CN105582949B - A kind of high-activity hydrodemetallizationcatalyst catalyst and preparation method thereof - Google Patents
A kind of high-activity hydrodemetallizationcatalyst catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of high-activity hydrodemetallizationcatalyst 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
Technical field
The present invention relates to a kind of high-activity hydrodemetallizationcatalyst catalyst and preparation method thereof.
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.In roasting process, active metal component easily has an effect to be formed with alumina support
Very strong M-O-Al keys, cause active component formation Spinel and lose activity, or make active component can not complete cure
So as to reduce 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 high-activity hydrodemetallizationcatalyst catalyst and preparation method thereof,
Carbon content distribution gradient in catalyst of the present invention, catalyst exterior active component is relatively strong with carrier function, and inside is living
Property component and carrier function are relatively weak, and the easy complete cure of active component significantly improves the demetalization and desulfurization of catalyst
Activity.
The high-activity hydrodemetallizationcatalyst catalyst of the present invention, including alumina support, active metal and carbon, with catalyst weight
On the basis of amount, active metal is in terms of oxide, and Mo and/or W weight content are 6.0wt%-15wt%, Co and/or Ni weight contains
Measure as 1.0wt%-4.0wt%, alumina support is 66wt% ~ 92wt%, preferably surplus, and carbon is calculated as 1wt%-15wt% with element, excellent
Select 5wt%-10wt%;It is 160-270m than surface2/ g, pore volume is 0.8-1.2ml/g;Carbon content meets following condition:Distance is urged
Catalyst particles cross-section center(Hereinafter referred to as center)The carbon content of carbon content and catalyst granules cross-section center at 1/4R
Than for 60%-80%, carbon content and center carbon content ratio are carbon content at 40%-60%, distance center 3/4R at distance center 1/2R
Be 20%-40% with center carbon content ratio, in the outer most edge of cross section the carbon content at any point with center carbon content than 10%-20%, R
In cross-section center and cross section outer most edge for catalyst granules between any point line segment distance.
The present invention is at any point in catalyst granules cross-section center 1/4R, 1/2R, 3/4R, cross section outer most edge
Carbon content and the carbon content of catalyst granules cross-section center urge and being measured by electron probe.
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.
The preparation method of the high-activity hydrodemetallizationcatalyst catalyst of the present invention, including following content:
(1)The polyalcohol and/or the monose aqueous solution of at least two various concentrations are prepared, according to the order of concentration from high to low
Spray on the alumina support so that it is in from low to high that the concentration of polyalcohol and/or monose forms ecto-entad on carrier
Gradient is distributed;
(2)Alumina support after dipping is subjected to hydro-thermal charing process, drying process in sealing container;
(3)With active metal maceration extract impregnation steps(2)Obtained alumina support, is dried, then anaerobic high-temperature process,
Obtain Hydrodemetalation catalyst.
In the inventive method, step(1)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(1)Described polyalcohol and/or the mass concentration of the monose aqueous solution are 5% ~ 50%.
In the inventive method, step(1)It is described according to concentration from high to low spray order, adjacent polyalcohol twice
And/or the concentration difference of the monose aqueous solution is 5% ~ 30%, preferably 10% ~ 20%;It is preferred that prepare 2 ~ 4 kinds of various concentrations polyalcohol and/
Or the monose aqueous solution.
In the inventive method, step(1)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(1)It is preferred that the polyalcohol and/or the monose aqueous solution of preparing 3 kinds of various concentrations are sprayed
Leaching, detailed process is as follows:Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, polyalcohol and/
Or the 20%-30% that the consumption of the monose aqueous solution is alumina support water absorption;Spray for the second time, polyalcohol and/or monose are water-soluble
The mass concentration of liquid is 10%-30%, and the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of alumina support water absorption;
Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, polyalcohol and/or the monose aqueous solution use
Measure as the 10%-40% of alumina support water absorption.
In the inventive method, step(1)Described alumina support is graininess, can be that spherical or cylindricality is wherein spherical
Can be spheroidal or elliposoidal, cylindricality can cylinder, square column type or abnormity(Clover, bunge bedstraw herb or five tooth balls).Oxidation
Alumina supporter can use commercially available, it would however also be possible to employ be suitable for the oxygen of Hydrodemetalation catalyst carrier made from conventional method
Change aluminium.The one kind or several that can also be added as needed in the auxiliary elements such as Si, Ti, Zr, B or F in described alumina support
Kind.
In the inventive method, step(2)Described hydro-thermal charing process temperature be 180-250 DEG C, preferably 200-230 DEG C,
Hydrothermal conditions are 6-12 hours, and preferably 8-10 hours, hydro-thermal process pressure was self-generated pressure, under this hydro-thermal carbonization condition
It ensure that polyalcohol and/or monose are carbonized completely.Wherein, self-generated pressure is relevant with treatment temperature, when temperature is 100 DEG C, pressure
Force value(Gauge pressure)General 0.1MPa, at 150 DEG C, pressure value is generally 0.43MPa, and at 250 DEG C, pressure value is generally 1.95MPa.
