CN105618072B - The preparation method of Hydrodemetalation catalyst - Google Patents
The preparation method of Hydrodemetalation catalyst Download PDFInfo
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- CN105618072B CN105618072B CN201410604041.1A CN201410604041A CN105618072B CN 105618072 B CN105618072 B CN 105618072B CN 201410604041 A CN201410604041 A CN 201410604041A CN 105618072 B CN105618072 B CN 105618072B
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Abstract
The invention discloses a kind of preparation method of Hydrodemetalation catalyst, including following content：（1）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 so that the concentration of polyalcohol and/or monose forms ecto-entad in gradient distribution from low to high on carrier；（2）Alumina support after dipping is dried, above-mentioned alumina support is then impregnated using the maceration extract containing active component and urea and humectant is subjected to hydro-thermal process in sealing container；（3）By step（2）Obtained dry materials, then anaerobic high-temperature process, obtains Hydrodemetalation catalyst.Carbon content distribution gradient in catalyst prepared by the inventive method, the easy complete cure of active component, active metal component is evenly distributed in carrier surface, significantly improves the metal removal activity of catalyst.
Description
Technical field
The invention belongs to field of catalyst preparation, more particularly to a kind of preparation method of Hydrodemetalation catalyst.
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 preparation method of Hydrodemetalation catalyst, present invention side
Carbon content distribution gradient in catalyst prepared by method, the easy complete cure of active component, active metal component is in carrier surface
It is evenly distributed, significantly improves the metal removal activity of catalyst.
The preparation method of the Hydrodemetalation 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 dried, then using on the maceration extract dipping containing active component and urea
State alumina support and humectant is subjected to hydro-thermal process in sealing container；
（3）By step（2）Obtained dry materials, then anaerobic high-temperature process, obtains 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）The described maceration extract containing active component and urea be containing group vib and/or
The aqueous solution of group VIII metal element and urea, wherein group vib metallic element are selected from molybdenum and/or tungsten, the choosing of group VIII metal element
One or more from nickel and/or cobalt.Group vib metallic element 5-40g/100ml in terms of oxide, group VIII metal element with
Oxide meter 1-10g/100ml, urea 20-30g/100ml.
In the inventive method, step（2）Described load active component used volume impregnation, incipient impregnation or spray
Impregnating method, dip time is 1-5 hours.Wherein, the soluble compound of active component, such as chlorine are chosen in the preparation of maceration extract
Change nickel, nickel nitrate, nickel sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, phosphomolybdic acid, ammonium molybdate, ammonium metatungstate
With ammonium tungstate etc..
In the inventive method, step（2）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（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.
Polyalcohol and/or the monose aqueous solution spray dip forming alumina support of the inventive method various concentrations, spray
Drench in dipping process, polyalcohol and/or the monose aqueous solution are under the effect of carrier duct capillary force from carrier surface gradually to center
Infiltration, because when multistep, which is sprayed, to be impregnated, the concentration of polyalcohol and/or monose is gradually reduced in maceration extract, it is ensured that polyalcohol and/
Or the concentration of monose is distributed by carrier surface to center in incremental.Dried carrier impregnation contains group vib and/or group VIII metal
The maceration extract of element and urea simultaneously uses two sections of hydro-thermal process, and when low-temperature hydrothermal is handled, polyalcohol and/or monose are met
Reaction forms polymer and is adsorbed onto alumina carrier surface, and polymer, which is carbonized, during High-temperature water heat treatment to form carbon-coating and be adsorbed onto carrier
Surface, because the concentration of polyalcohol and/or monose is distributed by carrier surface to center in incremental, the thickness of carbon-coating is same after charing
From carrier surface to center in incremental distribution, i.e., the relatively thin internal carbon-coating of carbon-coating is thicker outside carrier.Urea occurs while charing
Hydrolysis, the NH of generation3Reacted with the group vib in solution and VIII active component, form corresponding precipitation, precipitation passes through hydrogen bond
Even action is adsorbed onto on carbon-coating.Material after hydro-thermal process is in anaerobic high-temperature process, and the presence of carbon-coating effectively hinders
The strong interaction between metal component and carrier is stopped, because the gradient of carbon layers having thicknesses is distributed, between active metal and carrier
Effect gradually weakens from outside to inside, i.e., catalyst activity is gradually stepped up from outside to inside, during HDM, is promoted and is urged
Reaction inside agent duct, effectively prevent makes demetalization reaction acutely cause because active component activity in outer surface is higher
Catalyst duct is blocked and makes the phenomenon of catalyst inactivation, and the use longevity of catalyst is extended while catalyst activity is improved
Life.
