CN103801312B - A kind of preparation method of hydrotreating catalyst - Google Patents
A kind of preparation method of hydrotreating catalyst Download PDFInfo
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- CN103801312B CN103801312B CN201210443029.8A CN201210443029A CN103801312B CN 103801312 B CN103801312 B CN 103801312B CN 201210443029 A CN201210443029 A CN 201210443029A CN 103801312 B CN103801312 B CN 103801312B
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Abstract
The preparation method that the invention discloses a kind of hydrotreating catalyst.The method includes: at the alkaline solution containing aluminum and the acid solution containing aluminum and flow the process of plastic, simultaneously and flow addition additive and organic formwork agent, control suitable reaction condition and carry out plastic, it is subsequently adding alkaline solution and regulates pH value, then through filtration, washing, obtain alumina dry glue after drying, then through molding, dry and roasting obtains alumina support, then supported active metals component.The specific surface area of catalyst of the method gained is big, pore volume is big, pore structure is reasonable, is particularly well-suited to residuum hydrodesulfurization or hydrogenation conversion catalyst.
Description
Technical field
The preparation method that the present invention relates to a kind of hydrotreating catalyst, is particularly suited for the preparation method processing the hydrotreating catalyst of poor residuum.
Background technology
Along with aggravation and market being continuously increased high-quality light-weight fuel oil demand of crude oil in poor quality trend, light materialization of heavy oil and to clean process day by day notable to the economic benefit increasing refinery.Hydrotreating techniques, as improving one of inferior heavy oil quality the most effective technical scheme providing high-quality raw oil for downstream unit, currently receives significant attention.
Residual oil (reduced crude, decompression residuum) is crude oil time processing (often, decompression distillation) remaining most important part afterwards.With light ends oil phase ratio, residual oil composition complexity, mean molecule quantity is big, and viscosity is high, and density is big, and hydrogen-carbon ratio is low, and carbon residue is high, and most of sulfur in crude oil, nitrogen, carbon residue and metal impurities are enriched in residual oil.The These characteristics of residual oil requires that the duct of catalyst for hydrotreatment of residual oil is suitable for the diffusion of reactant macromole.Current most widely used hydrotreating catalyst is generally loaded catalyst, and its carrier is generally aluminium oxide and by its derivative complex carrier, such as TiO2-Al2O3、SiO2-Al2O3Deng, or in alumina support, add some auxiliary agents be modified, such as phosphorus, boron, fluorine etc..Some auxiliary agent also can add in the process of active metal solution impregnation.Aluminium oxide is as one of the most frequently used raw material of industry, at field important roles such as catalyst, pottery, refractory materials.Owing to aluminium oxide has good mechanical strength, heat stability, can the Acidity of modulation and pore structure, be therefore widely used in catalytic field as catalyst carrier.The attention of hydrogen addition technology is made catalyst market that the demand of hydrogenation catalyst be continuously increased by the current world.Along with people's further investigation to hydrogenation catalyst, the importance of the carrier property of catalyst be there has also been new understanding, the pore structure (specific surface area, pore volume and pore-size distribution) of carrier not only dispersion important to active component, and it is directly connected to the diffusion in course of reaction and mass transfer, pore size and pass can affect the inner diffusing rate of reactant, product, thus affecting the activity and selectivity of catalyst.Therefore, for the activity of catalyst, selectivity, service life, mechanical strength and regeneration capacity important.Aluminium hydroxide is the important presoma preparing aluminium oxide, and the crystalline phase of aluminium oxide, surface acid property etc. are had certain decisive action by its pore structure.Therefore, excellent and affordable the catalyst carrier for hydrgenating of processability has important practical significance for exploitation high-performance hydrotreating catalyst.
