CN103865568B

CN103865568B - VB metal component-containing hydrogenation catalyst, preparation and application thereof

Info

Publication number: CN103865568B
Application number: CN201210536264.XA
Authority: CN
Inventors: 孙淑玲; 杨清河; 胡大为; 刘佳; 王奎; 刘涛; 聂红; 李大东
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: 2012-12-12
Filing date: 2012-12-12
Publication date: 2017-03-22
Anticipated expiration: 2032-12-12
Also published as: CN103865568A

Abstract

The invention relates to a group VB metal component-containing hydrogenation catalyst, preparation and an application thereof. The catalyst contains a carrier and a hydrogenation activity metal component loaded on the carrier, wherein the hydrogenation activity metal component is a combination comprising one at least selected from a group VIB metal component and one at least selected from a group VB metal component, the carrier contains alumina, the pore volume of the alumina is 0.9-1.2 ml/g, the specific surface area is 50-300 m＜2＞/g, the pore volume of the pores having a diameter of 10-30 nm accounts for 55-80% of the total pore volume, and the pore volume of the pores having a diameter of 300-500 nm accounts for 10-35% of the total pore volume, wherein the carrier preparation method comprises: mixing pseudoboehmite-containing hydrated alumina P1 and a modifier P2 of the P1, molding, drying and calcinating, wherein a weight mixing ratio of the P1 to the P2 is (20-95):(5-80), the k value of the P2 is more than or equal to 0 and is less than or equal to 0.9, the k is equal to DI2/DI1, the DI1 is the acid dispersion index of the pseudoboehmite-containing hydrated alumina P1, and the DI2 is the acid dispersion index of the modifier P2 of the P1. Compared with the group VB metal component-containing hydrogenation catalyst in the prior art, the group VB metal component-containing hydrogenation catalyst of the present invention has significantly-increased hydrogenation demetallization and asphaltene-removing activity.

Description

With the hydrogenation catalyst containing VB metal components and its preparation and application

Technical field

The present invention is to be related to a kind of hydrogenation catalyst, preparation and its application, and more particularly to one kind is suitable for processing of heavy oil Hydrogenation catalyst, preparation and its application.

Background technology

With worldwide crude oil heaviness, in poor quality and the petrochemicals diversification of demand, the lance of lighting Shield is becoming increasingly acute, and the main task of petroleum chemical industry is will focus in heavy oil lighting.Residual oil is most heavy fraction in crude oil, Molecular weight is big Jing after distillation for crude oil, baroque ampholyte species in residual oil, these impurity to the follow-up course of processing and Product property has material impact, thus must first go through hydrotreating by these impurity removals.Compared with distillate, in heavy oil In addition to impurity such as sulfur, nitrogen, the also metal impurities such as Ni, V containing higher proportion, and asphalt content are high, carbon residue It is higher.If the wherein metal impurities such as Ni, V effectively cannot be removed, downstream catalyst can be had a negative impact, clog downstream is urged Agent duct, so that cause the inactivation of downstream catalyst.Therefore, developing the high Hydrodemetalation catalyst of metal removal activity can be with Effectively extend the service life of downstream catalyst, so as to play a part of to protect downstream catalyst and extension fixture service cycle. Due to the These characteristics of residual oil, in commercial Application, the activity stability of residual oil hydrocatalyst is particularly significant, both at home and abroad many families Patent business releases various residuum hydrogenating and metal-eliminating agent.

CN1054393C discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and its feature is to adopt physics Two kinds of means of method and chemical method improve the pore structure of residuum hydrogenating and metal-eliminating agent.

CN1267537C discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and its feature is in load used Contain a kind of halogen in body, the ratio of halogen accounts for 0.1-5 weight % of carrier so as to which the acidity of carrier is less than 0.2 mM/gram （Carrier acid amount is relatively low）, while making catalyst keep higher HDM activity, coke content is low.

CN1946831A and US7608558 disclose a kind of hydrotreating catalyst comprising VB races metal, and its feature exists In metal component（Calculated with oxide）At least 50 weight % of catalyst are constituted, the mol ratio wherein between metal component meets Following formula：（Group vib+VB races）：（VIII）=0.5-2:1.

US5275994 describes the hydrotreating catalyst suitable for hydrocarbon charging, and which includes group VIII metal component, VIB Race's metal component and VB races metal component.This trimetallic catalyst must be supported on silicon dioxide or aluminium oxide and preferred With comprising the metal component less than 28 weight %（In terms of oxide）It is characterized.In catalyst preparation, VB races metal component is necessary Add as alkoxide in water-less environment, and preferably by catalyst overall at least 500 DEG C roastings.

The content of the invention

The technical problem to be solved in the present invention be to provide it is a kind of it is new, with high HDM, depitching matter isoreactivity And the catalyst of stability, the preparation and its application of the catalyst.

It was found by the inventors of the present invention that the stability of heavy oil hydrogenation demetal reacting middle catalyst and the heat in course of reaction Effect is relevant.The hydrodesulfurization for wherein occurring is strong exothermal reaction, is a kind of key factor for causing such catalyst inactivation.Cause This, by the selection to catalyst activity metal component, can make catalyst while high HDM activity is kept, incite somebody to action Hydrodesulfurization activity is controlled in an appropriate level, and then improves the stability of such catalyst.

