CN104226298B

CN104226298B - Heavy oil hydrotreatment catalyst, and preparation and application thereof

Info

Publication number: CN104226298B
Application number: CN201310233638.5A
Authority: CN
Inventors: 孙淑玲; 刘佳; 杨清河; 胡大为; 曾双亲; 王奎; 邵志才; 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: 2013-06-13
Filing date: 2013-06-13
Publication date: 2017-05-24
Anticipated expiration: 2033-06-13
Also published as: CN104226298A

Abstract

The invention discloses a heavy oil hydrotreatment catalyst, and preparation and application thereof. The catalyst comprises a carrier and a hydrogenation active metal composition supported by the carrier; the carrier comprises aluminium oxide and boron, is characterized by employing a mercury intrusion method, has the pore volume of 0.95-1.2 mL/g and the specific area of 50-300 m＜2＞/g, and shows double-peak pore distribution at the diameter of 10-30 nm and the diameter of 300-500 nm, wherein the pore volume of pores with the diameter of 10-30 nm accounts for 55-80% of the total pore volume, and the pore volume of pores with the diameter of 300-500 nm accounts for 10-35%; and the hydrogenation active metal composition comprises at least one of group VIB metal compositions and at least one of group VB metal compositions, and based on the total weight of the catalyst in terms of oxides, the content of the group VIB metal compositions is 0.2-15% by weight, and the content of the group VB metal compositions is 0.2-12% by weight. Compared with catalysts provided by the prior art, the provided catalyst is substantially improved in hydrogenation demetalization and deasphalting activity.

Description

A kind of heavy oil hydrogenating treatment catalyst 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 urge treatment agent, prepare and its apply.

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 will focus in heavy oil lighting.Residual oil is most heavy cut in crude oil, Crude oil molecular weight after distillation is big, baroque ampholyte species in residual oil, these impurity to follow-up process 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 sulphur, 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 cannot be removed effectively, can have a negative impact to downstream catalyst, clog downstream is urged Agent duct, so as to cause the inactivation of downstream catalyst.Therefore, exploitation metal removal activity Hydrodemetalation catalyst high can be with The effective service life of extension downstream catalyst, so as to play a part of protection downstream catalyst and extension fixture service cycle. Due to the These characteristics of residual oil, the activity stability of residual oil hydrocatalyst is particularly significant in commercial Application, domestic and international 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 use 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 the 0.1-5 weight % of carrier, the acidity of its carrier is less than 0.2 mM/gram （Carrier acid amount is relatively low）, while catalyst is kept HDM activity higher, 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 wherein mol ratio between metal component meets Following formula：（Group vib+VB races）：（VIII）=0.5-2:1.

US5275994 describes to be applied to the hydrotreating catalyst of hydrocarbon charging, and it includes group VIII metal component, VIB Race's metal component and VB races metal component.This trimetallic catalyst must be supported on silica or aluminum 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 Added as alkoxide in water-less environment, and it is preferably that catalyst is 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 HDM high, depitching matter isoreactivity And the catalyst of stability, the preparation and its application of the catalyst.

The present invention relates to following invention：

1st, a kind of heavy oil hydrogenating treatment catalyst, containing carrier and load hydrogenation active metals component on this carrier, The carrier contains aluminum oxide and boron, is characterized with mercury injection method, and the pore volume of the carrier is 0.95-1.2 mls/g, specific surface area It is 50-300 meters²/ gram, the carrier is in bimodal pore distribution in a diameter of 10-30nm and a diameter of 300-500nm, wherein, diameter The 55-80% of total pore volume is accounted for for the pore volume in 10-30nm holes, the pore volume in a diameter of 300-500nm holes accounts for the 10- of total pore volume 35%, the hydrogenation active metals component is selected from least one vib metals component and at least one Group VB metal component, Counted by oxide and on the basis of catalyst, the content of the vib metals component is 0.2-15 weight %, Group VB metal The content of component is 0.2-12 weight %.

2nd, the catalyst according to 1, it is characterised in that the pore volume of the aluminum oxide is 0.95-1.15 mls/g, than Surface area is 80-200 meters²/ 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；The metal component of the vib is selected from molybdenum and/or tungsten, Group VB metal component Selected from vanadium and/or niobium, counted by oxide and on the basis of catalyst, the content of the vib metals component is 0.5-12 weights Amount %, the content of Group VB metal component is 0.5-9 weight %.

