CN105582948B

CN105582948B - A kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof

Info

Publication number: CN105582948B
Application number: CN201410563797.6A
Authority: CN
Inventors: 王少军; 季洪海; 凌凤香; 沈智奇; 杨卫亚; 王丽华; 郭长友
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2014-10-22
Filing date: 2014-10-22
Publication date: 2017-07-28
Anticipated expiration: 2034-10-22
Also published as: CN105582948A

Abstract

The present invention discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, including alumina support, active metal and carbon, on the basis of catalyst weight, active metal is in terms of oxide, Mo and/or W weight content is 6.0wt% 15wt%, Co and/or Ni weight contents are 1.0wt% 4.0wt%, and carbon is calculated as 1wt% 15wt%, preferably 5wt% 10wt% with element；Carbon content is gradually reduced from catalyst granules center to outer surface.Preparation method is as follows：The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, is sprayed on the alumina support according to the order of concentration from high to low, hydro-thermal charing process is carried out in sealing container, dry, impregnate active component, dry, anaerobic high-temperature process, obtains Hydrodemetalation catalyst.Carbon content distribution gradient in catalyst of the present invention, the easy complete cure of active component significantly improves the demetalization of catalyst and desulphurizing activated.

Description

A kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof

Technical field

The invention belongs to field of catalyst preparation, more particularly to a kind of residuum hydrogenating and metal-eliminating catalyst and its preparation side Method.

Background technology

Presently the most common hydrogenation catalyst is usually for carrier, with Co, Ni, Mo, W with aluminum oxide, silica etc. Deng the loaded catalyst that metal is active component.Active component is loaded on carrier using the method for dipping or kneading, then Catalyst is made by drying, roasting.When humectant after dipping is dried, the active component in maceration extract is with the gradually steaming of solvent Hair, easily forms larger active specy particle in carrier hole, causes the cell channels in carrier to be blocked, while solvent exists Migration in evaporation process can also make Active components distribution uneven, the activity of final influence catalyst.In addition, in roasting process In, active metal component easily has an effect to form very strong M-O-Al keys with alumina support, causes active component to form point Spar phase and lose activity, or make active component can not complete cure so as to reducing catalyst activity.

CN101439289A discloses a kind of preparation method of hydrogenation catalyst.The catalyst metal components are by including Co, Ni One or both of and one or both of Mo, W metal ingredient constitute, using urea or ammoniacal liquor as reaction promoter, using load The method of reaction in-situ makes metal active constituent generate nickel molybdate in body opening（Cobalt）Or nickel tungstate（Cobalt）Class compound, so as to The reaction of metal and carrier is avoided, while making metal active constituent be easier to cure, the activity of hydrogenation catalyst can be improved. But catalyst different activities component interphase interaction prepared by this method forms new compound, it is unfavorable for active component in load Dispersed and active further raising on body, in addition, preparation process is more complicated.

CN102451704A discloses a kind of preparation method of hydrocracking catalyst, the catalyst with amorphous silica-alumina and Aluminum oxide is carrier, and group VIII and group vib metal are hydrogenation active component, preferably comprise active material B₂O₃.Present invention catalysis Agent is by after amorphous silica-alumina and aluminum oxide mixed-forming, through drying process, then infusion process supported active metals, then through drying Obtained with roasting.This method is compared with conventional infusion process, and shaping carrier is not fired, simplifies preparation process, and reduce Strong interaction between active metal and carrier, is conducive to Active components distribution, is more beneficial for the performance of metal active, also keeps away Exempt from the specific surface area caused by many one-step bakings to lose.But because shaping carrier is without calcination process, the mechanical strength of catalyst It is undesirable.

The content of the invention

For existing technical deficiency, the present invention provides a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, this Active metallic content and carbon content distribution gradient in invention catalyst, catalyst exterior active component and carrier function are relatively By force, internal active component and carrier acts on relatively weak, the easy complete cure of active component, significantly improves the de- gold of catalyst Category activity.