The present invention relates to following invent：

1st, a kind of hydrogenation catalyst of the metal component of race containing VB, containing carrier and load hydrogenation activity gold on this carrier Category component, described hydrogenation active metals component be selected from least one group vib metal component with least one selected from VB races Metal component combination, wherein, the carrier contains aluminium oxide, and the pore volume of the aluminium oxide is 0.9-1.2 ml/g, than Surface area is 50-300 rice²/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 55-80% of total pore volume, a diameter of 300-500nm The pore volume in hole accounts for the 10-35% of total pore volume.

2nd, the catalyst according to 1, it is characterised in that the pore volume of the aluminium oxide is 0.95-1.15 ml/g, than Surface area is 80-200 rice²/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 60-75% of total pore volume, a diameter of 300-500nm The pore volume in hole accounts for the 15-30% of total pore volume.

3rd, the catalyst according to 1, it is characterised in that counted by oxide and on the basis of catalyst, the group vib gold The content of category component is 0.2-15 weight %, and the content of VB races metal component is 0.2-12 weight %.

4th, the catalyst according to 1 or 3, it is characterised in that the metal component of the group vib is selected from molybdenum and/or tungsten, VB Race's metal component is selected from vanadium and/or niobium, is counted by oxide and on the basis of catalyst, and the content of the group vib metal component is 0.5-12 weight %, the content of VB races metal component is 0.5-9 weight %.

5th, the catalyst according to 4, it is characterised in that the metal component of the group vib is molybdenum or tungsten, VB races metal group It is divided into vanadium, is counted by oxide and on the basis of catalyst, the content of the group vib metal component is 5-12 weight %, VB races metal The content of component is 1-9 weight %.

6th, a kind of preparation method of the hydrogenation catalyst of the metal component of race containing VB, including prepare salic carrier and The supported on carriers hydrogenation active metals component, wherein, the preparation method of the carrier is included the water containing boehmite Modifier P2 mixing, molding, drying the roasting of aluminium oxide P1 and P1 is closed, the Mixing ratio by weight of the P1 and P2 is 20-95：5- 80, P2 κ values are the κ=DI 0 to less than or equal to 0.9₂/DI₁, DI₁It is the acid of the hydrated alumina P1 containing boehmite Peptization index, DI₂It is the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.

7th, the method according to 6, it is characterised in that the Mixing ratio by weight of the P1 and P2 is 70-95：5-25.

8th, the method according to 6, it is characterised in that the k value of the P2 is 0 to less than or equal to 0.6.

9th, the method according to 6 or 7, it is characterised in that the hole of the hydrated alumina P1 containing boehmite Hold for 0.9-1.4 ml/g, specific surface is 100-350 rice²/ gram, most can and bore dia 8-30nm.

10th, the method according to 9, it is characterised in that the pore volume of the hydrated alumina P1 containing boehmite For 0.95-1.3 ml/g, specific surface is 120-300 rice²/ gram, most can and bore dia 10-25nm.

11st, the method according to 6,7 or 8 any one, it is characterised in that particulate matters of the P2 for 80-300 mesh.

12nd, the method according to 11, it is characterised in that particulate matters of the P2 for 100-200 mesh.

13rd, the method according to 6, it is characterised in that the condition of the drying includes：Temperature is 40-350 DEG C, the time For 1-24 hours, the condition of the roasting includes：Temperature is that the time is 1-8 hours more than 500 to less than or equal to 1200 DEG C.

14th, the method according to 13, it is characterised in that the condition of the drying includes：Temperature is 100-200 DEG C, when Between be 2-12 hours, the condition of the roasting includes：Temperature is that roasting time is 2-6 more than 800 to less than or equal to 1000 DEG C Hour.

15th, the method according to 6, it is characterised in that by P1 be modified as one of method of P2 be will it is described containing intend it is thin Its all or part is ground, is sieved by the hydrated alumina P1 molding of diaspore, drying afterwards, the condition of the drying Including：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are the article shaped roastings for obtaining one of method, roasting Temperature is that roasting time is 1-8 hours, afterwards its all or part is ground, is sieved more than 350 to less than or equal to 1400 DEG C Point；The three of method are that the hydrated alumina P1 containing boehmite is dodged dry, and it is to being less than or equal to more than 150 to dodge dry temperature 1400 DEG C, flash-off time is 0.05-1 hours；The four of method be by one of method, method two and with the three of method obtain change Two or more in property thing are mixed to get.

16th, the method according to 15, it is characterised in that the condition of the drying in methods described one includes：Temperature is 100-200 DEG C, the time is 2-12 hours；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 0.1-6 is little When；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5 hours.

17th, the method according to 15 or 16, it is characterised in that the P2 is the granule of 80-300 mesh in P1 modifiers Thing.

18th, the method according to 17, it is characterised in that the P2 is the particulate matter of 100-200 mesh in P1 modifiers.

19th, the method according to 6, it is characterised in that described hydrogenation active metals component is selected from least one VIB The combination of the metal component of race and at least one metal component selected from VB races, it is described in supported on carriers hydrogenation active metals Multi-component approach is infusion process, including：a）Prepare the solution of metallic compound containing group vib and/or VB races metallic compound；b）With step Rapid a）The solution impregnation of alumina carrier of preparation；c）It is dried and calcination stepses b）The impregnation product for obtaining；Wherein, in terms of oxide And on the basis of catalyst, the concentration of the impregnation liquid and consumption cause containing for group vib metal component described in final catalyst Measure as 0.2-15 weight %, the content of VB races metal component is 0.2-12 weight %, the drying condition is：Temperature 80-200 DEG C, Time 1-8 hour, roasting condition is：Temperature 400-600 DEG C, time 2-8 hour.