3rd, the catalyst according to 1, it is characterised in that the boron-containing alumina be selected from boracic with γ-, η-, θ- With δ-single or multiphase bimodal porous aluminum oxide, on the basis of the carrier and in terms of oxide, boron in the carrier Content be 0.5-8 weight %.

4th, the catalyst according to 3, it is characterised in that on the basis of the carrier and in terms of oxide, the carrier The content of middle boron is 1-6 weight %.

5th, the catalyst according to 4, it is characterised in that on the basis of the carrier and in terms of oxide, the carrier The content of middle boron is 1.5-4 weight %.

6th, the catalyst according to 1 or 2, it is characterised in that the metal component of the 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 vib metals component is 5-12 weights Amount %, the content of Group VB metal component is 1-9 weight %.

7th, the preparation method of the hydrogenation catalyst according to 1, including prepare salic carrier and on this carrier Load hydrogenation active metals component, wherein, the preparation method of the carrier is included the hydrated alumina containing boehmite The modifier P2 mixing of P1 and P1, and introduce the compound of boracic in the mixture, aftershaping, drying and be calcined, it is described The Mixing ratio by weight of P1 and P2 is 20-95：The κ values of 5-80, P2 are the κ=DI 0 to less than or equal to 0.9₂/DI₁, DI₁Be containing The sour peptization index of the hydrated alumina P1 of boehmite, DI₂It is the modified of the hydrated alumina P1 containing boehmite The sour peptization index of thing P2, the method in supported on carriers hydrogenation active metals component be infusion process, including prepare containing plus The solution of the compound of hydrogen activity metal simultaneously uses the solution impregnating carrier, is dried afterwards, is calcined or is not calcined, the hydrogenation Active metal component is selected from the metal component of at least one group VIB and the metal component of at least one Group VB, with oxide Count and on the basis of catalyst, the compound containing hydrogenation active metals is in the concentration of the solution and the consumption of the solution Make the content of the metal component of group VIB in final catalyst for 0.2-15 weight %, the metal component of the Group VB contains Amount 0.2-12 weight %；The drying condition includes：Temperature is 100-250 DEG C, and the time is 1-10 hours；The roasting condition bag Include：Temperature is 360-500 DEG C, and the time is 1-10 hours.

8th, the method according to 7, it is characterised in that the Mixing ratio by weight of the P1 and P2 is 70-95：5-25；It is described The k values of P2 are 0 to less than or equal to 0.6.

9th, the method according to 7, it is characterised in that counted by oxide and on the basis of the carrier, it is described containing boronation The introduction volume of compound makes the content of diboron trioxide component in final carrier be 0.1-6 weight %.

10th, the method according to 9, it is characterised in that counted by oxide and on the basis of the carrier, it is described containing boronation The introduction volume of compound makes the content of diboron trioxide component in final carrier be 0.3-4 weight %.

11st, the method according to 7 or 8, it is characterised in that the hole of the hydrated alumina P1 containing boehmite It is 0.9-1.4 mls/g to hold, and specific surface is 100-350 meters²/ gram, most can and bore dia 8-30nm.

12nd, the method according to 11, it is characterised in that the pore volume of the hydrated alumina P1 containing boehmite It it is 0.95-1.3 mls/g, specific surface is 120-300 meters²/ gram, most can and bore dia 10-25nm.

13rd, the method according to 7 or 8, it is characterised in that the P2 is the particulate matter of 80-300 mesh.

14th, the method according to 13, it is characterised in that the P2 is the particulate matter of 100-200 mesh.

15th, the method according to 7, it is characterised in that the dry condition includes：Temperature is 40-350 DEG C, time It it is 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.

16th, the method according to 15, it is characterised in that the dry condition 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.

17th, the method according to 7, 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 The hydrated alumina P1 of diaspore is molded, dries, and is afterwards ground its all or part, sieves, and obtains powder thing for P2, The dry condition includes：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are the shapings for obtaining method one Thing is calcined, and sintering temperature is that roasting time is 1-8 hours, afterwards by its all or part more than 350 to less than or equal to 1400 DEG C It is ground, sieves, obtains powder thing for P2；The three of method are that the hydrated alumina P1 containing boehmite is dodged into dry, are dodged Dry temperature is that flash-off time is 0.05-1 hours more than 150 to less than or equal to 1400 DEG C, obtains powder thing for P2；The four of method It is to be mixed to get one or more in one of method, the two of method and the modifier that obtains with the three of method.