In the inventive method, step(2)Described alumina support carries out sealing heat treatment preferably before charing process,
Heat treatment condition is:80 ~ 130 DEG C are handled 0.5 ~ 2 hour.
In the inventive method, step(3)Described load active component used volume impregnation, incipient impregnation or spray
Impregnating method, dip time is 1-5 hours, preferably crosses volume impregnation.Wherein, maceration extract preparation choose active component can
Soluble compound, such as nickel chloride, nickel nitrate, nickel sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, phosphomolybdic acid,
Ammonium molybdate, ammonium metatungstate and ammonium tungstate etc., the concentration of active component is calculated as with corresponding oxide content in maceration extract:MoO3With/
Or WO32 ~ 20g/100ml of 10 ~ 80g/100ml, NiO and/or CoO, the specific concentration of maceration extract can be according to final catalyst
On active metallic content depending on.
In the inventive method, described drying condition is to be dried 6-10 hours at 80-120 DEG C.
In the inventive method, step(3)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.
Catalyst of the present invention reacts applied to HDM, and general process conditions are:Reaction temperature is 350 ~ 400
DEG C, hydrogen dividing potential drop is 10 ~ 20MPa, and liquid hourly space velocity (LHSV) is 0.5 ~ 2.0h-1, hydrogen to oil volume ratio is 500:1~1000:1.
Polyalcohol and/or the monose aqueous solution spray dip forming alumina support of the inventive method various concentrations, so
Afterwards by hydro-thermal charing process, carbon-coating is formed on carrier surface and duct inwall;Spray in dipping process, maceration extract is in carrier
Gradually permeated under the effect of duct capillary force from carrier surface to center, due to when multistep, which is sprayed, to be impregnated, in maceration extract polyalcohol and/
Or the concentration of monose is gradually reduced, it is ensured that the concentration of polyalcohol and/or monose is by carrier surface to center in incremental distribution.Charcoal
The thickness of carbon-coating is from carrier surface to center in incremental distribution after change, i.e., the relatively thin internal carbon-coating of carbon-coating is thicker outside carrier.In carbon
Sealing heat treatment is carried out to the carrier after dipping before precursor charing, the shape of absorption and carbon-coating of the carbon precursor on carrier is promoted
Into;The material after active component is impregnated in anaerobic high-temperature process, and the presence of carbon-coating effectively prevents metal component and load
Strong interaction between body, because the gradient of carbon layers having thicknesses is distributed, is acted on from outside to inside gradually between active metal and carrier
Weaken, i.e., catalyst activity is gradually stepped up from outside to inside, during HDM, is promoted anti-inside catalyst duct
Should, effectively prevent due to outer surface active component activity it is higher make demetalization reaction acutely and cause catalyst duct block and
Make the phenomenon of catalyst inactivation, the service life of catalyst is extended while catalyst activity is improved.
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
1g/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 spray rolling pot, under rotary state, impregnating effect concentration is sprayed as 40% xylitol using carrier of the atomizing type into rolling pot
Aqueous solution 25ml;Then continue to spray oxide impregnation alumina supporter for 20% xylose alcohol solution 40ml with mass concentration;Finally use
Mass concentration continues to spray oxide impregnation alumina supporter for 10% xylose alcohol solution 40ml.Dipping terminates to turn alumina support
Enter in autoclave and autoclave is placed in baking oven and be heat-treated 120 minutes in 80 DEG C of sealings, then heat to 180 DEG C, spontaneous pressure
Charing process 9 hours, naturally cool to room temperature under power.Alumina support after hydro-thermal process is in dry 3 hours at 120 DEG C.It is dry
Load after dry contains MoO with 150ml315 grams(Molybdenum source comes from ammonium molybdate), NiO2 grams(Nickel source comes from nickel chloride)Maceration extract dipping
Above-mentioned carrier 3 hours, filters redundant solution, is dried 8 hours at 110 DEG C, dried material is in a nitrogen atmosphere in 550 DEG C
Lower roasting 5 hours, is made Hydrodemetalation catalyst C1 of the present invention, and catalyst property is shown in Table 1.
Embodiment 2
Be the same as Example 1, with the aqueous solution of the 30ml mass concentrations for 30% sorbierite when simply spray impregnates for the first time, the
With the aqueous solution of the 50ml mass concentrations for 10% sorbierite when secondary spraying impregnates, 20ml mass is used during third time spray dipping
Concentration is the aqueous solution of 5% sorbierite, and heat treatment temperature is 130 DEG C, and heat treatment time is 60 minutes.Temperature during charing process
For 200 DEG C, carbonization time is 8 hours.Contain MoO with 150ml during activity component impregnation310.5 grams(Molybdenum source comes from molybdic acid
Ammonium), 2 grams of NiO(Nickel source comes from nickel nitrate)Maceration extract impregnates.Hydrodemetalation catalyst C2 of the present invention, catalyst property is made
It is shown in Table 1.