20th, the method according to 19, it is characterised in that the metal component of the group vib is selected from molybdenum and/or tungsten, VB races Metal component is selected from vanadium and/or niobium, is counted by oxide and on the basis of catalyst, and the concentration of the impregnation liquid and consumption are caused most The content of group vib metal component described in whole catalyst is 0.5-12 weight %, and the content of VB races metal component is 0.5-9 weights % is measured, the drying condition is：Temperature 100-150 DEG C, time 2-6 hour, roasting condition is：Temperature 420-500 DEG C, time 3-6 Hour.

21st, the method according to 20, it is characterised in that counted by oxide and on the basis of catalyst, the impregnation liquid Concentration and consumption cause group vib metal component described in final catalyst content be 5-12 weight %, VB races metal component Content is 1-9 weight %.

22nd, a kind of heavy oil hydrogenation demetal method, is included in heavy raw oil under heavy oil hydrogenation demetal reaction condition Contact with Hydrodemetalation catalyst, the catalyst is the catalyst described in aforementioned any one of 1-5.

According to the catalyst that the present invention is provided, require that carrier therein can be made into various easily operated molding depending on difference Thing, such as spherical, cellular, nest like, tablet or bar shaped（Herba Trifolii Pratentis, butterfly, cylinder etc.）.Molding can be entered according to a conventional method The combination of a kind of method or several method OK, for example, in spin, tabletting and extruded moulding.In molding, such as extrusion into Type, is to ensure that the molding is smoothed out, can add in described mixture water, extrusion aid and/or adhesive, containing or not Containing expanding agent, then extrusion molding, it is dried afterwards and roasting.The extrusion aid, the species of peptizer and consumption are ability Well known to field technique personnel, such as common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, poly- second One or more in alcohol, the peptizer can be mineral acid and/or organic acid, and described expanding agent can be starch, conjunction Into one or more in cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein be preferably hydroxymethyl cellulose, One or more in methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol are preferably poly- second two One or more in alcohol, poly- propanol, polyvinyl alcohol, surfactant be preferably fat alcohol polyethylene ether, fatty alkanol amide and Its derivant, molecular weight are one or more in the propylene alcohol copolymer and maleic acid copolymer of 200-10000.

Wherein, described sour peptization index D I refers to that the hydrated alumina containing boehmite is added by certain sour aluminum ratio After nitric acid, by the hydrated alumina containing boehmite of peptization with Al within certain response time₂O₃The percent of meter, DI=（1-W₂/W₁) × 100%, W₁And W₂Before respectively intending thin water aluminum and acid reaction and with acid reaction after with Al₂O₃The weight of meter.

The measure of DI includes：(1) the calcination base content of the hydrated alumina containing boehmite is determined（Calcination base（Also referred to as For butt）Content referred to quantitative boehmite in 600 DEG C of roastings 4 hours, after its burning weight with burn before weight ratio）, 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 Gram（W₁/a=W₀）, weigh W gram of deionized water, W=40.0-W₀, by the hydrated alumina containing boehmite for weighing under stirring Add in beaker with deionized water and mix；(3) the dilute nitric acid solution that 20mL, concentration are 0.74N is pipetted with 20mL pipets, should Acid solution is added to step（2）Beaker in, the lower reaction of stirring 8 minutes；(4) by step（3）Reacted serosity is in centrifuge It is centrifuged, precipitate is inserted in the crucible weighed, afterwards, by which in 125 DEG C of dryings 4 hours, 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.

The hydrated alumina containing boehmite can be boehmite prepared by any prior art, also may be used With the mixture for being boehmite with other hydrated aluminas, other hydrated aluminas selected from a water aluminium oxide, One or more in gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment, characterized with X diffraction, institute In stating the hydrated alumina containing boehmite, boehmite content is not less than 50%, more preferably not less than 60%.

In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and most can and aperture, be by The hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours is characterized by BET N2 adsorptions and is obtained.

Inventors of the present invention have surprisingly found that, the hydrated alumina P1 containing boehmite is carried out into heat treatment and is modified Afterwards, the peptization index of its modifier changes, by this modifier is with not thermally treated P1 mixed-formings, drying and roasts After burning, resulting carrier has obvious bimodal pore distribution.Particularly by the granule of 80-300 mesh therein, preferably 100- After the granule of 200 mesh and not thermally treated part mixed-forming, drying roasting, resulting carrier it is bimodal in each Unimodal pore size distribution is especially concentrated.Here, the granule of the 80-300 mesh, the granule of preferably 100-200 mesh refer to described being modified Thing is through sieve（The step of including broken or grinding if necessary）, its screening thing（Siftage）Meet the granule of 80-300 mesh, preferably The particulate matter of 100-200 mesh accounts for the percent of total amount（By weight）Not less than 60%, further preferably not less than 70%.

During the Mixing ratio by weight of the P1 and P2 refers to the mixture of the P1 and P2 parts per hundred parts, P1 and P2 is shared heavy respectively The ratio of amount number.Wherein, the preferred span of the parts by weight of P1 is 20-95, more preferably 70-95；The weight of P2 The preferred span of number is 5-80, more preferably 5-25.