18th, the method according to 17, it is characterised in that the dry condition 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 small 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.

19th, the method according to 17 or 18, it is characterised in that the P2 is the particle of 80-300 mesh in P1 modifiers Thing.

20th, the method according to 19, it is characterised in that the P2 is the particulate matter of 100-200 mesh in P1 modifiers.

21st, the method according to 7, it is characterised in that counted by oxide and on the basis of catalyst, the maceration extract Concentration and consumption cause that the content of vib metals component described in final catalyst is 0.5-12 weight %, Group VB metal group The content divided is 0.5-9 weight %.

22nd, the method according to 21, it is characterised in that counted by oxide and on the basis of catalyst, the maceration extract Concentration and consumption cause the content of vib metals component described in final catalyst for 5-12 weight %, Group VB metal group The content divided is 1-9 weight %.

23rd, application of the hydrotreating catalyst in claim 1-7 described in any one in hydrocarbon oil hydrogenation treatment.

Depending on different requirements, the carrier in heretofore described catalyst can be made into various easily operated article shapeds, for example Spherical, cellular, nest like, tablet or bar shaped（Clover, butterfly, cylinder etc.）.Wherein, boehmite is contained by described The method of modifier P2 mixing of hydrated alumina P1 and P1 be conventional method, for example, by the P1 and P2 of powder according to feeding intake Mix in ratio input stirring-type batch mixer.It is routine side to the method for introducing boron-containing compound in P1 the and P2 mixtures Method, for example, it may be being directly mixed into the desired amount of boron-containing compound in foregoing P1 and P2 mixed processes.

In a specific implementation method for preparing carrier, to the hydrated alumina P1 containing boehmite and The method that boron-containing compound is introduced in the mixture of the modifier P2 of P1 is that boron-containing compound is configured into the aqueous solution, and this is water-soluble Liquid is mixed into while the P1 and P2 mixes or is again mixed into the aqueous solution after the P1 and P2 mixing, Zhi Houcheng Type, drying are simultaneously calcined.The boron-containing compound can be one or more in the water soluble compound of arbitrary boracic.Example Such as, one or more in the water-soluble inorganic salt of boracic.

In the present invention, the shaping can be carried out according to a conventional method, for example, one kind side in spin, compressing tablet and extruded moulding The combination of method or several method.In shaping, such as extruded moulding, to ensure that the shaping is smoothed out, can be to described Water, extrusion aid and/or adhesive are added in mixture, with or without expanding agent, then extrusion molding is dried and roasts afterwards Burn.The extrusion aid, the species of peptizing agent and consumption are known to those skilled in the art, such as common extrusion aid can be selected One or more from sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, the peptizing agent can be inorganic acid And/or organic acid, described expanding agent can be the one kind or several in starch, synthetic cellulose, polymeric alcohol and surfactant Kind.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber poly alkyl alcohol One or more in vinethene, polymeric alcohol is preferably one or more in polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, surface It is the propenyl copolymerization of 200-10000 that activating agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and its derivative, molecular weight One or more in thing and maleic acid copolymer.

Sour peptization index D I in the carrier preparation refers to the hydrated alumina containing boehmite by certain sour aluminium After adding nitric acid, by the hydrated alumina containing boehmite of peptization with Al within certain reaction time₂O₃The hundred of meter Fraction, DI=（1-W₂/W₁) × 100%, W₁And W₂Respectively intend before thin water aluminium and acid reaction and with acid reaction after with Al₂O₃The weight of meter Amount.

The measure of DI includes：(1) the calcination base content of the hydrated alumina containing boehmite is determined（Calcination base（Also referred to as It is butt）Content refers to that quantitative boehmite is calcined 4 hours in 600 DEG C, weight and the preceding weight ratio of burning after its burning）, It is calculated as a；(2) the hydrated alumina W containing boehmite is weighed with assay balance₀Gram, W₀Amount meet with Al₂O₃The W of meter₁It is 6 Gram（W₁/a=W₀）, weigh W grams of deionized water, W=40.0-W₀, the hydrated alumina containing boehmite that will be weighed under stirring Mix in adding beaker with deionized water；(3) the dilute nitric acid solution that 20mL, concentration are 0.74N is pipetted with 20mL pipettes, by this Acid solution is added to step（2）Beaker in, the lower reaction of stirring 8 minutes；(4) by step（3）Reacted slurries are in centrifuge It is centrifuged, sediment is inserted in the crucible weighed, afterwards, by it in 125 DEG C of dryings 4 hours, in Muffle furnace 850 DEG C are calcined 3 hours, weigh and obtain calcination sample size W₂Gram；（5）According to formula DI=(1-W₂/W₁) × 100% is calculated.

