CN105582949A - Hydrodemetallization catalyst with high activity and preparation method thereof - Google Patents
Hydrodemetallization catalyst with high activity and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrodemetallization catalyst with high activity and a preparation method thereof. The catalyst comprises an aluminum oxide carrier, active metals and carbon. The catalyst comprises the following components based on the weight of the catalyst in percentages by weight: 6.0-15% of Mo and/or W, 1.0-4.0% of Co and/or Ni, wherein the active metals are calculated based on oxides, 1-15% of carbon, preferably 5-10% of carbon, wherein the carbon is calculated based on carbon element; carbon content is gradually reduced from the center to the external surface of a catalyst particle. The preparation method is as follows: aqueous solutions of polyol and/or monosaccharide of at least two different concentrations are prepared; the aqueous solutions are sprayed on the aluminum oxide carrier for dipping according to a sequence from a high concentration to a low concentration; hydro-thermal carbonization treatment is carried out in a sealing container, drying is carried out, active components are used for dipping, drying is carried out, anoxic high-temperature treatment is carried out, and the hydrodemetallization catalyst is carried out. The carbon content in the catalyst is distributed in gradient distribution, complete sulfuration for active components is easy, and demetalization and desulphurization activities of the catalyst are substantially improved.
Description
Technical field
The present invention relates to a kind of high-activity hydrogenation catalyst for demetalation and preparation method thereof.
Background technology
The most common hydrogenation catalyst is generally taking aluminium oxide, silica etc. as carrier at present, the loaded catalyst taking metals such as Co, Ni, Mo, W as active component. Active component adopts the method for dipping or kneading to load on carrier, then makes catalyst through super-dry, roasting. In roasting process, active metal component is easily had an effect and is formed very strong M-O-Al key with alumina support, causes active component form Spinel and lose activity, thereby or makes the active component cannot complete cure reduction catalyst activity.
CN101439289A discloses a kind of preparation method of hydrogenation catalyst. This catalyst metal components is made up of one or both metal ingredients in one or both and Mo, the W that comprise in Co, Ni, taking urea or ammoniacal liquor as reaction promoter, adopt the method for reaction in-situ in carrier hole to make metal active constituent generate nickel molybdate (cobalt) or wolframic acid nickel (cobalt) compounds, thereby can avoid reacting of metal and carrier, make metal active constituent more easily cure simultaneously, can improve the activity of hydrogenation catalyst. But catalyst different activities component interphase interaction prepared by the method has formed new compound, be unfavorable for active component dispersed and active further raising on carrier, in addition, preparation process is more complicated.
CN102451704A discloses a kind of preparation method of hydrocracking catalyst, and this catalyst is taking amorphous aluminum silicide and aluminium oxide as carrier, and group VIII and group vib metal are hydrogenation activity component, preferably contain active material B2O3. Catalyst of the present invention is by after amorphous aluminum silicide and aluminium oxide mixed-forming, drying processing, then infusion process supported active metal, then drying and roasting and obtain. The method is compared with conventional infusion process, and shaping carrier, without roasting, has been simplified preparation process, and reduce the strong interaction between active metal and carrier, be conducive to Active components distribution, be more conducive to the performance of metal active, also avoided the specific area loss causing because of multistep roasting. But because shaping carrier is without calcination process, the mechanical strength of catalyst is undesirable.
Summary of the invention
For existing technical deficiency, the invention provides a kind of high-activity hydrogenation catalyst for demetalation and preparation method thereof, carbon content distribution gradient in catalyst of the present invention, catalyst exterior active component and carrier function are relatively strong, inner active component and carrier function relatively a little less than, the easy complete cure of active component, has significantly improved the demetalization of catalyst and desulphurizing activated.
High-activity hydrogenation catalyst for demetalation of the present invention, comprise alumina support, active metal and carbon, taking catalyst weight as benchmark, active metal is in oxide, and the weight content of Mo and/or W is 6.0wt%-15wt%, and Co and/or Ni weight content are 1.0wt%-4.0wt%, alumina support is 66wt% ~ 92wt%, preferably surplus, carbon is counted 1wt%-15wt% with element, preferably 5wt%-10wt%; Specific surface is 160-270m2/ g, pore volume is 0.8-1.2ml/g; Carbon content meets the following conditions: be 60%-80% apart from the carbon content at catalyst granules cross-section center (hereinafter to be referred as center) 1/4R place and the carbon content of catalyst granules cross-section center ratio, distance center 1/2R place carbon content is 40%-60% with center carbon content ratio, distance center 3/4R place carbon content is 20%-40% with center carbon content ratio, in cross section outer most edge the carbon content of any point with center carbon content than 10%-20%, the distance of line segment between any point in the cross-section center that R is catalyst granules and cross section outer most edge.