In being embodied as, the P2 can be conveniently obtained by following method：

(1) based on P2 is dried to obtain, including by the hydrated alumina P1 containing boehmite, according to a conventional method prepared by molding During regular oxidation alumina supporter, the tailing of drying by-product, for example：In extruded moulding, bar shaped article shaped is being dried, integer The tailing of process by-product（Traditionally it is referred to as being dried waste material）, the tailing is milled, is sieved and is obtained P2.

(2) obtained based on roasting, including by the hydrated alumina P1 containing boehmite, molding is often prepared according to a conventional method During rule alumina support, the tailing of fired by-product（Traditionally it is referred to as roasting waste material）, for example, in roller forming, ball The tailing of shape granule by-product in roasting process, the tailing is milled, is sieved and is obtained P2；Or directly P1 sudden strains of a muscle are done Arrive, when P1 is dodged dry directly, flash-off time is preferably 0.05-1 hours, more preferably 0.1-0.5 hours.

(3) two or more in the modifier P2 for being obtained based on preceding method are mixed to get.When being obtained using mixed method When obtaining P2, the mixed proportion of the modifier P2 respectively obtained to aforementioned several method is not limited.

According to the catalyst that the present invention is provided, wherein described carrier optionally contains adjuvant component, be selected from silicon, One or more adjuvant components in boron, alkaline-earth metal and halogen.On the basis of the carrier, being selected from terms of oxide The content of one or more adjuvant components in silicon, boron, alkaline-earth metal is less than 10 weight %, and the content of halogen in terms of element is not More than 10 weight %.

When the carrier contains adjuvant component, the preparation of the carrier also includes the step of introducing the adjuvant component. In a detailed embodiment, the preparation of the carrier includes changing hydrated alumina P1 and P1 containing boehmite Property thing P2 mixing introduce the compound of alkaline including earth metal in the mixture, aftershaping, drying simultaneously roasting.Wherein, by institute The method for stating the modifier P2 mixing of hydrated alumina P1 and P1 containing boehmite is conventional method, for example, by powder body P1 and P2 according to ingredient proportion input stirring-type batch mixer in mix.Introduce containing adjuvant component in P1 the and P2 mixture The method of compound be conventional method, for example, aqueous solution will be configured to containing the compound of adjuvant component, by the aqueous solution in institute State and be mixed into while P1 and P1 mix or again the aqueous solution be mixed into after the P1 and P1 mixing, aftershaping, drying And roasting.The compound containing adjuvant component can be the one kind in the water soluble compound of the arbitrary adjuvant component or It is several.

The group vib metal component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, and VB races metal component is preferred For vanadium and/or niobium, more preferably vanadium.Counted by oxide and on the basis of catalyst, the vib metals component contains Amount is preferably 0.2-15 weight %, more preferably 0.5-12 weight %, more preferably 5-12 weight %；Group VB metal group The content divided is preferably 0.2-12 weight %, more preferably 0.5-9 weight %, more preferably 1-9 weight %.

According to the catalyst that the present invention is provided, the present invention can not also be affected to provide catalyst performance or can change containing any The material of the catalytic performance of the catalyst that rare book invention is provided.Such as can be containing components such as phosphorus, in terms of oxide and with catalyst On the basis of, the content of said components is less than 10 weight %, preferably 0.5-5 weight %.

When in the catalyst also containing components such as phosphorus, the introducing method of the component such as described phosphorus can be arbitrary side Method, the compound of the component such as phosphorus as described in can be to contain directly is mixed with the boehmite, molding simultaneously roasting；Can be Compound containing components such as the phosphorus and the compound containing hydrogenation active metals component are configured to after mixed solution and institute State carrier contact；Can also be individually to prepare the compound containing components such as phosphorus and contact with the carrier after solution and roasting. When the components such as phosphorus and hydrogenation active metals introduce the carrier respectively, preferably first with containing auxiliary compound solution with it is described Carrier contact roasting, are contacted with the solution of the compound containing hydrogenation active metals component afterwards again, such as by dipping Method, the sintering temperature are 400-600 DEG C, and preferably 420-500 DEG C, roasting time is 2-6 hours, preferably 3-6 hours.

According to the method for preparing catalyst that the present invention is provided, wherein, the preparation of the alumina support is included using any Existing method the precursor of the aluminium oxide is carried out into roasting so as to be converted into as mentioned γ-, η-, θ-, δ-and χ-oxidation One or more in aluminum.Optionally, before including the aluminium oxide and/or aluminium oxide before or after described roasting Body thing molding, the step of to prepare the article shaped required for suitable practical operation, for example, prepares globulate, tabletting and bar shaped.Institute Stating molding can be carried out according to a conventional method, such as the method such as tabletting, spin, extrusion.In molding, such as extruded moulding is guarantor Demonstrate,prove the molding to be smoothed out, can add in the precursor of described aluminium oxide and/or aluminium oxide water, extrusion aid and/or Adhesive, with or without expanding agent, then extrusion molding, be dried afterwards and roasting.The species of the extrusion aid, peptizer And consumption is known to those skilled in the art, such as common extrusion aid can selected from sesbania powder, methylcellulose, starch, One or more in polyvinyl alcohol, PVOH, the peptizer can be mineral acid and/or organic acid, described expanding agent Can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein is preferably One or more in hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymerization Alcohol is preferably one or more in Polyethylene Glycol, poly- propanol, polyvinyl alcohol, and surfactant is preferably fatty alcohols polyethylene Ether, fatty alkanol amide and its derivant, molecular weight are in the propylene alcohol copolymer and maleic acid copolymer of 200-10000 Plant or several..The temperature of the drying can be 40-350 DEG C, and preferably 100-200 DEG C, the time is 1-24 hours, preferably 2-12 hours；Sintering temperature is 350-1000 DEG C, and preferably 600-950 DEG C, roasting time is 1-10 hours, and preferably 2-6 is little When.The precursor of the aluminium oxide is in Alumina hydrate, monohydrate alumina and amorphous hydroted alumina or several Mixture.They can be that commercially available commodity also can be prepared by any one method in prior art.