On the premise of being enough to make final carrier meet application claims, the present invention is to the water containing boehmite Close aluminum oxide P1 not specially require, can be the boehmite, or boehmite of any prior art preparation With the mixture of other hydrated aluminas, other hydrated aluminas are selected from a water aluminum oxide, gibbsite and nothing One or more in hydrated amorphous alumina.For example, pore volume is 0.9-1.4 mls/g, specific surface is 100-350 meters²/ gram, Most can and bore dia 8-30nm；It is preferred that pore volume is 0.95-1.3 mls/g, specific surface is 120-300 meters²/ gram, most can and Kong Zhi The hydrated alumina containing boehmite of footpath 10-25nm is just particularly suitable for the present invention.In the present invention, contain the thin water of plan The pore volume of the hydrated alumina of aluminium stone, specific surface area and most can and aperture, be by the aqua oxidation containing boehmite After aluminium is calcined 4 hours in 600 DEG C, is characterized by BET N2 adsorptions and obtained.

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

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

In specific implementation, the P2 can conveniently be obtained by following method：

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

(2) obtained based on roasting, including preparation is molded often by the hydrated alumina P1 containing boehmite 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 particle by-product in roasting process, the tailing is milled, and sieving obtains P2；Or direct dodge P1 is done Arrive, when P1 directly is dodged into dry, 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.Obtained when using mixed method When obtaining P2, the mixed proportion of the modifier P2 respectively obtained to foregoing several method is not limited.

The vib metals component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, Group VB metal component Preferably vanadium and/or niobium, more preferably vanadium.Counted by oxide and on the basis of catalyst, the vib metals component Content be preferably 0.2-15 weight %, more preferably more preferably 0.5-12 weight %, 5-12 weight %；Group VB gold The content for belonging to component is preferably 0.2-12 weight %, more preferably more preferably 0.5-9 weight %, 1-9 weight %.

On the premise of being 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 be infusion process, including prepare containing the metal compound leaching 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 vib as an example, can be selected from such as molybdenum oxide, molybdate, para-molybdic acid One or more in salt, molybdenum oxide preferably wherein, ammonium molybdate, ammonium paramolybdate；By taking the tungsten of vib as an example, can be selected from Such as one or more in tungstates, metatungstate, ethyl metatungstate, ammonium metatungstate preferably wherein, ethyl ammonium metatungstate； By taking the vanadium of Group VB as an example, can be selected from such as the one kind in vanadic anhydride, ammonium vanadate, ammonium metavanadate, vanadic sulfate, vanadium heteropoly acid Or several, ammonium metavanadate preferably wherein, ammonium vanadate.

According to the catalyst that the present invention is provided, the present invention can not also be influenceed to provide catalyst performance or can change containing any The material of the catalytic performance of the catalyst that rare book invention is provided.Phosphorus component can such as be contained, in terms of oxide and with catalyst On the basis of, the content of said components is no more 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, that can be that the compound of the phosphorus component containing as described in is directly mixed, is molded and is calcined with the boehmite；Can be The compound that the component such as the phosphorus will be contained and the compound containing hydrogenation active metals component are configured to after mixed solution and institute State carrier contact；Can also be and contact and be calcined with the carrier after the compound containing components such as phosphorus is individually prepared into solution. 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 is contacted and is calcined, and the solution again with the compound containing hydrogenation active metals component is contacted afterwards, such as by dipping Method, the sintering temperature is 400-600 DEG C, and preferably 420-500 DEG C, roasting time is 2-6 hours, preferably 3-6 hours.

According to heavy oil hydrogenation treatment method provided by the present invention, to the no spy of reaction condition of heavy-oil hydrogenation treatment Do not limit, in a preferred embodiment, the HDM reaction condition is：300-550 DEG C of reaction temperature, it is further excellent Select 330-480 DEG C, 4-20 MPas of hydrogen dividing potential drop, further preferred 6-18 MPas, volume space velocity 0.1-3.0 hours^-1, further preferably 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 feedstock oil at hydrotreating reaction conditions with institute State and carry out in the catalytic reactor of catalyst, for example, in the fixed bed reactors, moving-burden bed reactor or ebullated bed are anti- Answer and carry out in device.