γ-A12O3Duct be mainly made up of several parts, including interlayer hole (intragranular hole), intergranular pore (mesopore), offspring hole and poly particle hole.Wherein intergranular pore is to provide the most important hole of catalyst pore volume, aperture and specific surface area, the factor such as its form depending mainly on the size of the size of boehmite primary particle, shape and accumulation mode and offspring.And offspring hole and poly particle hole are bigger for the duct contribution of hundred nano-scale.There is substantial connection in the preparation condition of these factors and boehmite (such as reaction and aging temperature, pH value, mixing speed, the time of staying and washing and drying condition).The primary particle of boehmite particle and the form of offspring and accumulation mode etc. greatly affect the pore structure of aluminium oxide prepared therefrom as can be seen here.
The preparation method that CN1257754A discloses a kind of catalyst carrier, wherein adopts waterglass and aluminum sulfate to prepare sial dry glue, and the carrier pore volume of preparation is 0.45 ~ 0.75mL/g, and average pore size is 5 ~ 10nm.This one-tenth gluing method prepare containing silicon carrier, aperture is less, be not suitable for be used as heavy oil or catalyst for hydrotreatment of residual oil.
CN102039195A discloses a kind of carrying alumina preparation.The method is to adopt carbonizatin method to add organic expanding agent and defoamer when preparing alumina dry glue.Although the alumina support that the method provides can reach 12 ~ 13nm in several apertures, but its pore volume and specific surface area are all relatively low.When this carrier is for catalyst for hydroprocessing of heavy oil, it is impossible to more chain carrier is provided.
The preparation method that CN102309998A discloses a kind of catalyst for hydroprocessing of heavy oil carrier.The method is to adopt pH value swing method to carry out plastic at a lower temperature, more at high temperature aging a period of time.Although this one-tenth gluing method can prepare the alumina support with larger aperture, but it is less less than the pore size distribution within the scope of 15nm.After preparing into catalyst using this aluminium oxide as catalyst for hydroprocessing of heavy oil carrier, its pore structure is likely to demetalization reaction favourable, but is unfavorable for desulfurization and hydroconversion reactions.
CN1768948A discloses a kind of preparation method suitable in Hydrodemetalation catalyst carrier, wherein with sodium metaaluminate and aluminum sulfate solution for raw material, adopts cocurrent cooling operation to prepare alumina support.Although alumina support average pore size prepared by this one-tenth gluing method is big, but specific surface area is little, is unfavorable for mink cell focus hydrodesulfurization and hydroconversion reactions using it as catalyst carrier.
Summary of the invention
For the deficiencies in the prior art, the preparation method that the invention provides a kind of hydrotreating catalyst.Catalyst prepared by the inventive method, has that pore volume is big, specific surface area is moderate, reasonable pore distribution and a suitable feature of surface acid property, is particularly suitable for mink cell focus hydroprocessing processes, especially residuum hydrodesulfurization and carbon residue conversion process.
The preparation method of hydrotreating catalyst of the present invention, including:
(1) at the alkaline solution containing aluminum and the acid solution containing aluminum and flow the process of plastic, simultaneously and flow addition additive and organic formwork agent, regulating pH value is 6.0 ~ 8.0, and reaction temperature is 50 ~ 100 DEG C, and the response time is 30 ~ 120min；Described additive is carbon number is the alcohols of 2 ~ 4, and addition accounts for the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight；Described organic formwork agent is cellulose ether compounds, and addition is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight；
(2) adding alkaline solution in the product of step (1) gained, regulating pH value is 7.5 ~ 10.0, and reaction temperature is 60 DEG C ~ 100 DEG C, and the response time is 30 ~ 120min；
(3) being filtered by the serosity of step (2) gained, filter cake is scrubbed, obtains alumina dry glue after drying；
(4) by the alumina dry gum forming of step (3) gained, through super-dry, roasting, catalyst carrier is obtained,
(5) impregnation method is adopted hydrogenation active metals component to be incorporated in the catalyst carrier of step (3) gained, drying, roasting, obtain hydrotreating catalyst.
In the inventive method, step (2) gained serosity is through Aging Step, described aging referring to makes solution keep the regular hour under stirring or resting state, aging temperature is 60 ~ 100 DEG C, preferably 80 ~ 95 DEG C, more preferably 85 ~ 90 DEG C, ageing time is 10 ~ 120min, preferably 15 ~ 60min, more preferably 20 ~ 40min.