Embodiment 3
Be the same as Example 1, is for the first time 50% with 20ml mass concentrations during spray dipping simply using four spray dippings
The aqueous solution of mannitol, with the aqueous solution of the 40ml mass concentrations for 30% sorbierite during second of spray dipping, third time is sprayed
During dipping with 20ml mass concentrations for 20% sorbierite the aqueous solution, the 4th time spray dipping when with 20ml mass concentrations be 10%
Sorbierite the aqueous solution, heat treatment temperature be 100 DEG C, heat treatment time be 90 minutes.Temperature is 240 DEG C during charing process,
Carbonization time is 12 hours.Contain MoO with 150ml during activity component impregnation311.5 grams(Molybdenum source comes from ammonium molybdate), NiO
2.5 gram(Nickel source comes from basic nickel carbonate)Maceration extract impregnates.Hydrodemetalation catalyst C3 of the present invention is made, catalyst property is shown in
Table 1.
Embodiment 4
Be the same as Example 1, is for the first time 40% with 50ml mass concentrations during spray dipping simply using spray dipping twice
The aqueous solution of arabite, with the aqueous solution of the 55ml mass concentrations for 20% arabite, charcoal during second of spray dipping
It is 250 DEG C to change temperature, and carbonization time is 6 hours.Hydrodemetalation catalyst C4 of the present invention is made, catalyst property is shown in Table 1.
Embodiment 5
Be the same as Example 1, it is 1 that simply xylitol, which changes mass ratio into,:1:1:1 xylitol, arabite, sorbierite and sweet
Reveal the mixing alcohol solution dipping of alcohol, temperature is 220 DEG C during charing process, processing time is 10 hours.Present invention hydrogenation is made
Catalyst for demetalation C5, catalyst property is shown in Table 1.
Embodiment 6
Be the same as Example 1, simply xylose alcohol solution change into glucose the aqueous solution dipping, during charing process temperature be 230
DEG C, processing time is 9 hours.Hydrodemetalation catalyst C6 of the present invention is made, catalyst property is shown in Table 1.
Embodiment 7
Be the same as Example 1, simply xylose alcohol solution change into the ribose aqueous solution dipping, during charing process temperature be 190 DEG C,
Processing time is 6 hours.Hydrodemetalation catalyst C7 of the present invention is made, catalyst property is shown in Table 1.
Embodiment 8
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 dipping, during charing process temperature be 240 DEG C, processing time be 9 hours.Hydrodemetalation catalyst of the present invention is made
C8, catalyst MoO3Weight content is 7.9wt%, and NiO weight contents are 1.2wt%, and carbon is calculated as 8.2wt% with element, and surplus is
Alumina support;It is 207m than surface2/ g, pore volume is 0.95ml/g.
Comparative example 1
Be the same as Example 1, simply alumina support dipping active component before without alcohol and/or sugar juice dipping and hydro-thermal at
Reason, is made comparative catalyst C9, and catalyst property is shown in Table 1.
Comparative example 2
Be the same as Example 1, simply impregnates without polyalcohol and/or monosaccharide solutions before alumina support dipping active component, uses
Deionized water dipping simultaneously carries out hydro-thermal process in autoclave, and comparative catalyst C10 is made, and catalyst property is shown in Table 1.
Comparative example 3
Be the same as Example 1, mixes once spray by the xylose alcohol solution of same volume and mass concentration when simply impregnating and soaks
Comparative catalyst C11 is made in stain, and catalyst property is shown in Table 1.
The catalyst property of table 1.
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 1-8 urges
Catalyst C9-C11 prepared by agent C1-C8 and comparative example 1-3 catalytic performance, catalyst is long 2 ~ 3 millimeters bar, catalyst
Loading amount is 100 milliliters, and reaction temperature is 390 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 | C11 | |
Nickel removal, wt% | 70.2 | 65.6 | 69.4 | 66.9 | 71.6 | 71.4 | 70.7 | 69.9 | 37.7 | 45.4 | 57.6 |
Vanadium removal, wt% | 78.8 | 74.7 | 79.5 | 75.9 | 81.7 | 80.8 | 78.1 | 77.4 | 52.2 | 56.7 | 65.9 |
Desulfurization, wt% | 57.9 | 50.4 | 55.3 | 53.5 | 58.8 | 58.9 | 56.9 | 55.2 | 40.3 | 44.7 | 49.5 |
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 (16)
1. a kind of high-activity hydrodemetallizationcatalyst catalyst, including alumina support, active metal and carbon, it is characterised in that:To urge
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 content is 1.0wt%-4.0wt%, and alumina support is 66wt% ~ 92wt%, and carbon is calculated as 1wt%-15wt% with element;Carbon content
Meet following condition:The carbon of carbon content and catalyst granules cross-section center at catalyst granules cross-section center 1/4R
Content ratio is that carbon content and center carbon content ratio are carbon at 40%-60%, distance center 3/4R at 60%-80%, distance center 1/2R
Content and the carbon content that center carbon content ratio is any point in 20%-40%, cross section outer most edge are with center carbon content ratio
10%-20%, R are the distance of line segment between any point in the cross-section center and cross section outer most edge of catalyst granules.