According to the conventional method in this area, the hydrotreating catalyst before the use, can generally exist in hydrogen Under, presulfurization is carried out with sulphur, hydrogen sulfide or 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.

Compared with the catalyst that prior art is provided, the bimodal of carrier that the catalyst that the present invention is provided is used is concentrated on 10nm-30nm and 300nm-500nm.When processing of heavy oil is used it for, the catalyst shows preferably to be hydrogenated with depitching matter Performance.The catalyst that the present invention is provided be can be used alone, it is also possible to be used with other catalyst combinations, and the catalyst is especially fitted Share carries out hydrotreating in heavy oil particularly poor residuum, to be subsequent technique（Such as catalytic cracking process）It is qualified to provide Feedstock oil.

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.

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 It is amorphous alumina to measure, 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）.

Embodiment 1-5 explanations prepare 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 contain nitric acid afterwards（The factory's product of Tianjin chemical reagent three）10 milliliters of the aqueous solution 1440 Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar obtained dried strip in 120 DEG C of dryings 4 hours, By dried strip shaping, sieving, the dried strip material by length less than 2mm（Commonly referred to as industrially drying bar waste material）Milled, Sieving, takes wherein 100~200 mesh sieves point, obtains the modifier P2A of P1-1.The k values of P2A are shown in Table 1.

Embodiment 2

1000 grams of P1-1 are weighed, dodges dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1.The k values of P2B are shown in Table 1.

Embodiment 3

Each 200 grams of the P2B that the P2A and embodiment 2 that embodiment 1 is obtained are obtained uniformly mixes, and obtains the modifier of P1-1 P2C.The k values of P2C are shown in Table 1.

Embodiment 4

1000 grams of P1-2 are weighed, is added contain nitric acid afterwards（The factory's product of Tianjin chemical reagent three）10 milliliters of the 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, by carrier strip shaping, sieving, the carrier strip material by length less than 2mm（Commonly referred to as industrial carrier gives up Material）Milled, sieved, taken wherein 100~200 mesh sieves point, obtained final product the modifier P2D of P1-2.The k values of P2D are shown in Table 1.

Embodiment 5

1000 grams of P1-2 are weighed, dodges dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2.The k values of P2E are 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

Embodiment 6-13 explanations prepare the preparation method of catalyst of the present invention boracic Bimodal-pore alumina support.Comparative example 1-3 illustrates the preparation method of conventional catalyst carrier.

Embodiment 6

800 grams of P1-1 are weighed, after 200 grams of raw material P2A uniformly mix obtained in embodiment 1, is added and is contained nitric acid（Tianjin Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 2.4g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 900 DEG C of roastings of the article shaped Burn 3 hours, obtain carrier Z1.The property of carrier Z1 is listed in table 2.

Embodiment 7

200 grams of P1-1 are weighed, after 800 grams of raw material P2B uniformly mix obtained in embodiment 2, Tianjin containing nitric acid is added Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 2.4g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 900 DEG C of roastings of the article shaped Burn 3 hours, obtain carrier Z2.The property of carrier Z2 is listed in table 2.

Embodiment 8

500 grams of P1-1 are weighed, after 500 grams of raw material P2C uniformly mix obtained in embodiment 3, Tianjin containing nitric acid is added Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 2.4g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 950 DEG C of roastings of the article shaped Burn 3 hours, obtain carrier Z3.The property of carrier Z3 is listed in table 2.

Comparative example 1

1000 grams of P1-1 are weighed, the factory's product of the chemical reagent of Tianjin containing nitric acid three is added）10 milliliters, containing in terms of diboron trioxide It is 1440 milliliters of the boric acid aqueous solution of 2.4g, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar is in 120 DEG C drying 4 hours, obtains article shaped, and by the article shaped, 900 DEG C are calcined 3 hours, obtain carrier DZ1.The property of carrier DZ1 is listed in Table 2.

Embodiment 9

800 grams of P1-2 are weighed, after 200 grams of raw material P2D uniformly mix obtained in embodiment 4, is added and is contained nitric acid（Tianjin Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 14g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 1000 DEG C of the article shaped Roasting 3 hours, obtains carrier Z4.The property of carrier Z4 is listed in table 2.