The residuum hydrogenating and metal-eliminating catalyst of the present invention, including alumina support, active metal and carbon, with catalyst weight On the basis of, active metal is in terms of oxide, and Mo and/or W weight content are 6.0wt%-15wt%, Co and/or Ni weight contents For 1.0wt%-4.0wt%, carbon is calculated as 1wt%-15wt%, preferably 5wt%-10wt% with element, alumina support be 66wt% ~ 92wt%, preferably surplus；It is 160-270m than surface²/ g, pore volume is 0.8-1.2ml/g；Carbon content meets following condition：Distance Catalyst granules cross-section center（Hereinafter referred to as center）The carbon of carbon content and catalyst granules cross-section center at 1/4R contains Amount is than being 50%-90%, preferably 60%-80%, and distance center 1/2R places carbon content and center carbon content ratio are 30%-70%, preferably Carbon content and center carbon content ratio are 10%-50%, preferably 20%-40%, cross section outer most edge at 40%-60%, distance center 3/4R The carbon content at upper any point is 5%-40%, preferably 10%-20% with center carbon content ratio；Active metallic content meets following bar Part：Distance center 1/4R active metallic contents are activity at 80%-100%, distance center 1/2R with central active tenor ratio Tenor is active metallic content and central active gold at 70%-80%, distance center 3/4R with central active tenor ratio Belong to the active metallic content that content ratio is any point in 60%-70%, cross section outer most edge is with central active tenor ratio 50%-60%。

Catalyst of the present invention is（It is solid）It is granular, rather than the amorphous state such as powder.It is used as described The shape of grain, it is conventional use of variously-shaped to enumerate this area Hydrodemetalation catalyst, such as can further enumerate Spherical and column.As described spherical, such as it can enumerate spheroidal and elliposoidal etc.；As the column, such as it can lift Go out cylindric, flat column and profiled-cross-section（Such as clover, bunge bedstraw herb etc.）Column etc..

In the present invention, so-called " cross section of catalyst granules " is referred to along the minimum dimension side of a catalyst granules The whole surface of exposure after to the geometric center cutting by its shape.Such as, it is described when the catalyst granules is spherical Cross section refers to the whole surface of exposure after being cut along the radius or short-axis direction of the ball by its centre of sphere（Referring to Fig. 1）. Or, when the catalyst granules is column, the cross section refers to passing through this perpendicular to the length dimension direction of the post The whole surface of exposure after the central point cutting of length dimension（Such as referring to Fig. 2）.

In the present invention, the periphery of the exposed surface is referred to as to the outer most edge of the cross section, by the geometric center（Such as The foregoing centre of sphere or the central point of length dimension）Central point referred to as on the cross section.

Carbon content and active metallic content on catalyst granules cross section of the present invention are measured by electron probe.

The preparation method of the residuum hydrogenating and metal-eliminating catalyst of the present invention, including following content：

（1）With aqueous solution of urea oxide impregnation alumina supporter, the alumina support after dipping is through drying process；

（2）The maceration extract containing polyalcohol and/or monose and active metal component of at least two various concentrations is prepared, according to The order of concentration from high to low is sprayed in step（1）On alumina support so that polyalcohol and/or monose and active metal component Concentration formed on carrier ecto-entad in from low to high gradient distribution；Order wherein according to concentration from high to low, phase Between adjacent two kinds of various concentrations maceration extracts, the concentration of the concentration and active component of polyalcohol and/or monose increaseds or decreases trend It is identical；

（3）By step（2）Alumina support after dipping, which is transferred in sealing container, carries out hydro-thermal process；

（4）By step（3）Obtained dry materials, then anaerobic high-temperature process, obtains residuum hydrogenating and metal-eliminating catalyst.

In the inventive method, step（1）The mass concentration of described aqueous solution of urea is 20%-40%, aqueous solution of urea Consumption is at least the saturated water adsorptive value of alumina support, and dip time is 1-2 hours.