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：It is respectively 1/4R, 1/ at measurement catalyst cross-section center and with catalyst cross-section center distance
Carbon content and active metallic content at 2R, 3/4R and R, wherein R are cross-section center and any point in the outer most edge of cross section
Between line segment distance, then by division calculation, obtain the ratio between each content.
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.
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.Alumina support after dipping is in 110
DEG C dry 8 hours.Then MoO is contained with 150ml310 grams/100ml（Molybdenum source comes from ammonium molybdate）, NiO1.5 grams/100ml（Nickel source is come
From nickel chloride）, 26 grams/100ml of urea maceration extract impregnates above-mentioned carrier 5 hours, filters redundant solution, humectant is transferred into high pressure
In kettle and autoclave is placed in baking oven and be heat-treated 5 hours in 110 DEG C of sealings, then heat to 200 DEG C of sealing heat treatments 8 small
When, naturally cool to room temperature.Alumina support after hydro-thermal process is in dry 6 hours at 120 DEG C.Dried material is in nitrogen
In being calcined 5 hours at 550 DEG C under atmosphere, Hydrodemetalation catalyst C1 of the present invention is made, catalyst property is shown in Table 1.
Embodiment 2
Be the same as Example 1, simply alumina support is clover bar shaped, is with 30ml mass concentrations during spray dipping for the first time
The aqueous solution of 30% sorbierite, with the aqueous solution of the 50ml mass concentrations for 10% sorbierite, the 3rd during second of spray dipping
With the aqueous solution of the 20ml mass concentrations for 5% sorbierite during secondary spray dipping.Activity component impregnation liquid is containing MoO38 grams/
100ml（Molybdenum source comes from ammonium molybdate）, NiO1 grams/100ml（Nickel source comes from nickel chloride）, 22 grams/100ml of urea maceration extract dipping
Above-mentioned carrier.It is heat-treated 6 hours in 130 DEG C of sealings first during hydro-thermal process, then heats to 220 DEG C of sealings and be heat-treated 10 hours
Hydrodemetalation catalyst C2 of the present invention is made, catalyst property 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.Activity component impregnation liquid is containing MoO312 grams/100ml（Molybdenum source comes from ammonium molybdate）, NiO2 grams/
100ml（Nickel source comes from nickel chloride）, 28 grams/100ml of the urea above-mentioned carrier of maceration extract dipping.First 120 during hydro-thermal process
DEG C sealing heat treatment 8 hours, then heat to 240 DEG C sealing heat treatment 6 hours be made Hydrodemetalation catalyst C3 of the present invention,
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 during second of spray dipping.Leaching
The content of urea is 24 grams/100ml in stain liquid, is heat-treated 7 hours, then heats in 140 DEG C of sealings first during hydro-thermal process
Hydrodemetalation catalyst C4 of the present invention is made in 12 hours in 180 DEG C of sealing heat treatments, and 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 it is 1 that xylitol, which changes mass ratio into,:1:1:1 xylose
Alcohol, arabite, the mixing alcohol solution dipping of sorbierite and mannitol.In maceration extract the content of urea be 20 grams/
100ml, is heat-treated 10 hours in 100 DEG C of sealings first during hydro-thermal process, then heats to 250 DEG C of sealing heat treatments and makes for 6 hours
Hydrodemetalation catalyst C5 of the present invention is obtained, catalyst property is shown in Table 1.