Embodiment 10

900 grams of P1-1 are weighed, after 100 grams of raw material P2E uniformly mix obtained in embodiment 5, Tianjin containing nitric acid is added Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 14g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 1000 DEG C of the article shaped Roasting 3 hours, obtains carrier Z5.The property of carrier Z5 is listed in table 2.

Embodiment 11

850 grams of P1-2 are weighed, after 150 grams of raw material P2C uniformly mix obtained in embodiment 3, Tianjin containing nitric acid is added Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 14g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 850 DEG C of roastings of the article shaped Burn 3 hours, obtain carrier Z6.The property of carrier Z6 is listed in table 2.

Comparative example 2

1000 grams of P1-2 are weighed, the factory's product of the chemical reagent of Tianjin containing nitric acid three is added）10 milliliters, containing in terms of diboron trioxide It is 1440 milliliters of the boric acid aqueous solution of 14g, the butterfly bar of external diameter φ 1.4mm is extruded on double screw banded extruder.Wet bar is in 120 DEG C Dry 4 hours, obtain article shaped, 1000 DEG C are calcined 3 hours by the article shaped, obtain carrier DZ2.The property of carrier DZ2 is listed in Table 2.

Embodiment 12

900 grams of P1-2 are weighed, after 100 grams of raw material P2D uniformly mix obtained in embodiment 4, Tianjin containing nitric acid is added Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 28g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 1000 DEG C of the article shaped Roasting 3 hours, obtains carrier Z7.The property of carrier Z7 is listed in table 2.

Embodiment 13

850 grams of P1-2 are weighed, after 150 grams of raw material P2E uniformly mix obtained in embodiment 5, Tianjin containing nitric acid is added Learn the factory's product of reagent three）10 milliliters, containing 1440 milliliters of the boric acid aqueous solution that 28g is calculated as with diboron trioxide, in twin-screw extrusion The butterfly bar of external diameter φ 1.4mm is extruded on machine.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, by 900 DEG C of roastings of the article shaped Burn 3 hours, obtain carrier Z8.The property of carrier Z8 is listed in table 2.

Comparative example 3

According to the method that patent CN1782031A embodiments 7 are provided, it is extruded into external diameter φ 1.4mm's on double screw banded extruder Butterfly bar.Wet bar obtained article shaped in 120 DEG C of dryings 4 hours, and by the article shaped, 900 DEG C are calcined 3 hours, obtain carrier DZ3. The property of carrier DZ3 is listed in table 2.

Table 2

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

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

Embodiment 14

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

Embodiment 15

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

Embodiment 16

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

Comparative example 4

200 grams of carrier DZ1 are taken, MoO is contained 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, and 400 DEG C are calcined 2 hours, obtain the group of Hydrodemetalation catalyst DC1, DC1 Into being listed in Table 3 below.

Comparative example 5

200 grams of DZ2 are taken, MoO is contained with 220 milliliters₃80 g/l, NiO16 g/l of ammonium heptamolybdate and nickel nitrate mixing is molten Immersion stain 1 hour, 120 DEG C dry 4 hours, and 400 DEG C are calcined 2 hours, obtain the composition row of Hydrodemetalation catalyst DC2, DC2 In table 3.

Comparative example 6

200 grams of carrier DZ3 are taken, MoO is contained 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 are calcined 3 hours, obtain Hydrodemetalation catalyst DC3, DC3's Composition is listed in Table 3 below.

Embodiment 17

200 grams of carrier Z4 are taken, MoO is contained with 220 milliliters₃90 g/l, V₂O₅20 g/l of ammonium heptamolybdate and ammonium metavanadate is mixed Close solution impregnation 1 hour, 120 DEG C dry 4 hours, and 400 DEG C are calcined 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, WO is contained 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 are calcined 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, WO is contained with 220 milliliters₃100 g/l, V₂O₅30 g/l of ammonium tungstate and ammonium metavanadate mixed solution Dipping 1 hour, 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain Hydrodemetalation catalyst C6.Hydrodemetallisation catalyst The composition of agent C6 is listed in Table 2 below.