The present invention urges by electron probe and measuring apart from the carbon content at any point place in catalyst granules cross-section center 1/4R, 1/2R, 3/4R, cross section outer most edge and the carbon content of catalyst granules cross-section center.
Catalyst of the present invention is that (solid) is granular, instead of the amorphous state such as powder. As the shape of described particle, can enumerate the conventional various shapes that use of this area Hydrodemetalation catalyst, such as can further enumerating spherical and column. As described spherical, such as enumerating spheroidal and elliposoidal etc.; As described column,, flat column cylindric such as enumerating and profiled-cross-section (such as clover, bunge bedstraw herb etc.) column etc.
In the present invention, so-called " cross section of catalyst granules " refers to along the minimum dimension direction of a catalyst granules and cuts the rear whole surface exposing by the geometric center of its shape. Such as, at described catalyst granules while being spherical, described cross section refers to the whole surface (referring to Fig. 1) exposing after by its centre of sphere cutting along the radius of this ball or short-axis direction. Or, in the time that described catalyst granules is column, the whole surface (such as referring to Fig. 2) that described cross section exposes after referring to and cutting by the central point of this length dimension perpendicular to the length dimension direction of this post.
In the present invention, the periphery of described exposed surface is called to the outer most edge of this cross section, described geometric center (such as the central point of the aforesaid centre of sphere or length dimension) is called to the central point on this cross section.
The preparation method of high-activity hydrogenation catalyst for demetalation of the present invention, comprises following content:
(1) polyalcohol and/or the monose aqueous solution of at least two kinds of variable concentrations of preparation, spray on alumina support according to concentration order from high to low, makes the concentration of polyalcohol and/or monose on carrier, form the gradient that ecto-entad is from low to high and distribute;
(2) alumina support after dipping is carried out to hydro-thermal charing processing in airtight container, dry processing;
(3) alumina support obtaining by active metal maceration extract impregnation steps (2), dry, then anaerobic high-temperature process, obtains Hydrodemetalation catalyst.
In the inventive method, the described polyalcohol of step (1) comprises one or more in xylitol, sorbierite, sweet mellow wine or arabite etc.; Described monose comprises one or more in glucose, ribose or fructose etc.
In the inventive method, the polyalcohol that step (1) is described and/or the mass concentration of the monose aqueous solution are 5% ~ 50%.
In the inventive method, step (1) described according to concentration from high to low spray order, the concentration difference of adjacent twice polyalcohol and/or the monose aqueous solution is 5% ~ 30%, preferably 10% ~ 20%; Preferably polyalcohol and/or the monose aqueous solution of 2 ~ 4 kinds of variable concentrations of preparation.
In the inventive method, the described maceration extract consumption at every turn spraying of step (1) is the 10%-60% of alumina support saturated water adsorptive value, preferably 20%-30%, the saturated water adsorptive value that the total consumption of maceration extract repeatedly spraying is alumina support is to guarantee the saturated dipping of alumina support.
In the inventive method, polyalcohol and/or the monose aqueous solution that step (1) is preferably prepared 3 kinds of variable concentrations spray, detailed process is as follows: spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, and the consumption of polyalcohol and/or the monose aqueous solution is the 20%-30% of alumina support water absorption; Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, and the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of alumina support water absorption; Spray for the third time, the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, and the consumption of polyalcohol and/or the monose aqueous solution is the 10%-40% of alumina support water absorption.
In the inventive method, the described alumina support of step (1) is graininess, can be spherical or cylindricality wherein spherical can be spheroidal or elliposoidal, cylindricality can be cylindrical, square column type or abnormity (clover, bunge bedstraw herb or five tooth balls). Alumina support can adopt commercially available, the aluminium oxide that is suitable for Hydrodemetalation catalyst carrier that also can adopt conventional method to make. In described alumina support, also can add as required one or more in the auxiliary elements such as Si, Ti, Zr, B or F.