In the inventive method, step（1）Described alumina support is graininess, can be spherical or cylindricality, wherein ball Shape can be spheroidal or elliposoidal, and cylindricality can cylinder, square column type or abnormity（Clover, bunge bedstraw herb or five tooth balls）.Oxygen Changing alumina supporter can use commercially available, it would however also be possible to employ be suitable for Hydrodemetalation catalyst carrier made from conventional method Aluminum oxide.The one kind that can also be added as needed in the auxiliary elements such as Si, Ti, Zr, B or F in described alumina support or It is several.

In the inventive method, step（2）Described polyalcohol includes xylitol, sorbierite, mannitol or arabite etc. In one or more；Described monose includes the one or more in glucose, ribose or fructose etc..

In the inventive method, step（2）Described active component is group vib and/or group VIII metal element, wherein VIB One or more of race's metallic element in molybdenum and/or tungsten, the one kind or several of group VIII metal element in nickel and/or cobalt Kind.

In the inventive method, step（2）The concentration of polyalcohol and/or monose in described maceration extract is 5-50 g/ 100ml。

In the inventive method, step（2）Group vib metal element content in described maceration extract is calculated as 5- with oxide 40g/100ml, group VIII metal constituent content is calculated as 1-10g/100ml with oxide.Wherein, active metal component is selected from solvable Property compound, such as nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, phosphomolybdic acid, molybdenum Sour ammonium, ammonium metatungstate and ammonium tungstate etc..

In the inventive method, step（2）Described maceration extract according to concentration from high to low, it is many in adjacent maceration extract twice The concentration difference of first alcohol and/or monose water is 5-30g/100ml, preferably 1-20g/100ml；Group vib metallic element is in terms of oxide Concentration difference is 4-10g/100ml, and group VIII metal element counts concentration difference as 0.5-2g/100ml using oxide.

In the inventive method, step（2）It is preferred that preparing the polyalcohol and/or monose and active metal of 2-4 kind various concentrations The maceration extract of component.

In the inventive method, step（2）The described maceration extract consumption sprayed every time is alumina support saturated water adsorptive value 10%-60%, preferably 20%-30%, the total consumption of maceration extract repeatedly sprayed for alumina support saturated water adsorptive value to ensure oxygen Change alumina supporter saturation dipping.

In the inventive method, step（2）It is preferred that the polyalcohol and/or monose and active metal group of 3 kinds of various concentrations of preparation Maceration extract is divided to be sprayed, detailed process is as follows：Spray for the first time, the concentration of polyalcohol and/or the monose aqueous solution is 30-50g/ 100ml, group vib metallic element counts concentration as 18-20g/100ml using oxide, group VIII metal element concentration in terms of oxide For 3-4g/100ml, the consumption of polyalcohol and/or monose and the active metal component aqueous solution is alumina support water absorption 20%-30%；Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10-30g/100ml, group vib metal member Element counts concentration as 10-15g/100ml using oxide, and group VIII metal element counts concentration as 1.5-3g/100ml using oxide, many The consumption of first alcohol and/or monose and the active metal component aqueous solution is the 40%-60% of alumina support water absorption；Third time is sprayed The mass concentration of leaching, polyalcohol and/or the monose aqueous solution is 5-10g/100ml, and group vib metallic element concentration in terms of oxide is 5-10g/100ml, group VIII metal element counts concentration as 1-1.5g/100ml using oxide, polyalcohol and/or monose and activity The consumption of the metal component aqueous solution is the 10%-40% of alumina support water absorption.

In the inventive method, step（3）Described hydro-thermal process is two sections of hydro-thermal process, is 100-140 first in temperature DEG C hydro-thermal process 5-10 hours, is then 180-250 DEG C in temperature, preferably 200-230 DEG C, hydrothermal conditions are that 6-12 is small When, preferably 8-10 hours.

In the inventive method, described drying condition is to be dried 6-10 hours at 80-120 DEG C.

In the inventive method, step（4）Described anaerobic high-temperature process condition is：Treatment temperature is 400-600 DEG C, processing Time is 3-6 hours；Wherein the atmosphere of anaerobic high-temperature process can be nitrogen or inert atmosphere, wherein inert atmosphere be helium, One or more in neon or argon gas.