In step (1), the alkaline solution containing aluminum, the acid solution containing aluminum, additive and template carry out and flow plastic reaction, regulate pH value and are preferably 6.5 ~ 8.0, control gelling temperature at least 50 DEG C, preferably 50 ~ 95 DEG C, the response time is preferably 40 ~ 100min, more preferably 60 ~ 80min.Wherein, additive and organic formwork agent can be added separately to, it is also possible to add after both being mixed, it is also possible to both be added in the alkaline solution containing aluminum or the acid solution containing aluminum and add, it is preferable that add after additive and organic formwork agent being mixed；Additive and organic formwork agent are added separately to or add fashionable after both mixing, it is desirable to adding in form of an aqueous solutions, in aqueous solution, the concentration of additive is 0.5 ~ 60g/L, and the concentration of organic formwork agent is 0.5 ~ 60g/L.The described acid solution containing aluminum, it is preferable that the solution of one or more of aluminum sulfate, aluminum nitrate, aluminum chloride etc., is more highly preferred to aluminum sulfate solution.The concentration of the acid solution containing aluminum is 20 ~ 80gAl2O3/L.The described alkaline solution containing aluminum, it is preferable that the solution of sodium metaaluminate, potassium metaaluminate or their mixture, is more highly preferred to sodium aluminate solution.The concentration of the alkaline solution containing aluminum is 100 ~ 200gAl2O3/L.Described additive is one or more in hydroxyl small molecule alcohol such as ethanol, isopropanol, propanol, propylene glycol, it is preferable that ethanol and isopropanol.Described template is cellulose ether compounds, including one or more in methylcellulose (MC), ethyl cellulose (EC), hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), ethylmethylcellulose (EMC), hydroxyethylmethyl-cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), carboxymethyl hydroxymethyl cellulose (CMHMC), it is preferable that methylcellulose and hydroxypropyl methyl cellulose.
In step (2), described alkaline solution is one or more the solution in sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate, potassium hydroxide, ammonia, it is preferable that sodium carbonate liquor.It is 7.5 ~ 10.0 that step (2) regulates pH value, and reaction temperature is 60 DEG C ~ 100 DEG C, pH value preferably 8.0 ~ 9.0, more preferably 8.2 ~ 8.8, reaction temperature preferably 70 ~ 95 DEG C, more preferably 80 ~ 90 DEG C, response time is 30 ~ 120min, it is preferable that 50 ~ 90min, more preferably 60 ~ 80min.
In step (3), described washing is generally adopted deionized water wash to neutral, described drying condition: 100 ~ 150 DEG C dry 2 ~ 6 hours, it is preferable that 110 ~ 130 DEG C, dry 4 ~ 6 hours.
In the inventive method, in carrier preparation process, shaping assistant and expanding agent etc. can be added as required.Described shaping assistant can be peptization acid, extrusion aid, binding agent etc..Described expanding agent is one or more of white carbon black, ammonium phosphate, ammonium carbonate, Polyethylene Glycol, polyvinyl alcohol, methylcellulose, polyacrylamide etc..The addition of described expanding agent accounts for the 2% ~ 10% of raw mixture weight.
In the inventive method, the drying condition of step (4) is dry 2 ~ 20 hours at 80 DEG C ~ 200 DEG C, and roasting condition is roasting 1 ~ 8 hour at 450 DEG C ~ 1000 DEG C.Described molding can adopt existing conventional method, such as extrusion molding or rolling ball method etc..