In the inventive method, the described hydro-thermal charing treatment temperature of step (2) is 180-250 DEG C, preferably 200-230 DEG C, the hydrothermal treatment consists time is 6-12 hour, preferably 8-10 hour, hydrothermal treatment consists pressure is self-generated pressure, can ensure polyalcohol and/or the complete charing of monose under this hydro-thermal carbonization condition. Wherein, self-generated pressure is relevant with treatment temperature, when temperature is 100 DEG C, and the general 0.1MPa of force value (gauge pressure), 150 DEG C time, force value is generally 0.43MPa, and 250 DEG C time, force value is generally 1.95MPa.
In the inventive method, the described alumina support of step (2) preferably, before charing is processed, seals heat treatment, and heat-treat condition is: process 0.5 ~ 2 hour for 80 ~ 130 DEG C.
In the inventive method, the described load active component of step (3) adopted volume dipping, incipient impregnation or spray impregnating method, and dip time is 1-5 hour, the preferred volume dipping of crossing. Wherein, the soluble compound of active component is chosen in the preparation of maceration extract, as nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, phosphomolybdic acid, ammonium molybdate, ammonium metatungstate and ammonium tungstate etc., in maceration extract, the concentration of active component is counted with corresponding oxide content: MoO3And/or WO310 ~ 80g/100ml, NiO and/or CoO2 ~ 20g/100ml, the concrete concentration of maceration extract can be determined according to the active metallic content on final catalyst.
In the inventive method, described drying condition is dry 6-10 hour at 80-120 DEG C.
In the inventive method, the described anaerobic high-temperature process condition of step (3) is: treatment temperature is 400-600 DEG C, and the processing time is 3-6 hour; Wherein the atmosphere of anaerobic high-temperature process can be nitrogen or inert atmosphere, and wherein inert atmosphere is one or more in helium, neon or argon gas.
Catalyst of the present invention is applied to HDM reaction, and general process conditions are: 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.
Polyalcohol and/or the monose aqueous solution spray dip forming alumina support of variable concentrations for the inventive method then, by hydro-thermal charing processing, form carbon-coating on carrier surface and duct inwall, in spray dipping process, maceration extract under the capillary force effect of carrier duct by carrier surface gradually to central permeate, during due to multistep spray dipping, in maceration extract, the concentration of polyalcohol and/or monose reduces gradually, has ensured that the concentration of polyalcohol and/or monose is and is increased progressively distribution by carrier surface to center. after charing, the thickness of carbon-coating is and increases progressively distribution from carrier surface to center, and the thinner inner carbon-coating of the outside carbon-coating of carrier is thicker. before the charing of carbon precursor, the carrier after dipping is sealed to heat treatment, promoted the absorption of carbon precursor on carrier and the formation of carbon-coating, material after dipping active component is in anaerobic high-temperature process, the existence of carbon-coating has effectively stoped the strong interaction between metal component and carrier, because the gradient of carbon-coating thickness distributes, between active metal and carrier, effect weakens from outside to inside gradually, be that catalyst activity improves from outside to inside gradually, in HDM process, promote the reaction of inside, catalyst duct, effectively avoid because outer surface active component activity makes demetalization reaction acutely cause catalyst duct to stop up the phenomenon that makes catalysqt deactivation compared with high, in improving catalyst activity, extend the service life of catalyst.
Brief description of the drawings
Fig. 1 catalyst granules is spherical cross sectional representation.
Fig. 2 catalyst granules is columniform cross sectional representation.
Detailed description of the invention
Further illustrate the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples. The commercially available formed alumina carrier adopting in embodiment, the pore volume of alumina support is 0.8-1.5ml/g, specific area is 160-300m2/ g, the hole that bore dia is 10-20nm accounts for the 70%-90% of total pore volume, and crushing strength is 130-160N/cm, water absorption 1g/g.
In catalyst of the present invention, carbon and active metallic content are measured by NEC's JXA-8230 electron probe, and the accelerating potential of selecting when mensuration is 15KV, and probe current is 8 × 10-8A, beam spot size is 3 μ m.
Metering system: carbon content and the active metallic content measuring respectively catalyst cross-section center place and be 1/4R, 1/2R, 3/4R and R place with catalyst cross-section center place distance, wherein R is the distance of line segment between any point in cross-section center and cross section outer most edge, then by division calculation, obtain the ratio between each content.