On the premise of it be enough to be carried on described hydrogenation active metals component on described alumina support, the present invention The carrying method is not particularly limited, preferred method is infusion process, including the leaching for preparing the compound containing the metal Stain solution, afterwards with the alumina support described in the solution impregnation.Described dipping method is conventional method, for example, it may be Excessive immersion stain, hole saturation infusion process.

Wherein, the compound containing the metal is selected from one or more in their water soluble compound（It is included in and helps Water-soluble compound in the presence of solvent）.By taking the molybdenum of group vib as an example, can be selected from such as molybdenum oxide, molybdate, paramolybdate In one or more, molybdenum oxide preferably wherein, ammonium molybdate, ammonium paramolybdate；By taking the tungsten of group vib as an example, can be selected from such as tungsten One or more in hydrochlorate, metatungstate, ethyl metatungstate, ammonium metatungstate preferably wherein, ethyl ammonium metatungstate；With VB As a example by the vanadium of race, can be selected from the one kind or several in such as vanadic anhydride, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada polyacid Kind, ammonium metavanadate preferably wherein, ammonium vanadate.

According to heavy oil hydrogenation demetal method provided by the present invention, the reaction condition of the heavy oil hydrogenation demetal is not had There is especially restriction, in a preferred embodiment, the HDM reaction condition is：Reaction temperature 300-550 DEG C, enters one Preferred 330-480 DEG C is walked, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hours^-1, further It is preferred that 0.15-2 hours^-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.

The device of the hydrogenation reaction can it is any be enough to make the raw oil at hydrotreating reaction conditions with institute Carry out in stating the catalytic reactor of catalyst, for example, in the fixed bed reactors, moving-burden bed reactor or ebullated bed are anti- Carry out in answering device.

According to the conventional method in this area, the hydrotreating catalyst before the use, can in presence of hydrogen, in Carry out with sulfur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG CPresulfurization, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, the active metal component loaded by which is converted into metal sulfide component.

The catalyst that the present invention is provided can be used alone, it is also possible to use with other catalyst combinations, and the catalyst is special It is not suitable for heavy oil and is particularly poor residuum carrying out HDM, so as to for subsequent technique（Such as catalytic cracking process）There is provided Qualified raw oil.

Compared with the mink cell focus Hydrodemetalation catalyst that prior art is provided, the hydrodemetallisation catalyst that the present invention is provided The HDM activity of agent, asphaltene removal and de- carbon residue activity are significantly improved.

Specific embodiment

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

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

Bimodal hole carrier that the embodiment 1-13 explanation present invention is provided and preparation method thereof.The explanation of comparative example 1-2 is conventional to urge Agent carrier and preparation method thereof.

The boehmite for using below in an example includes：

P1-1：The dry glue powder of Chang Ling catalyst branch company production（Pore volume is 1.2 mls/g, and specific surface is 280 meters²/ gram, Most can and 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 values 15.8）.

P1-2：The dry glue powder of Yantai Heng Hui Chemical Co., Ltd.s production（Pore volume is 1.1 mls/g, and specific surface is 260 Rice²/ gram, most can and bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weights Amount %, balance of amorphous alumina, DI values 17.2）.

The explanation of embodiment 1-5 prepares modifier P2 of the P1 of carrier of the present invention and preparation method thereof.

Embodiment 1

1000 grams of P1-1 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）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 obtains dried strip in 120 DEG C of dryings 4 hours, By dried strip shaping, sieve, length is less than into the dried strip material of 2mm（Commonly referred to as industrially drying bar waste material）Milled, Sieve, take wherein 100～200 mesh sieves point, obtain the modifier P2A of P1-1.The k value of P2A is shown in Table 1.

Embodiment 2

1000 grams of P1-1 are weighed, is dodged dry 6 minutes in 240 DEG C, is obtained the modifier P2B of P1-1.The k value of P2B is shown in Table 1.

Embodiment 3

The each 200 grams of uniform mixing of P2B that the P2A and embodiment 2 that embodiment 1 is obtained is obtained, obtain the modifier of P1-1 P2C.The k value of P2C is shown in Table 1.

Embodiment 4

1000 grams of P1-2 are weighed, is added containing nitric acid afterwards（Three factory's product of Tianjin chemical reagent）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, carrier is obtained, carrier strip shaping is sieved, length is less than into the carrier strip material of 2mm（Commonly referred to as industrial carrier gives up Material）Milled, sieved, taken wherein 100～200 mesh sieves point, obtain final product the modifier P2D of P1-2.The k value of P2D is shown in Table 1.