Embodiment 6
Be the same as Example 1, simply xylose alcohol solution change the aqueous solution dipping of glucose into, the content of urea is in maceration extract
30 grams/100ml, Hydrodemetalation catalyst C6 of the present invention is made, catalyst 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, simply impregnated the non-hydrothermal treatment of the material after active component, and comparative catalyst C8 is made, urges
Agent property is shown in Table 1.
Comparative example 2
Be the same as Example 1, simply impregnates, system before alumina support dipping active component without polyalcohol and/or monosaccharide solutions
Comparative catalyst C9 is obtained, 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 C10 is made in stain, and catalyst property is shown in Table 1.
Comparative example 4
Be the same as Example 1, does not add urea simply and comparative catalyst C11 is made, catalyst property is shown in Table 1 in maceration extract.
The catalyst property of table 1.
As it can be seen from table 1 the catalysis carbon prepared using the inventive method is in catalyst radial direction distribution gradient, activity gold
Category component is radially evenly distributed in catalyst.
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-C11 prepared by agent C1-C7 and comparative example 1-4 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.
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 (11)
1. a kind of preparation method of Hydrodemetalation catalyst, including following content：（1）Prepare many of at least two various concentrations
First alcohol and/or monose aqueous solution, is sprayed on the alumina support according to the order of concentration from high to low so that polyalcohol and/or
The concentration of monose forms ecto-entad in gradient distribution from low to high on carrier；（2）By the carrying alumina soma after dipping
It is dry, above-mentioned alumina support is then impregnated using the maceration extract containing active component and urea and enters humectant in sealing container
Water-filling is heat-treated；（3）By step（2）Obtained dry materials, then anaerobic high-temperature process, obtains Hydrodemetalation catalyst；
Step（2）The described maceration extract containing active component and urea is the water containing group vib and/or group VIII metal element and urea
Solution, wherein group vib metallic element are selected from molybdenum and/or tungsten, and group VIII metal element is selected from nickel and/or cobalt；Group vib metallic element
The 5-40g/100mL in terms of oxide, group VIII metal element 1-10g/100mL in terms of oxide, urea is 20-30g/100mL；
Step（2）Described hydro-thermal process is two sections of hydro-thermal process, is 100-140 DEG C of hydro-thermal process 5-10 hours in temperature first, so
It it is afterwards 180-250 DEG C in temperature, hydrothermal conditions are 6-12 hours.
2. in accordance with the method for claim 1, it is characterised in that：Step（1）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.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described polyalcohol and/or the monose aqueous solution
Mass concentration is 5% ~ 50%.
4. according to the method described in claim 1 or 3, it is characterised in that：Step（1）The described spray according to concentration from high to low
Leaching order, the concentration difference of adjacent polyalcohol twice and/or the monose aqueous solution is 5% ~ 30%.
5. according to the method described in claim 1 or 3, it is characterised in that：Step（1）Prepare the polyalcohol of 2 ~ 4 kinds of various concentrations
And/or the monose aqueous solution.
6. in accordance with the method for claim 1, 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.
7. in accordance with the method for claim 1, 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.
8. in accordance with the method for claim 1, it is characterised in that：Step（1）Described alumina support is granular product,
Grain shape is spherical or cylindricality.
9. in accordance with the method for claim 1, it is characterised in that：Step（2）Described dipping used volume impregnation, etc. body
Product dipping or spray dipping method, dip time is 1-5 hours.
10. in accordance with the method for claim 1, it is characterised in that：Described drying condition is to be dried at 80-120 DEG C
6-10 hours.
11. in accordance with the method for claim 1, 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.
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| CN110975911B (en) * | 2019-08-22 | 2023-02-28 | 中国石油天然气股份有限公司 | Bulk phase catalyst, preparation method thereof and hydrogenation catalyst comprising bulk phase catalyst |
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| CN101927176B (en) * | 2009-06-26 | 2012-05-30 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase distribution of concentration of active metal and acid additive and preparation method thereof |
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