Embodiment 1
Taking pore volume is 0.9ml/g, and specific area is 220m2100 grams of the γ phase cylinder bar shaped alumina supports of/g are put into spray and are rolled pot, under rotary state, taking atomizing type to rolling carrier spray impregnating effect concentration in the pot xylitol aqueous solution 25ml as 40%; Then the xylitol aqueous solution 40ml that is 20% by mass concentration continues spray oxide impregnation alumina supporter; The xylitol aqueous solution 40ml that is finally 10% by mass concentration continues spray oxide impregnation alumina supporter. Dipping finishes alumina support to proceed in autoclave and autoclave is placed in to baking oven in 80 DEG C of sealing heat treatments 120 minutes, is then warming up to charing under 180 DEG C, self-generated pressure and processes 9 hours, naturally cools to room temperature. Alumina support after hydrothermal treatment consists is dried 3 hours at 120 DEG C. Within dried year, contain MoO with 150ml315 grams (molybdenum source is from ammonium molybdate), the maceration extract of NiO2 gram (nickel source is from nickel chloride) floods above-mentioned carrier 3 hours, filter redundant solution, at 110 DEG C, be dried 8 hours, dried material is roasting 5 hours at 550 DEG C under nitrogen atmosphere, make Hydrodemetalation catalyst C1 of the present invention, catalyst property is in table 1.
Embodiment 2
With embodiment 1, the aqueous solution of the sorbierite that is 30% by 30ml mass concentration when just spray floods for the first time, the aqueous solution of the sorbierite that is 10% by 50ml mass concentration when spray floods for the second time, the aqueous solution of the sorbierite that is 5% by 20ml mass concentration when spray floods for the third time, heat treatment temperature is 130 DEG C, and heat treatment time is 60 minutes. When charing is processed, temperature is 200 DEG C, and carbonization time is 8 hours. In activity component impregnation process, contain MoO with 150ml310.5 grams (molybdenum source is from ammonium molybdate), NiO2 gram of (nickel source is from nickel nitrate) maceration extract dipping. Make Hydrodemetalation catalyst C2 of the present invention, catalyst property is in table 1.
Embodiment 3
With embodiment 1, just adopt spray dipping four times, the aqueous solution of the sweet mellow wine that is 50% by 20ml mass concentration when spray floods for the first time, the aqueous solution of the sorbierite that is 30% by 40ml mass concentration when spray floods for the second time, the aqueous solution of the sorbierite that is 20% by 20ml mass concentration when spray floods for the third time, the aqueous solution of the sorbierite that is 10% by 20ml mass concentration when the 4th spray dipping, heat treatment temperature is 100 DEG C, heat treatment time is 90 minutes. When charing is processed, temperature is 240 DEG C, and carbonization time is 12 hours. In activity component impregnation process, contain MoO with 150ml311.5 grams (molybdenum source is from ammonium molybdate), NiO2.5 gram of (nickel source is from basic nickel carbonate) maceration extract dipping. Make Hydrodemetalation catalyst C3 of the present invention, catalyst property is in table 1.
Embodiment 4
With embodiment 1, just adopt spray dipping twice, the aqueous solution of the arabite that is 40% by 50ml mass concentration when spray floods for the first time, the aqueous solution of the arabite that is 20% by 55ml mass concentration when spray floods for the second time, carbonization temperature is 250 DEG C, and carbonization time is 6 hours. Make Hydrodemetalation catalyst C4 of the present invention, catalyst property is in table 1.
Embodiment 5
With embodiment 1, just xylitol changes the mixed alcohol aqueous solution dipping of xylitol, arabite, sorbierite and sweet mellow wine that mass ratio is 1:1:1:1 into, and when charing is processed, temperature is 220 DEG C, and the processing time is 10 hours. Make Hydrodemetalation catalyst C5 of the present invention, catalyst property is in table 1.
Embodiment 6
With embodiment 1, just the xylitol aqueous solution changes the aqueous solution dipping of glucose into, and when charing is processed, temperature is 230 DEG C, and the processing time is 9 hours. Make Hydrodemetalation catalyst C6 of the present invention, catalyst property is in table 1.