Embodiment 5

1000 grams of P1-2 are weighed, is dodged dry 10 minutes in 650 DEG C, is obtained the modifier P2E of P1-2.The k value of P2E is shown in Table 1.

Table 1

Embodiment	Raw material	k
			1	P2A	0.5
2	P2B	0.4
			3	P2C	0.4
4	P2D	0
			5	P2E	0.3

The explanation of embodiment 6-13 prepares the preparation method of carriers for catalysts of the present invention.Comparative example 1-2 illustrates Conventional catalytic The preparation method of agent carrier.

Embodiment 6

800 grams of P1-1 are weighed, after uniformly mixing with 1 obtained 200 gram of raw material P2A of embodiment, is added containing nitric acid（Tianjin Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 900 DEG C of the article shaped, obtains carrier Z1.Carrier Z1 Property be listed in table 2.

Embodiment 7

200 grams of P1-1 are weighed, after uniformly mixing with 2 obtained 800 grams of raw material P2B of embodiment, Tianjin containing nitric acid is added Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 900 DEG C of the article shaped, obtains carrier Z2.Carrier Z2 Property be listed in table 2.

Embodiment 8

500 grams of P1-1 are weighed, after uniformly mixing with 3 obtained 500 grams of raw material P2C of embodiment, Tianjin containing nitric acid is added Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 950 DEG C of the article shaped, obtains carrier Z3.Carrier Z3 Property be listed in table 2.

Comparative example 1

1000 grams of P1-1 are weighed, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）1440 milliliters of 10 milliliters of aqueous solution, The butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, should The roasting 3 hours of 900 DEG C of article shaped, obtains carrier DZ1.The property of carrier DZ1 is listed in table 2.

Embodiment 9

800 grams of P1-2 are weighed, after uniformly mixing with 4 obtained 200 grams of raw material P2D of embodiment, is added containing nitric acid（Tianjin Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier Z4.Carrier The property of Z4 is listed in table 2.

Embodiment 10

900 grams of P1-1 are weighed, after uniformly mixing with 5 obtained 100 grams of raw material P2E of embodiment, Tianjin containing nitric acid is added Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier Z5.Carrier The property of Z5 is listed in table 2.

Embodiment 11

850 grams of P1-2 are weighed, after uniformly mixing with 3 obtained 150 grams of raw material P2C of embodiment, Tianjin containing nitric acid is added Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 850 DEG C of the article shaped, obtains carrier Z6.Carrier Z6 Property be listed in table 2.

Comparative example 2

1000 grams of P1-2 are weighed, three factory's product of the chemical reagent of Tianjin containing nitric acid is added）1440 milliliters of 10 milliliters of aqueous solution, The butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, should The roasting 3 hours of 1000 DEG C of article shaped, obtains carrier DZ2.The property of carrier DZ2 is listed in table 2.

Embodiment 12

900 grams of P1-2 are weighed, after uniformly mixing with 4 obtained 100 grams of raw material P2D of embodiment, Tianjin containing nitric acid is added Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 1000 DEG C of the article shaped, obtains carrier Z7.Carrier The property of Z7 is listed in table 2.

Embodiment 13

850 grams of P1-2 are weighed, after uniformly mixing with 5 obtained 150 grams of raw material P2E of embodiment, Tianjin containing nitric acid is added Learn three factory's product of reagent）1440 milliliters of 10 milliliters of aqueous solution, is extruded into the butterfly of external diameter φ 1.4mm on double screw banded extruder Bar.Wet bar obtains article shaped in 120 DEG C of dryings 4 hours, by the roasting 3 hours of 900 DEG C of the article shaped, obtains carrier Z8.Carrier Z8 Property be listed in table 2.

Comparative example 3

According to carrier DZ3 prepared by the method that patent CN 1782031A embodiments 8 are provided, support is listed in Table 2 below

Table 2

Can be seen by the result of table 2, compared with conventional method, the alumina support tool prepared by the method provided by the present invention There is obvious structure of double peak holes.

Embodiment 14～21 is used for illustrating that the present invention provides catalyst for heavy oil hydrogenation demetal and preparation method thereof.

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

Embodiment 14

200 grams of carrier Z1 are taken, contains MoO with 220 milliliters₃80 g/l, V₂O₅16 g/l of ammonium heptamolybdate and ammonium metavanadate are mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C1, the composition of C1 It is listed in Table 3 below.

Embodiment 15

200 grams of carrier Z2 are taken, contains MoO with 220 milliliters₃80 g/l, V₂O₅16 g/l of ammonium heptamolybdate and ammonium metavanadate are mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C2, the composition of C2 It is listed in Table 3 below.

Embodiment 16

200 grams of carrier Z3 are taken, contains MoO with 220 milliliters₃80 g/l, V₂O₅16 g/l of ammonium heptamolybdate and ammonium metavanadate are mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst CZ3, the group of C3 Into being listed in Table 3 below.

Comparative example 4

200 grams of carrier Z1 are taken, contains MoO with 220 milliliters₃80 g/l, NiO16 g/l of ammonium heptamolybdate and nickel nitrate are mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 2 hours obtain Hydrodemetalation catalyst DC1, the group of DC1 Into being listed in Table 3 below.

Comparative example 5

200 grams of DZ1 are taken, contains MoO with 220 milliliters₃80 g/l, NiO16 g/l of ammonium heptamolybdate and nickel nitrate mixing it is molten Immersion stain 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 2 hours, obtain Hydrodemetalation catalyst DC2, the composition row of DC2 In table 3.