Embodiment 20

200 grams of Z7 are taken, MoO is contained with 220 milliliters₃60 g/l, V₂O₅60 g/l of ammonium tungstate and ammonium metavanadate mixed solution Dipping 1 hour, 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain Hydrodemetalation catalyst C7.Hydrodemetallisation catalyst The composition of agent C7 is listed in Table 2 below.

Embodiment 21

200 grams of Z8 are taken, WO is contained with 220 milliliters₃60 g/l, V₂O₅60 g/l of ammonium tungstate and ammonium metavanadate mixed solution Dipping 1 hour, 120 DEG C dry 4 hours, and 400 DEG C are calcined 3 hours, obtain Hydrodemetalation catalyst C8.Hydrodemetallisation catalyst The composition of agent C8 is listed in Table 2 below.

Table 3

Embodiment 22-29

The demetallization per of the hydrotreating catalyst that the embodiment 22-29 explanation present invention is provided, depitching matter rate, de- carbon residue 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 diameter 2-3 millimeters of particle, 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, hydrogen to oil volume ratio is 1000, reaction Sampled 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 7-9

Method according to embodiment 22 evaluates demetallization per, depitching matter rate, the de- carbon yield of catalyst DC1, DC2, DC3 And desulfurization degree, the results are shown in Table 5.

Table 4

Feedstock 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 hydrotreating catalyst that the present invention is provided, depitching matter and de- carbon residue activity are substantially high In reference agent.

Claims

1. a kind of heavy oil hydrogenating treatment catalyst, described containing carrier and load hydrogenation active metals component on this carrier Carrier contains aluminum oxide and boron, is characterized with mercury injection method, and the pore volume of the carrier is 0.95-1.2 mls/g, and specific surface area is 50- 300 meters²/ gram, the carrier is in bimodal pore distribution in a diameter of 10-30nm and a diameter of 300-500nm, wherein, a diameter of 10- The pore volume in 30nm holes accounts for the 55-80% of total pore volume, and the pore volume in a diameter of 300-500nm holes accounts for the 10-35% of total pore volume, institute State hydrogenation active metals component and be selected from least one vib metals component and at least one Group VB metal component, to aoxidize Thing meter and on the basis of catalyst, the content of the vib metals component is 0.2-15 weight %, Group VB metal component Content is 0.2-12 weight %；The preparation method of the carrier is included hydrated alumina P1 and P1 containing boehmite Modifier P2 mixes, and introduces the compound of boracic in the mixture, aftershaping, drying and be calcined, the P1's and P2 Mixing ratio by weight is 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 to contain the thin water aluminium of plan The sour peptization index of the hydrated alumina P1 of stone, DI₂It is the acid of the modifier P2 of the hydrated alumina P1 containing boehmite Peptization index.

2. catalyst according to claim 1, it is characterised in that the pore volume of the aluminum oxide is 0.95-1.15 milliliters/ Gram, specific surface area is 80-200 meters²/ gram, the pore volume in a diameter of 10-30nm holes accounts for the 60-75% of total pore volume, a diameter of 300- The pore volume in 500nm holes accounts for the 15-30% of total pore volume；The metal component of the vib is selected from molybdenum and/or tungsten, Group VB gold Category component is selected from vanadium and/or niobium, is counted by oxide and on the basis of catalyst, and the content of the vib metals component is 0.5-12 weight %, the content of Group VB metal component is 0.5-9 weight %.

3. catalyst according to claim 1, it is characterised in that the carrier be selected from boracic with γ-, η-, θ-and δ-single or multiphase bimodal porous aluminum oxide, on the basis of the carrier and in terms of oxide, boron in the carrier Content is 0.5-8 weight %.

4. catalyst according to claim 3, it is characterised in that described on the basis of the carrier and in terms of oxide The content of boron is 1-6 weight % in carrier.

5. catalyst according to claim 4, it is characterised in that described on the basis of the carrier and in terms of oxide The content of boron is 1.5-4 weight % in carrier.

6. catalyst according to claim 1 and 2, it is characterised in that the metal component of the vib is molybdenum or tungsten, Group VB metal component is vanadium, is counted by oxide and on the basis of catalyst, and the content of the vib metals component is 5-12 Weight %, the content of Group VB metal component is 1-9 weight %.