Embodiment 7
With embodiment 1, just the xylitol aqueous solution changes ribose aqueous solution dipping into, and when charing is processed, temperature is 190 DEG C, and the processing time is 6 hours. Make Hydrodemetalation catalyst C7 of the present invention, catalyst property is in table 1.
Embodiment 8
With embodiment 1, just xylitol changes glucose, the fructose that mass ratio is 1:1:1:1 into, the aqueous solution dipping of xylitol and sorbierite, and when charing is processed, temperature is 240 DEG C, the processing time is 9 hours. Make Hydrodemetalation catalyst C8 of the present invention, this catalyst MoO3Weight content is 7.9wt%, and NiO weight content is 1.2wt%, and carbon is counted 8.2wt% with element, and surplus is alumina support; Specific surface is 207m2/ g, pore volume is 0.95ml/g.
Comparative example 1
With embodiment 1, just before alumina support dipping active component, flood and hydrothermal treatment consists without alcohol and/or sugar juice, make comparative catalyst C9, catalyst property is in table 1.
Comparative example 2
With embodiment 1, just alumina support dipping active component is front carries out hydrothermal treatment consists without polyalcohol and/or monose solution impregnation with deionized water dipping and in autoclave, makes comparative catalyst C10, and catalyst property is in table 1.
Comparative example 3
With embodiment 1, while just dipping, the xylitol aqueous solution of same volume and mass concentration is once sprayed to dipping and make comparative catalyst C11, catalyst property is in table 1.
Table 1 catalyst property.
Embodiment 9
The following examples illustrate Hydrodemetalation catalyst provided by the invention and comparative catalyst's catalytic performance.
Taking the listed decompression residuum of table 2 as raw material, the catalytic performance of catalyst C9-C11 prepared by the catalyst C1-C8 that on the hydrogenation reaction device of 200 milliliters prepared by evaluation example 1-8 and comparative example 1-3, the bar that catalyst is long 2 ~ 3 millimeters, catalyst loading amount is 100 milliliters, reaction temperature is 390 DEG C, hydrogen dividing potential drop is 15MPa, and liquid hourly space velocity (LHSV) is 1.0 hours-1, hydrogen to oil volume ratio is 900, reacts after 200 hours and measures the content that generates each impurity in oil, calculates removal efficiency, evaluation result is in table 3.
Table 2 feedstock oil character.
Table 3 catalyst hydrogenation performance comparison.
| 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 |
Can be found out by table 3 data, compared with comparative catalyst, catalyst provided by the invention has higher HDM activity and hydrodesulfurization activity.
Above-described embodiment and the prepared catalyst of comparative example are carried out to activity rating, and the temperature rise of operation 5000h is in table 3.
Table 4 reaction temperature lift-off value.
Find out from the result of table 4, react after 5000 hours, adopt Hydrodemetalation catalyst provided by the invention, in order to keep high demetallization per, desired reaction temperature increase rate is far smaller than comparative catalyst, and this illustrates that Hydrodemetalation catalyst provided by the invention has higher activity stability.
Claims (16)
1. a high-activity hydrogenation catalyst for demetalation, comprise alumina support, active metal and carbon, it is characterized in that: taking catalyst weight as benchmark, active metal is in oxide, the weight content of Mo and/or W is 6.0wt%-15wt%, Co and/or Ni weight content are 1.0wt%-4.0wt%, and alumina support is 66wt% ~ 92wt%, and carbon is counted 1wt%-15wt% with element; Carbon content meets the following conditions: be 60%-80% apart from the carbon content at catalyst granules cross-section center 1/4R place and the carbon content of catalyst granules cross-section center ratio, distance center 1/2R place carbon content is 40%-60% with center carbon content ratio, distance center 3/4R place carbon content is 20%-40% with center carbon content ratio, in cross section outer most edge, the carbon content of any point is 10%-20% with center carbon content ratio, the distance of line segment between any point in the cross-section center that R is catalyst granules and cross section outer most edge.
2. according to catalyst claimed in claim 1, it is characterized in that: the specific 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 claim 1 or 2, it is characterized in that comprising following content: polyalcohol and/or the monose aqueous solution of at least two kinds of variable concentrations of (1) preparation, spray on alumina support according to concentration order from high to low, make the concentration of polyalcohol and/or monose on carrier, form the gradient that ecto-entad is from low to high and distribute; (2) alumina support after dipping is carried out to hydro-thermal charing processing in airtight container, dry processing; (3) alumina support obtaining by active metal maceration extract impregnation steps (2), dry, then anaerobic high-temperature process, obtains Hydrodemetalation catalyst.