2. according to the catalyst described in claim 1, it is characterised in that:The ratio surface of catalyst is 160-270m2/ g, pore volume is
0.8-1.2mL/g。
3. the preparation method of the catalyst described in a kind of claim 1 or 2, it is characterised in that including following content:(1)It is formulated into
The polyalcohol and/or the monose aqueous solution of few two kinds of various concentrations, are sprayed in alumina support according to the order of concentration from high to low
On so that the concentration of polyalcohol and/or monose forms ecto-entad in gradient distribution from low to high on carrier;(2)Will leaching
Alumina support after stain carries out hydro-thermal charing process, drying process in sealing container;(3)Impregnated with active metal maceration extract
Step(2)Obtained alumina support, is dried, then anaerobic high-temperature process, obtains Hydrodemetalation catalyst.
4. in accordance with the method for claim 3, it is characterised in that:Step(1)Described polyalcohol includes xylitol, sorb
One or more in alcohol, mannitol or arabite;Described monose include one kind in glucose, ribose or fructose etc. or
It is several.
5. in accordance with the method for claim 3, it is characterised in that:Step(1)Described polyalcohol and/or the monose aqueous solution
Mass concentration is 5% ~ 50%.
6. in accordance with the method for claim 3, it is characterised in that:Step(1)Described the spraying from high to low according to concentration
Sequentially, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5% ~ 30%.
7. in accordance with the method for claim 3, it is characterised in that:Step(1)Described the spraying from high to low according to concentration
Sequentially, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 10% ~ 20%.
8. in accordance with the method for claim 3, it is characterised in that:Step(1)The middle polyalcohol for preparing 2 ~ 4 kinds of various concentrations
And/or the monose aqueous solution.
9. in accordance with the method for claim 3, it is characterised in that:Step(1)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.
10. in accordance with the method for claim 3, it is characterised in that:Step(1)Prepare 3 kinds of various concentrations polyalcohol and/or
The monose aqueous solution is sprayed, and detailed process is as follows:Spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is
The consumption of 30%-50%, polyalcohol and/or the monose aqueous solution is the 20%-30% of alumina support water absorption;Spray for the second time, it is many
The mass concentration of first alcohol and/or monose aqueous solution is 10%-30%, and the consumption of polyalcohol and/or the monose aqueous solution is carrying alumina
The 40%-60% of body water absorption;Third time is sprayed, and the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, polyalcohol
And/or the 10%-40% that the consumption of the monose aqueous solution is alumina support water absorption.
11. in accordance with the method for claim 3, it is characterised in that:Step(2)Described hydro-thermal charing process temperature is 180-
250 DEG C, hydrothermal conditions are 6-12 hours, and hydro-thermal process pressure is self-generated pressure.
12. in accordance with the method for claim 3, it is characterised in that:Step(2)Described alumina support is in charing process
Before, sealing heat treatment is carried out, heat treatment condition is:80 ~ 130 DEG C are handled 0.5 ~ 2 hour.
13. in accordance with the method for claim 3, it is characterised in that:Step(3)Described impregnation method used volume to soak
One or more in stain, incipient impregnation or spray dipping, dip time is 1-5 hours;Active component is dense in maceration extract
Degree is calculated as with corresponding oxide content:MoO3And/or WO32 ~ 20g/100mL of 10 ~ 80g/100mL, NiO and/or CoO.
14. in accordance with the method for claim 3, it is characterised in that:Described drying condition is that 6- is dried at 80-120 DEG C
10 hours.
15. in accordance with the method for claim 3, it is characterised in that:Step(3)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.
16. the catalyst described in a kind of claim 1 or 2 reacts applied to HDM, it is characterised in that:Process conditions
For:Reaction temperature is 350 ~ 400 DEG C, and hydrogen dividing potential drop is 10 ~ 20MPa, and liquid hourly space velocity (LHSV) is 0.5 ~ 2.0h-1, hydrogen to oil volume ratio is 500:1
~1000:1.
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CN101928592A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Grading composition of hydrogenation catalyst |
CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
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