In the hydrotreating catalyst of the present invention, the hydrogenation active metals of employing includes group VIII and vib metal, and group viii metal is generally Ni or/and Co, and vib metal is W or/and Mo.With the weight of catalyst for benchmark, group viii metal is calculated as 0.5wt% ~ 9.0wt% with oxide, and vib metal is calculated as 10.0wt% ~ 30.0wt% with oxide.In the inventive method, infusion process is adopted to be introduced in catalyst by hydrogenation metal component.Described dipping can adopt conventional impregnation methods, it is desirable to adopts saturated infusion process.Dipping solution adopts conventional method preparation.After impregnated activated metal component, drying and roasting, obtain hydrotreating catalyst.Wherein baking temperature is room temperature～120 DEG C, drying time 0.5～24h, sintering temperature 400～550 DEG C, roasting time 1 ~ 6h.
Hydrotreating catalyst character prepared by the inventive method is as follows: pore volume is 0.45 ~ 0.75mL/g, specific surface 120 ~ 280m2/ g, pore size distribution is as follows: the pore volume in the hole of bore dia < 6nm accounts for < the 20% of total pore volume, the pore volume that bore dia is the hole of 6 ~ 15nm accounts for the 35% ~ 55% of total pore volume, the pore volume in the hole of bore dia > 15nm accounts for more than the 25% of total pore volume, being generally 25% ~ 40%, the pore volume in the hole of its median pore diameter > 100nm accounts for the 5% ~ 20% of total pore volume；Meleic acid amount 0.250 ~ 0.550mmol/g.
Hydrotreating catalyst of the present invention can include suitable auxiliaries, one or more in P, B, F, Ti, Zr etc..Auxiliary agent can add in plastic or carrier preparation process, it is also possible to adds when impregnated activated metal component.
Catalyst prepared by the inventive method may be used for the processes such as the hydrodesulfurization of heavy oil, hydrodenitrogeneration, hydro-conversion.Operating condition is generally: reaction pressure is 5 ~ 25MPa, and temperature is 300 ~ 500 DEG C, and during liquid, volume space velocity is 0.1 ~ 5.0h-1, hydrogen to oil volume ratio is 100 ~ 5000.
In the inventive method, when preparing catalyst carrier, under the cooperating of low molecule alcohols and organic formwork agent, boehmite crystal grain in reaction system is mainly grown along a certain fixed-direction in further growth process, and radial growth is very slow, therefore the grain formation particle shape with certain draw ratio of boehmite can be promoted, such as bar-shaped or chain pattern, make the connectivity in duct formed good, be conducive to the diffusion of reactant, and improving the utilization rate in duct, deposit is not easy in duct to deposit, extend the service life of catalyst.The inventive method is by effectively controlling the growth course of boehmite crystal grain, and the alumina grain size, the accumulation mode that obtain are uniform.The catalyst thus prepared has the feature of big pore volume, high-ratio surface and reasonable pore distribution, thus being conducive to macromolecular reaction thing diffusion in catalyst duct in mink cell focus or residual oil, be conducive to again the carrying out of macromolecular reaction thing removing impurities matter especially desulfurization and denitrification reaction.Therefore, the catalyst that prepared by the inventive method, it is not necessary to the extra expanding agent that adds just can meet Production requirement.
Catalyst prepared by the inventive method is suitable for heavy oil or residuum hydrodesulfurization or hydrogenation conversion catalyst, reacts performance in the mink cell focus hydrogenation process of severity at height more stable.
The inventive method technical process is simple, it does not have the discharge of pollutant, non-environmental-pollution, cost is low.
Central hole structure of the present invention and specific surface area adopt mercury injection method analysis.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that embodiment 1 prepares aluminium oxide；
Fig. 2 is the scanning electron microscope (SEM) photograph that comparative example 1 prepares aluminium oxide.
Detailed description of the invention
It is addressed further under the technical characteristic of the present invention by the examples below, but is not limited to embodiment.Wt% is mass fraction.
Embodiment 1
(1) prepared by alumina dry glue
Preparation sodium aluminate solution concentration is 140gAl2O3/ L, amounts to 2.5L；Aluminum sulfate solution concentration is 40gAl2O3/ L amounts to 5.0L；In ethanol with hydroxypropyl methyl cellulose (HPMC) mixed solution, concentration of alcohol is 1.0g/L, HPMC concentration is 1.0g/L, amounts to 1.0L.