Polyalcohol and/or monose and the active metal component aqueous solution spray dip forming of the inventive method various concentrations In alumina support, spray dipping process, polyalcohol and/or monose and the active metal component aqueous solution are in carrier duct capillary force Gradually permeated under effect from carrier surface to center, when spraying dipping due to multistep, polyalcohol and/or monose and work in maceration extract The concentration of property metal component is gradually reduced, it is ensured that the concentration of polyalcohol and/or monose and active metal component is by carrier surface To center in incremental distribution.Carrier after dipping is using two sections of hydro-thermal process, polyalcohol and/or monose when low-temperature hydrothermal is handled Generation polymerisation formation polymer is adsorbed onto alumina carrier surface, and polymer carbonizes to form carbon-coating suction during High-temperature water heat treatment It is attached to carrier surface.Because the concentration of polyalcohol and/or monose is distributed by carrier surface to center in incremental, carbon-coating after charing Thickness is same thicker in the relatively thin internal carbon-coating of incremental distribution, i.e. carrier outside carbon-coating from carrier surface to center.While charing Urea is hydrolyzed, the NH of generation₃Reacted with the group vib in solution and VIII active component, form corresponding precipitation, precipitation It is adsorbed onto by hydrogen bond action on carbon-coating, it is therefore prevented that the migration of active metal component.Material after hydro-thermal process is in anaerobic high temperature In processing procedure, the presence of carbon-coating effectively prevents the strong interaction between metal component and carrier, due to carbon layers having thicknesses Gradient is distributed, and acts on and gradually weakening from outside to inside between active metal and carrier, i.e., catalyst activity is gradually stepped up from outside to inside. During HDM, catalytic inner active metal component content is higher, relatively weak with carrier function, and activity increases By force, the reaction inside catalyst duct is promoted, effectively prevent makes demetalization anti-because active component activity in outer surface is higher Acutely catalyst duct should be caused to block and make the phenomenon of catalyst inactivation, extend and urge while catalyst activity is improved The service life of agent.

Brief description of the drawings

Fig. 1 catalyst granules is spherical cross-sectional view.

Fig. 2 catalyst granules is cylindrical cross-sectional view.

Embodiment

The effect and effect of the inventive method are further illustrated with reference to embodiment, but is not limited to following implementation Example.The commercially available shaped alumina alumina supporter used in embodiment, the pore volume of alumina support is 0.8-1.5ml/g, and specific surface area is 160-300m²/ g, bore dia accounts for the 70%-90% of total pore volume for 10-20nm hole, and crushing strength is 130-160N/cm, water absorption 1.0g/g.Carbon and active metallic content are measured by JEOL's JXA-8230 electron probes in catalyst of the present invention, are surveyed The accelerating potential of timing selection is 15KV, and probe current is 8 × 10^-8A, beam spot size is 3 μm.

Metering system：Be respectively 1/4R at measurement catalyst cross-section center and with distance at catalyst cross-section center, Carbon content and active metallic content at 1/2R, 3/4R and R, wherein R be cross-section center with it is any one in the outer most edge of cross section The distance of line segment between point, then by division calculation, obtains the ratio between each content.

Embodiment 1

Pore volume is weighed for 0.9ml/g, specific surface area is 220m²/ g 100 grams of γ phase cylinder bar shapeds alumina support is put into In beaker, mass concentration is added into beaker and is impregnated 1.5 hours for 24% aqueous solution of urea 120ml, redundant solution is filtered, will Carrier is dried 5 hours in 110 DEG C.Dried carrier is placed in spray rolling pot, under rotary state, with atomizing type to rolling Carrier spray impreg sugar alcohol concentration in pot is 40g/100ml, MoO₃Concentration is 18.8 g/100ml（Molybdenum source comes from molybdic acid Ammonium）, NiO concentration is 3.5g/100ml（Nickel source comes from nickel chloride）Xylitol and active metal aqueous solution 25ml；Then with wood Sugar alcohol concentration is 20g/100ml, MoO₃Concentration is 11g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.9g/100ml （Nickel source comes from nickel chloride）Xylitol and active metal aqueous solution 40ml continue to spray oxide impregnation alumina supporter；Finally use