Comparative example 6

200 grams of carrier DZ2 are taken, contains MoO with 500 milliliters₃80 g/l, V₂O₅16 g/l of ammonium heptamolybdate and ammonium metavanadate Mixed solution impregnates 1 hour, and 120 DEG C dry 4 hours, and 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst DC3, DC3's Composition is listed in Table 3 below.

Comparative example 7

200 grams of carrier DZ3 are taken, contains WO with 500 milliliters₃90 g/l, V₂O₅20 g/l of ammonium heptamolybdate and ammonium metavanadate are mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst DC4, the group of DC4 Into being listed in Table 3 below.

Embodiment 17

200 grams of carrier Z4 are taken, contains MoO with 220 milliliters₃90 g/l, V₂O₅20 g/l of ammonium heptamolybdate and ammonium metavanadate are mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C4.The de- gold of hydrogenation The composition of metal catalyst C4 is listed in Table 3 below.

Embodiment 18

200 grams of Z5 are taken, contains WO with 220 milliliters₃90 g/l, V₂O₅20 g/l of ammonium tungstate and ammonium metavanadate mixed solution Dipping 1 hour, 120 DEG C dry 4 hours, and 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C5.Hydrodemetallisation catalyst The composition of agent C5 is listed in Table 2 below.

Embodiment 19

200 grams of Z6 are taken, contains WO with 220 milliliters₃100 g/l, V₂O₅30 g/l of ammonium tungstate and ammonium metavanadate mixing are molten Immersion stain 1 hour, 120 DEG C dry 4 hours, and 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C6.HDM is urged The composition of agent C6 is listed in Table 2 below.

Embodiment 20

200 grams of Z7 are taken, contains MoO with 220 milliliters₃60 g/l, V₂O₅60 g/l of ammonium tungstate and ammonium metavanadate mixing are molten Immersion stain 1 hour, 120 DEG C dry 4 hours, and 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C7.HDM is urged The composition of agent C7 is listed in Table 2 below.

Embodiment 21

200 grams of Z8 are taken, contains WO with 220 milliliters₃60 g/l, V₂O₅60 g/l of ammonium tungstate and ammonium metavanadate mixing are molten Immersion stain 1 hour, 120 DEG C dry 4 hours, and 400 DEG C of roastings 3 hours obtain Hydrodemetalation catalyst C8.HDM is urged The composition of agent C8 is listed in Table 2 below.

Table 3

Embodiment 22-29

It is the demetallization per of Hydrodemetalation catalyst that the embodiment 22-29 explanation present invention is provided, depitching matter rate, de- residual Charcoal rate and desulfurization degree.

With the normal slag of Kuwait as raw material, protective agent is evaluated on 100 milliliters of small fixed reactors.

Catalyst C1, C2, C3, C4, C5 are broken into into the granule of diameter 2-3 millimeters, catalyst loading amount is 100 milliliters.Instead The condition is answered to be：380 DEG C of reaction temperature, 14 MPas of hydrogen dividing potential drop, liquid hourly space velocity (LHSV) are 0.7 hour -1, and hydrogen to oil volume ratio is 1000, reaction Sample after 200 hours.

The circular of demetallization per, depitching matter rate, de- carbon yield and desulfurization degree is as follows：

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

Comparative example 8-11

According to the demetallization per of method evaluation catalyst DC1, DC2, DC3, DC4 of embodiment 22, depitching matter rate, take off residual Charcoal rate and desulfurization degree, the results are shown in Table 5.

Table 4

Raw oil title	The normal slag of Kuwait
		Density（20℃）, kg/m³	0.998
Mean molecule quantity	804
		Carbon residue, % (m)	15.9
Four components, % (m)
		Saturation point	20
Fragrance point	49.3
		Colloid	23
Asphalitine	7.7
		S, m%	5.0
N, m%	0.21
		Ni, ppm	26.5
V, ppm	80

Table 5

The result that table 5 is given carries out 200 hours results afterwards for evaluation response, compares as can be seen that relative to reference Catalyst, the HDM activity of the Hydrodemetalation catalyst that the present invention is provided, depitching matter and de- carbon residue activity are substantially Higher than reference agent.

Claims

1. a kind of hydrogenation catalyst of the metal component of race containing VB, containing carrier and load hydrogenation active metals group on this carrier Point, described hydrogenation active metals component is the metal component and at least one gold selected from VB races selected from least one group vib The combination of category component, wherein, the carrier contains aluminium oxide, and the pore volume of the aluminium oxide is 0.9-1.2 ml/g, specific surface Product is 50-300 rice²/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 55-80% of total pore volume, a diameter of 300-500nm holes Pore volume accounts for the 10-35% of total pore volume.

2. hydrogenation catalyst according to claim 1, it is characterised in that the pore volume of the aluminium oxide is 0.95-1.15 millis Rise/gram, specific surface area is 80-200 rice²/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 60-75% of total pore volume, a diameter of The pore volume in 300-500nm holes accounts for the 15-30% of total pore volume.

3. hydrogenation catalyst according to claim 1, it is characterised in that counted by oxide and on the basis of catalyst, institute The content for stating group vib metal component is 0.2-15 weight %, and the content of VB races metal component is 0.2-12 weight %.