Retort is added bottom water in advance, retort temperature is arranged 75 DEG C, open stirring.According to certain flow rate and flowing in addition retort process by the sodium aluminate solution prepared and aluminum sulfate solution, simultaneously and flow addition ethanol and hydroxypropyl methyl cellulose (HPMC) mixed solution, regulating pH value is 6.5.After material adds, adding alkaline solution in the product of gained, regulating pH value is 8.8, and reaction temperature is 90 DEG C, and the response time is 30min.Reaction enters the ageing step after terminating, and reaction temperature is 90 DEG C, and ageing time is 20min.Being filtered by the serosity of gained, filter cake is scrubbed, obtains alumina dry glue after drying.650 DEG C of roastings obtain aluminium oxide in 3 hours.
(2) catalyst preparing
Weigh alumina dry glue 1000g prepared by step (1), add 25g sesbania powder mix homogeneously, dissolve 26g nitric acid (67wt%) with the dilution of 900g deionized water and join in mixture, kneading extruded moulding, dry 2h at 120 DEG C, at 700 DEG C, roasting 3h obtains A-1 carrier.
Weigh A-1 carrier 100g.Weigh molybdenum oxide 20.5g, basic nickel carbonate 7.0g, phosphoric acid 5.6g, constant volume 85mL after adding deionized water dissolving and being cooled to room temperature, obtain dipping solution.Adopt spray mode to be immersed on carrier A-1 by above-mentioned impregnation liquid, dry 2 hours at 120 DEG C after at room temperature placing 2.0 hours, finally 3 hours prepared catalyst AC-1 of roasting at 450 DEG C.
Embodiment 2
Other condition, with embodiment 1, simply replaces with isopropanol ethanol, and the isopropyl alcohol concentration of preparation changes 35g/L, HPMC into and replaces with MC, and the MC concentration of preparation changes 20g/L into, prepares A-2 carrier and catalyst AC-2.
Embodiment 3
Other condition is with embodiment 1, and simply concentration of alcohol is changed into 55g/L, HPMC concentration changes 50g/L into, prepares A-3 carrier and catalyst AC-3.
Embodiment 4
Other condition, with embodiment 1, is simply set to 80 DEG C retort temperature, prepares A-4 carrier and catalyst AC-4.
Embodiment 5
Other condition is with embodiment 1, and simply ageing time is set as 40min, prepares A-5 carrier and catalyst AC-5.
Embodiment 6
Other condition is with embodiment 1, and simply the sodium aluminate solution concentration of preparation is 180gAl2O3/ L, aluminum sulfate solution concentration is 60gAl2O3/ L, prepares A-6 carrier and catalyst AC-6.
Comparative example 1
Other condition, with embodiment 1, is simply added without additive and template, prepares aluminium oxide, A-7 carrier and catalyst AC-7.
Catalyst physicochemical property obtained above is listed in table 1.
Table 1 catalyst physicochemical property
| Numbering | AC-1 | AC-2 | AC-3 | AC-4 | AC-5 | AC-6 | AC-7 |
| Character | |||||||
| Specific surface area/m2·g-1 | 221 | 216 | 225 | 210 | 215 | 208 | 193 |
| Pore volume/mL g-1 | 0.65 | 0.63 | 0.65 | 0.65 | 0.64 | 0.67 | 0.71 |
| Pore-size distribution/% | |||||||
| <6nm | 14.7 | 12.8 | 14.9 | 12.7 | 13.1 | 12.1 | 10.3 |
| 6~15nm | 48.0 | 51.9 | 48.2 | 47.4 | 49.6 | 45.3 | 43.2 |
| 15~100nm | 26.1 | 24.9 | 27.0 | 29.7 | 27.2 | 31.4 | 41.9 |
| >100nm | 11.2 | 10.4 | 9.9 | 10.2 | 10.1 | 11.2 | 0.6 |
| Total acid/mmol/g | 0.391 | 0.369 | 0.389 | 0.361 | 0.374 | 0.356 | 0.336 |
| Composition | |||||||
| MoO3/wt% | 16.1 | 15.9 | 16.1 | 16.2 | 16.0 | 16.3 | 16.2 |
| NiO/wt% | 3.3 | 3.2 | 3.1 | 3.2 | 3.1 | 3.2 | 3.0 |
| P/wt% | 1.3 | 1.2 | 1.2 | 1.3 | 1.2 | 1.2 | 1.2 |
Institute's controlling catalyst is carried out activity rating with fixing bed small hydrogenation device, and the physicochemical property of raw material used is in Table 2, and appreciation condition is in Table 3, and with the activity of comparative example A's C-7 catalyst for 100, other and the evaluation result after comparative example expression activitiy are in Table 4.