Xylose determining alcohol is 10g/100ml, MoO₃Concentration is 7.5g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.3g/100ml（Nickel source comes from nickel chloride）Xylitol and active metal aqueous solution 40ml continue to spray oxide impregnation alumina supporter. Humectant is transferred in autoclave and autoclave is placed in baking oven and is heat-treated 5 hours in 110 DEG C of sealings, 200 DEG C are then heated to Sealing heat treatment 8 hours, naturally cools to room temperature.Alumina support after hydro-thermal process is in dry 6 hours at 120 DEG C.Dry In being calcined 5 hours at 550 DEG C, Hydrodemetalation catalyst C1 of the present invention, catalyst performance is made in a nitrogen atmosphere in material afterwards Matter is shown in Table 1.

Embodiment 2

Be the same as Example 1, simply alumina support is clover bar shaped, and the mass concentration of urea is 32%, spray leaching for the first time With the concentration of 30ml sorbierites it is 30g/100ml, MoO during stain₃Concentration is 20g/100ml（Molybdenum source comes from ammonium molybdate）, NiO is dense Spend for 3.7g/100ml（Nickel source comes from nickel chloride）Sorbierite and the active metal aqueous solution impregnate.Used during second of spray dipping The concentration of 50ml sorbierites is 10g/100ml, MoO₃Concentration is 13g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 3g/ 100ml（Nickel source comes from nickel chloride）Sorbierite and the active metal aqueous solution impregnate.20ml sorbs are used during third time spray dipping The concentration of alcohol is 5g/100ml, MoO₃Concentration is 9g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.25g/100ml （Nickel source comes from nickel chloride）Sorbierite and the active metal aqueous solution impregnate.First in 130 DEG C of sealing heat treatments 6 during hydro-thermal process Hour, then heat to 220 DEG C of sealing heat treatments and Hydrodemetalation catalyst C2 of the present invention is made in 10 hours, catalyst property is shown in Table 1.

Embodiment 3

Be the same as Example 1, simply the mass concentration of urea is 40%, using four spray dippings during spray dipping,

It is for the first time 50g/100ml, MoO with the concentration of 20ml mannitol during spray dipping₃Concentration is 19.8g/100ml （Molybdenum source comes from ammonium molybdate）, NiO concentration is 4g/100ml（Nickel source comes from nickel chloride）Mannitol and the water-soluble immersion of active metal Stain.It is for the second time 30g/100ml, MoO with the concentration of 40ml sorbierites during spray dipping₃Concentration is 15g/100ml（Molybdenum source is come From ammonium molybdate）, NiO concentration is 2.6g/100ml（Nickel source comes from nickel chloride）Sorbierite and the active metal aqueous solution impregnate.The With the concentration of 20ml sorbierites it is 30g/100ml, MoO during three spray dippings₃Concentration is 10g/100ml（Molybdenum source comes from molybdic acid Ammonium）, NiO concentration is 1.5g/100ml（Nickel source comes from nickel chloride）Sorbierite and the active metal aqueous solution impregnate.4th spray With the concentration of 20ml sorbierites it is 10g/100ml, MoO when drenching dipping₃Concentration is 5g/100ml（Molybdenum source comes from ammonium molybdate）, NiO Concentration is 1g/100ml（Nickel source comes from nickel chloride）Sorbierite and the active metal aqueous solution impregnate.Exist first during hydro-thermal process 120 DEG C of sealings are heat-treated 8 hours, are then heated to 240 DEG C of sealing heat treatments and Hydrodemetalation catalyst of the present invention are made in 6 hours C3, catalyst property is shown in Table 1.