4. the hydrogenation catalyst according to claim 1 or 3, it is characterised in that the metal component of the group vib is selected from molybdenum And/or tungsten, VB races metal component is selected from vanadium and/or niobium, counted by oxide and on the basis of catalyst, the group vib metal group The content divided is 0.5-12 weight %, and the content of VB races metal component is 0.5-9 weight %.

5. hydrogenation catalyst according to claim 4, it is characterised in that the metal component of the group vib is molybdenum or tungsten, VB Race's metal component is vanadium, is counted by oxide and on the basis of catalyst, and the content of the group vib metal component is 5-12 weights Amount %, the content of VB races metal component is 1-9 weight %.

6. a kind of preparation method of the hydrogenation catalyst of the metal component of race containing VB described in claim 1, salic including preparing Carrier and load hydrogenation active metals component on this carrier, wherein, the preparation method of the carrier includes will be thin containing intending The modifier P2 mixing of the hydrated alumina P1 and P1 of diaspore, molding, drying roasting, the Mixing ratio by weight of the P1 and P2 For 20-95：The κ values of 5-80, P2 are the κ=DI 0 to less than or equal to 0.9₂/DI₁, DI₁It is the hydration containing boehmite The sour peptization index of aluminium oxide P1, DI₂It is the sour peptization index of the modifier P2 of the hydrated alumina P1 containing boehmite.

7. method according to claim 6, it is characterised in that the Mixing ratio by weight of the P1 and P2 is 70-95：5-25.

8. method according to claim 6, it is characterised in that the κ values of the P2 are 0 to less than or equal to 0.6.

9. the method according to claim 6 or 7, it is characterised in that the hydrated alumina P1 containing boehmite Pore volume be 0.9-1.4 ml/g, specific surface be 100-350 rice²/ gram, most probable bore dia 8-30nm.

10. method according to claim 9, it is characterised in that the hydrated alumina P1's containing boehmite Pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, most probable bore dia 10-25nm.

11. methods according to 6,7 or 8 any one of claim, it is characterised in that granules of the P2 for 80-300 mesh Thing.

12. methods according to claim 11, it is characterised in that particulate matters of the P2 for 100-200 mesh.

13. methods according to claim 6, it is characterised in that the condition of the drying includes：Temperature is 40-350 DEG C, Time is 1-24 hours, and the condition of the 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.

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

15. methods according to claim 6, it is characterised in that P1 is modified as one of method of P2 is contained described Its all or part is ground, is sieved by the hydrated alumina P1 molding of boehmite, drying afterwards, the drying Condition includes：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are the article shaped roastings for obtaining one of method, Sintering temperature is that roasting time is 1-8 hours, grinds its all or part afterwards more than 350 to less than or equal to 1400 DEG C Mill, screening；The three of method are that the hydrated alumina P1 containing boehmite is dodged dry, and it is to being less than more than 150 to dodge dry temperature Equal to 1400 DEG C, flash-off time is 0.05-1 hours；The four of method are obtained the three of one of method, the two of method and method Two or more in modifier are mixed to get.

16. methods according to claim 15, it is characterised in that the condition of the drying in one of methods described includes：Temperature Spend for 100-200 DEG C, the time is 2-12 hours；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1- 0.5 hour.

17. methods according to claim 15 or 16, it is characterised in that the P2 is 80-300 purposes in P1 modifiers Grain thing.

18. methods according to claim 17, it is characterised in that the P2 is the granule of 100-200 mesh in P1 modifiers Thing.

19. methods according to claim 6, it is characterised in that described hydrogenation active metals component is selected from least one The metal component of group vib and the combination of at least one metal component selected from VB races is planted, described lives in supported on carriers hydrogenation Property metal component method be infusion process, including：A) prepare the solution of metallic compound containing group vib and/or VB races metallic compound； B) solution impregnation of alumina carrier for using step a) to prepare；C) it is dried the impregnation product that simultaneously calcination stepses b) is obtained；Wherein, with oxygen Compound meter on the basis of catalyst, the concentration of the impregnation liquid and consumption cause group vib metal group described in final catalyst Point content be 0.2-15 weight %, the content of VB races metal component is 0.2-12 weight %, and the drying condition is：Temperature 80-200 DEG C, time 1-8 hour, roasting condition is：Temperature 400-600 DEG C, time 2-8 hour.

20. methods according to claim 19, it is characterised in that the metal component of the group vib is selected from molybdenum and/or tungsten, VB races metal component is selected from vanadium and/or niobium, is counted by oxide and on the basis of catalyst, and the concentration of the impregnation liquid and consumption make The content for obtaining group vib metal component described in final catalyst is 0.5-12 weight %, and the content of VB races metal component is 0.5-9 Weight %, the drying condition is：Temperature 100-150 DEG C, time 2-6 hour, roasting condition is：Temperature 420-500 DEG C, time 3-6 hours.

21. methods according to claim 20, it is characterised in that counted by oxide and on the basis of catalyst, the leaching The concentration of stain liquid and consumption cause group vib metal component described in final catalyst content be 5-12 weight %, VB races metal The content of component is 1-9 weight %.

A kind of 22. heavy oil hydrogenation demetal methods, are included in heavy raw oil under heavy oil hydrogenation demetal reaction condition and add Hydrogen catalyst for demetalation is contacted, and the catalyst is the catalyst described in any one of claim 1-5.