle Degree is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C；The four of method be by one of method, method it Two and method three modifiers obtaining in several be mixed to get.

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

14. methods according to claim 12 are it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in 80-300 mesh particulate matter.

15. methods according to claim 14 are it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in 100-200 mesh particulate matter.

16. methods according to claim 4 it is characterised in that described in supported on carriers hydrogenation active metals component Method is infusion process, and the solution including the compound prepared containing hydrogenation active metals simultaneously uses this solution impregnating carrier, carries out afterwards Drying, roasting or not roasting, described hydrogenation active metals group is selected from metal component and at least one of at least one vib The metal component of the VIIIth race, is counted and on the basis of catalyst by oxide, and the described compound containing hydrogenation active metals is described The consumption of the concentration of solution and described solution makes the content of the metal component of the vib in final catalyst be more than 10 to being less than Equal to 40 weight %, the content of the metal component of described VIIIth race is more than 3 to less than or equal to 10 weight %；Described drying condition bag Include：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.

17. methods according to claim 16 it is characterised in that described vib metal component be selected from molybdenum and/or Tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, is counted and on the basis of catalyst by oxide, described golden containing hydrogenation activity The compound belonging to makes the metal component of the vib in final catalyst in the concentration of described solution and the consumption of described solution Content is more than 11 to less than or equal to 30 weight %, and the content of the metal component of the VIIIth race is 3-6 weight %；Described drying condition bag Include：Temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting condition includes：Temperature is 360-450 DEG C, and the time is that 2-6 is little When.

Application in residual hydrocracking for the catalyst described in any one in 18. claim 1-3.