Embodiment 4

Be the same as Example 1, simply the mass concentration of urea is 20%, using spray dipping twice during spray dipping, is sprayed for the first time With the concentration of 50ml arabites it is 40g/100ml, MoO when drenching dipping₃Concentration is 18g/100ml（Molybdenum source comes from molybdic acid Ammonium）, NiO concentration is 3g/100ml（Nickel source comes from nickel chloride）Arabite and the active metal aqueous solution impregnate.Second With the concentration of 55ml arabites it is 20g/100ml, MoO during spray dipping₃Concentration is 10g/100ml（Molybdenum source comes from molybdic acid Ammonium）, NiO concentration is 1.5g/100ml（Nickel source comes from nickel chloride）Arabite and the active metal aqueous solution impregnate.Hydro-thermal It is heat-treated 7 hours in 140 DEG C of sealings first during processing, then heats to 180 DEG C of sealing heat treatment, 12 hours obtained present invention and add Hydrogen catalyst for demetalation C4, catalyst property is shown in Table 1.

Embodiment 5

Be the same as Example 1, simply alumina support is bunge bedstraw herb bar shaped, and the mass concentration of urea is 28%, and xylitol changes matter into Amount is than being 1:1:1:1 xylitol, arabite, the mixed alcohol of sorbierite and mannitol, impregnate during spray dipping for the first time MoO in liquid₃Concentration is 19g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 3.3g/100ml（Nickel source comes from nickel chloride）. MoO in maceration extract during second of spray dipping₃Concentration is 12.5g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 2.25g/ 100ml（Nickel source comes from nickel chloride）.MoO in maceration extract during third time spray dipping₃Concentration is 5g/100ml（Molybdenum source comes from molybdenum Sour ammonium）, NiO concentration is 1.5g/100ml（Nickel source comes from nickel chloride）.It is small in 100 DEG C of sealing heat treatments 10 first during hydro-thermal process When, then heat to 250 DEG C of sealing heat treatments and Hydrodemetalation catalyst C5 of the present invention is made in 6 hours, catalyst property is shown in Table 1。

Embodiment 6

Be the same as Example 1, simply the mass concentration of urea is 36%, and xylitol changes glucose into, is soaked for the first time during spray dipping MoO in stain liquid₃Concentration is 18.4g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 3.5g/100ml（Nickel source comes from chlorination Nickel）.MoO in maceration extract during second of spray dipping₃Concentration is 12g/100ml（Molybdenum source comes from ammonium molybdate）, NiO concentration is 1.5g/100ml（Nickel source comes from nickel chloride）.MoO in maceration extract during third time spray dipping₃Concentration is 6g/100ml（Molybdenum source is come From ammonium molybdate）, NiO concentration is 1g/100ml（Nickel source comes from nickel chloride）.Hydrodemetalation catalyst C6 of the present invention, catalysis is made Agent property is shown in Table 1.

Embodiment 7

Be the same as Example 1, it is 1 that simply xylitol, which changes mass ratio into,:1:1:1 glucose, fructose, xylitol and sorbierite The aqueous solution impregnates.Hydrodemetalation catalyst C7 of the present invention is made, catalyst property is shown in Table 1.Comparative example 1

Be the same as Example 1, the xylitol of same volume and mass concentration is simply used once spray with active metal solution The mode oxide impregnation alumina supporter of dipping, is made comparative catalyst C8, and catalyst property is shown in Table 1.

Comparative example 2

Be the same as Example 1, does not simply add xylitol in maceration extract, and comparative catalyst C9 is made, and catalyst property is shown in Table 1.

Comparative example 3

Comparative catalyst C10 is made in be the same as Example 1, the non-hydrothermal treatment of humectant after simply impregnating, and catalyst property is shown in Table 1.

The catalyst property of table 1.

As it can be seen from table 1 the catalyst carbon and active metal component that are prepared using the inventive method are in catalyst radial direction Distribution gradient, i.e. catalyst external surface carbon and active metal component content are relatively low, catalytic inner carbon and active metal Constituent content is of a relatively high.

Embodiment 9

The following examples illustrate the Hydrodemetalation catalyst of the invention provided and the catalytic performance of comparative catalyst.