7. the preparation method of catalyst according to claim 1, comprises the following steps：

（1）Carrier is prepared, including the modifier P2 of hydrated alumina P1 and P1 containing boehmite is mixed and is mixed at this The compound of boracic is introduced in compound, aftershaping, drying and be calcined, 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；

（2）Using infusion process in step（1）Hydrogenation active metals component is introduced on the carrier for obtaining, including is prepared containing hydrogenation activity The dipping solution of the compound of metal simultaneously uses the solution impregnating carrier, is dried afterwards, is calcined or is not calcined, and the hydrogenation is lived Property metal component be selected from least one group VIB metal component and at least one Group VB metal component, in terms of oxide And on the basis of catalyst, the concentration and consumption of the dipping solution make the metal component of the group VIB in final catalyst Content is 0.2-15 weight %, the content 0.2-12 weight % of the metal component of the Group VB；

Wherein, the step（1）Drying condition include：Temperature is 40-350 DEG C, and the time is 1-24 hours, roasting condition bag Include：Temperature is that the time is 1-8 hours more than 500 to less than or equal to 1200 DEG C；The step（2）Drying condition include：Temperature It it is 100-250 DEG C, the time is 1-10 hours；Roasting condition includes：Temperature is 360-500 DEG C, and the time is 1-10 hours.

8. method according to claim 7, it is characterised in that the Mixing ratio by weight of the P1 and P2 is 70-95：5-25； The k values of the P2 are 0 to less than or equal to 0.6；The step（1）Drying condition include：Temperature is 100-200 DEG C, and the time is 2-12 hours, roasting condition included：Temperature is that roasting time is 2-6 hours more than 800 to less than or equal to 1000 DEG C；The step Suddenly（2）Drying condition include：Temperature is 100-140 DEG C.

9. method according to claim 7, it is characterised in that counted by oxide and on the basis of the carrier, it is described to contain The introduction volume of boron compound makes the content of diboron trioxide component in final carrier be 0.1-6 weight %.

10. method according to claim 9, it is characterised in that counted by oxide and on the basis of the carrier, it is described to contain The introduction volume of boron compound makes the content of diboron trioxide component in final carrier be 0.3-4 weight %.

11. method according to claim 7 or 8, it is characterised in that the hydrated alumina P1 containing boehmite Pore volume be 0.9-1.4 mls/g, specific surface area be 100-350 meters²/ gram, most probable bore dia 8-30nm.

12. methods according to claim 11, it is characterised in that the hydrated alumina P1's containing boehmite Pore volume is 0.95-1.3 mls/g, and specific surface area is 120-300 meters²/ gram, most probable bore dia 10-25nm.

13. method according to claim 7 or 8, it is characterised in that the P2 is the particulate matter of 80-300 mesh.

14. methods according to claim 13, it is characterised in that the P2 is the particulate matter of 100-200 mesh.

15. methods according to claim 7, it is characterised in that P1 is modified as into one of method of P2 is contained described The hydrated alumina P1 of boehmite is molded, dries, and is afterwards ground its all or part, sieves, and obtains powder thing It is P2, the dry condition includes：Temperature is 40-350 DEG C, and the time is 1-24 hours；The two of method are to obtain one of method The article shaped roasting arrived, sintering temperature is that roasting time is 1-8 hours, afterwards that its is complete more than 350 to less than or equal to 1400 DEG C Portion or part are ground, sieve, and obtain powder thing for P2；The three of method are by the hydrated alumina P1 containing boehmite Dodge dry, it is that flash-off time is 0.05-1 hours more than 150 to less than or equal to 1400 DEG C to dodge dry temperature, obtains powder thing for P2；Side The four of method be by one of method, the two of method and method three modifiers for obtaining in several be mixed to get.

16. methods according to claim 15, it is characterised in that the dry condition in one of methods described includes：Temperature It is 100-200 DEG C to spend, and the time is 2-12 hours；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 1-6 is small 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.

17. method 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 particle of 100-200 mesh in P1 modifiers Thing.

19. methods according to claim 7, it is characterised in that counted by oxide and on the basis of catalyst, the dipping The concentration and consumption of solution cause that the content of vib metals component described in final catalyst is 0.5-12 weight %, Group VB The content of metal component is 0.5-9 weight %.

20. methods according to claim 19, it is characterised in that counted by oxide and on the basis of catalyst, the leaching The concentration and consumption of stain solution cause that the content of vib metals component described in final catalyst is 5-12 weight %, Group VB The content of metal component is 1-9 weight %.

The application of hydrotreating catalyst in 21. claim 1-6 described in any one in heavy-oil hydrogenation treatment.