4. it is characterized in that in accordance with the method for claim 3: the described polyalcohol of step (1) comprises one or more in xylitol, sorbierite, sweet mellow wine or arabite; Described monose comprises one or more in glucose, ribose or fructose etc.
5. it is characterized in that in accordance with the method for claim 3: the polyalcohol that step (1) is described and/or the mass concentration of the monose aqueous solution are 5% ~ 50%.
6. in accordance with the method for claim 3, it is characterized in that: step (1) described according to concentration from high to low spray order, the concentration difference of adjacent twice polyalcohol and/or the monose aqueous solution is 5% ~ 30%.
7. in accordance with the method for claim 3, it is characterized in that: step (1) described according to concentration from high to low spray order, the concentration difference of adjacent twice polyalcohol and/or the monose aqueous solution is 10% ~ 20%.
8. it is characterized in that in accordance with the method for claim 3: polyalcohol and/or the monose aqueous solution of 2 ~ 4 kinds of variable concentrations of preparation in step (1).
9. in accordance with the method for claim 3, it is characterized in that: the described maceration extract consumption at every turn spraying of step (1) is the 10%-60% of alumina support saturated water adsorptive value, the saturated water adsorptive value that the total consumption of maceration extract repeatedly spraying is alumina support.
10. in accordance with the method for claim 3, it is characterized in that: polyalcohol and/or the monose aqueous solution of 3 kinds of variable concentrations of step (1) preparation spray, detailed process is as follows: spray for the first time, the mass concentration of polyalcohol and/or the monose aqueous solution is 30%-50%, and the consumption of polyalcohol and/or the monose aqueous solution is the 20%-30% of alumina support water absorption; Spray for the second time, the mass concentration of polyalcohol and/or the monose aqueous solution is 10%-30%, and the consumption of polyalcohol and/or the monose aqueous solution is the 40%-60% of alumina support water absorption; Spray for the third time, the mass concentration of polyalcohol and/or the monose aqueous solution is 5%-10%, and the consumption of polyalcohol and/or the monose aqueous solution is the 10%-40% of alumina support water absorption.
11. in accordance with the method for claim 3, it is characterized in that: the described hydro-thermal charing treatment temperature of step (2) is 180-250 DEG C, and the hydrothermal treatment consists time is 6-12 hour, and hydrothermal treatment consists pressure is self-generated pressure.
12. in accordance with the method for claim 3, it is characterized in that: the alumina support described in step (2), before charing is processed, seals heat treatment, and heat-treat condition is: process 0.5 ~ 2 hour for 80 ~ 130 DEG C.
13. in accordance with the method for claim 3, it is characterized in that: the described load active component of step (3) adopted one or more in volume dipping, incipient impregnation or spray dipping, and dip time is 1-5 hour; In maceration extract, the concentration of active component is counted with corresponding oxide content: MoO3And/or WO310 ~ 80g/100ml, NiO and/or CoO2 ~ 20g/100ml.
14. in accordance with the method for claim 3, it is characterized in that: described drying condition is dry 6-10 hour at 80-120 DEG C.
15. in accordance with the method for claim 3, it is characterized in that: the described anaerobic high-temperature process condition of step (3) is: treatment temperature is 400-600 DEG C, and the processing time is 3-6 hour; Wherein the atmosphere of anaerobic high-temperature process is nitrogen or inert atmosphere, and wherein inert atmosphere is one or more in helium, neon or argon gas.
Catalyst described in 16. 1 kinds of claims 1 or 2 is applied to HDM reaction, it is characterized in that: process conditions are: 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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| CN103785400A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of high-activity hydrodemetalization catalyst for residuum |
| US20140221706A1 (en) * | 2013-02-05 | 2014-08-07 | Korea Institute Of Science And Technology | Method for synthesis of molybdenum carbide catalyst for hydrodeoxygenation |
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| CN105618069A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | High-activity flue gas desulfurization catalyst and preparation method thereof |
| CN105618069B (en) * | 2014-11-03 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of high activity desulfurization catalyst of flue gas and preparation method thereof |
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