Using decompression residuum listed by table 2 as raw material, what on 200 milliliters of hydrogenation reaction device prepared by evaluation example 1-7 urges Catalyst C8-C10 prepared by agent C1-C7 and comparative example 1-3 catalytic performance, catalyst is long 2 ~ 3 millimeters bar, catalyst Loading amount is 100 milliliters, and reaction temperature is 385 DEG C, and hydrogen dividing potential drop is 15MPa, and liquid hourly space velocity (LHSV) is 1.0 hours^-1, hydrogen to oil volume ratio is 900, reaction determines the content of each impurity in generation oil after 200 hours, calculate removal efficiency, and evaluation result is shown in Table 3.

The raw material oil nature of table 2.

The catalyst hydrogenation performance comparison of table 3.

	C1	C2	C3	C4	C5	C6	C7	C8	C9	C10
											Nickel removal, wt%	72.4	78.6	74.2	67.5	73.2	73.4	72.7	50.3	42.9	42.8
Vanadium removal, wt%	80.6	83.4	80.3	73.8	79.3	79.8	79.4	52.7	54.4	53.7
											Desulfurization, wt%	56.9	62.1	59.3	52.7	58.3	57.9	59.7	46.1	43.2	46.2

It can be seen from the data of table 3 compared with comparative catalyst, the catalyst that the present invention is provided is de- with higher hydrogenation Metal active and hydrodesulfurization activity.

Activity rating is carried out to the catalyst obtained by above-described embodiment and comparative example, operation 5000h temperature rise is shown in Table 3.

The reaction temperature lift-off value of table 4.

Find out from the result of table 4, after reacting 5000 hours, the Hydrodemetalation catalyst provided using the present invention, in order to High demetallization per is kept, required reaction temperature increase rate is far smaller than comparative catalyst, the hydrogenation that this explanation present invention is provided Catalyst for demetalation has higher activity stability.

Claims

1. a kind of residuum hydrogenating and metal-eliminating catalyst, it is characterised in that：Including alumina support, active metal and carbon, to be catalyzed On the basis of agent weight, active metal is in terms of oxide, and Mo and/or W weight content are 6.0wt%-15wt%, Co and/or Ni weight Amount content is 1.0wt%-4.0wt%, and carbon is calculated as 1wt%-15wt% with element, and alumina support is 66wt% ~ 92wt%；Carbon content expires It is enough lower condition：Apart from catalyst granules cross-section center（Hereinafter referred to as center）Carbon content and catalyst granules at 1/4R is horizontal The carbon content ratio of kernel of section is that carbon content and center carbon content ratio are 30%-70%, distance at 50%-90%, distance center 1/2R Carbon content and center carbon content ratio are the carbon content at any point and center in 10%-50%, cross section outer most edge at the 3/4R of center Carbon content ratio is 5%-40%；Active metallic content meets following condition：Distance center 1/4R active metallic contents and central active Tenor ratio is that active metallic content and central active tenor ratio are 70%-80% at 80%-100%, distance center 1/2R, Active metallic content and central active tenor ratio are any one in 60%-70%, cross section outer most edge at distance center 3/4R The active metallic content of point is 50%-60% with central active tenor ratio.

2. according to the catalyst described in claim 1, it is characterised in that：It is 160-270m than surface²/ g, pore volume is 0.8- 1.2mL/g。

3. the preparation method of the residuum hydrogenating and metal-eliminating catalyst described in a kind of claim 1 or 2, it is characterised in that including as follows Content：（1）With aqueous solution of urea oxide impregnation alumina supporter, the alumina support after dipping is through drying process；（2）Prepare at least two The maceration extract containing polyalcohol and/or monose and active metal component of various concentrations is planted, is sprayed according to the order of concentration from high to low It is immersed in step（1）On alumina support so that the concentration of polyalcohol and/or monose and active metal component formed on carrier by Outside to inside in gradient distribution from low to high；Order wherein according to concentration from high to low, adjacent two kinds of various concentrations maceration extracts Between, it is identical that the concentration of polyalcohol and/or monose reduces trend with the concentration of active component；（3）By step（2）Oxygen after dipping Change alumina supporter and be transferred to progress hydro-thermal process in sealing container；（4）By step（3）Obtained dry materials, then at anaerobic high temperature Reason, obtains residuum hydrogenating and metal-eliminating catalyst.

4. in accordance with the method for claim 3, it is characterised in that：Step（1）The mass concentration of described aqueous solution of urea is 20%-40%, the consumption of aqueous solution of urea is at least the saturated water adsorptive value of alumina support, and dip time is 1-2 hours.

5. in accordance with the method for claim 3, it is characterised in that：Step（2）Described polyalcohol includes xylitol, sorb One or more in alcohol, mannitol or arabite；Described monose includes one kind or several in glucose, ribose or fructose Kind.

6. in accordance with the method for claim 3, it is characterised in that：Step（2）Described active component is group vib and VIII Metallic element, wherein group vib metallic element are selected from molybdenum and/or tungsten, and group VIII metal element is selected from nickel and/or cobalt.

7. in accordance with the method for claim 3, it is characterised in that：Step（2）Polyalcohol and/or list in described maceration extract The concentration of sugar is 5-50 g/100mL.

8. in accordance with the method for claim 3, it is characterised in that：Step（2）Described maceration extract according to concentration from high to low, The concentration difference of polyalcohol and/or monose in adjacent maceration extract twice is 5-30g/100mL.

9. in accordance with the method for claim 3, it is characterised in that：Step（2）Described maceration extract according to concentration from high to low, Group vib metallic element in adjacent maceration extract twice counts concentration difference as 4-10g/100mL using oxide, group VIII metal element with Oxide meter concentration difference is 0.5-2g/100mL.

10. in accordance with the method for claim 3, it is characterised in that：Step（2）Prepare 2-4 kind various concentrations polyalcohol and/ Or the maceration extract of monose and active metal component.

11. in accordance with the method for claim 3, it is characterised in that：Step（2）The described maceration extract consumption sprayed every time is The 10%-60% of alumina support saturated water adsorptive value, the total consumption of maceration extract repeatedly sprayed is the saturated water adsorptive value of alumina support.

12. in accordance with the method for claim 3, it is characterised in that：Step（2）Prepare 3 kinds of various concentrations polyalcohol and/or Monose and active metal component maceration extract are sprayed, and detailed process is as follows：Spray for the first time, polyalcohol and/or monose are water-soluble The concentration of liquid is 30-50g/100mL, and group vib metallic element counts concentration as 18-20g/100mL using oxide, group VIII metal member Element counts concentration as 3-4g/100mL using oxide, and the consumption of polyalcohol and/or monose and the active metal component aqueous solution is oxidation The 20%-30% of alumina supporter water absorption；Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10-30g/ 100mL, group vib metallic element counts concentration as 10-15g/100mL using oxide, group VIII metal element concentration in terms of oxide For 1.5-3g/100mL, the consumption of polyalcohol and/or monose and the active metal component aqueous solution is alumina support water absorption 40%-60%；Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5-10g/100mL, group vib metallic element Concentration is counted as 5-10g/100mL using oxide, group VIII metal element counts concentration as 1-1.5g/100mL using oxide, polyalcohol And/or the 10%-40% that the consumption of monose and the active metal component aqueous solution is alumina support water absorption.

13. in accordance with the method for claim 3, it is characterised in that：Step（3）Described hydro-thermal process is at two sections of hydro-thermals Reason, is 100-140 DEG C of hydro-thermal process 5-10 hour in temperature first, is then 180-250 DEG C in temperature, hydrothermal conditions are 6-12 hours.

14. in accordance with the method for claim 3, it is characterised in that：Described drying condition is to be dried at 80-120 DEG C 6-10 hours.

15. in accordance with the method for claim 3, it is characterised in that：Step（4）Described anaerobic high-temperature process condition is：Place It is 400-600 DEG C to manage temperature, and processing time is 3-6 hours；Wherein the atmosphere of anaerobic high-temperature process be nitrogen or inert atmosphere, its Middle inert atmosphere is the one or more in helium, neon or argon gas.