Table 2 raw oil character
| Project | Raw oil |
| Density (20 DEG C), kg/m3 | 959 |
| Sulfur, wt% | 2.13 |
| Carbon residue, wt% | 9.58 |
| Nickel+vanadium, μ g/g | 49.8 |
Table 3 is fixed bed and is evaluated process conditions
| Condition | |
| Reaction temperature, DEG C | 385 |
| Reaction pressure, MPa | 14.7 |
| Volume space velocity during liquid, h-1 | 0.56 |
| Hydrogen to oil volume ratio | 1000 |
Table 4 evaluating catalyst result
| Project | AC-1 | AC-2 | AC-3 | AC-4 | AC-5 | AC-6 | AC-7 |
| Relative removal efficiency | |||||||
| De-(nickel+vanadium) | 113 | 113 | 112 | 112 | 109 | 105 | 100 |
| Desulfurization | 112 | 110 | 111 | 109 | 108 | 107 | 100 |
| De-carbon residue | 115 | 112 | 113 | 110 | 106 | 107 | 100 |
In Fig. 1 and Fig. 2, the scanning electron microscope image of two kinds of aluminium oxidies shows, in embodiment 1, alumina grain size is uniform, and the particle periphery of state of aggregation exists with " bar-shaped " or " chain " particle shape and piles up each other, forms the duct of a large amount of hundred nano-scale.And aluminium oxide particles size in comparative example is uneven, many between state of aggregation particle exist with " lamellar " particle shape.Table 4 shows, adopts catalyst prepared by the present invention compared with comparative example, and its hydrogenation activity significantly improves.
Claims (17)
1. a preparation method for hydrotreating catalyst, including:
(1) at the alkaline solution containing aluminum and the acid solution containing aluminum and flow the process of plastic, simultaneously and flow addition additive and organic formwork agent, regulating pH value is 6.0 ~ 8.0, and reaction temperature is 50 ~ 100 DEG C, and the response time is 30 ~ 120min；Described additive is carbon number is the alcohols of 2 ~ 4, and addition accounts for the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight；Described organic formwork agent is cellulose ether compounds, and addition is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight；
(2) adding alkaline solution in the product of step (1) gained, regulating pH value is 7.5 ~ 10.0, and reaction temperature is 60 DEG C ~ 100 DEG C, and the response time is 30 ~ 120min；
(3) being filtered by the serosity of step (2) gained, filter cake is scrubbed, obtains alumina dry glue after drying；
(4) by the alumina dry gum forming of step (3) gained, through super-dry, roasting, catalyst carrier is obtained,
(5) impregnation method is adopted hydrogenation active metals component to be incorporated in the catalyst carrier of step (3) gained, drying, roasting, obtain hydrotreating catalyst.
2. in accordance with the method for claim 1, it is characterised in that step (2) gained serosity is through Aging Step, and aging temperature is 60 ~ 100 DEG C, and ageing time is 10 ~ 120min.
3. in accordance with the method for claim 1, it is characterized in that in step (1), the alkaline solution containing aluminum, the acid solution containing aluminum, additive and template carry out and flow plastic reaction, and regulating pH value is 6.5 ~ 8.0, controlling gelling temperature is 50 ~ 95 DEG C, and the response time is 40 ~ 100min.
4. in accordance with the method for claim 1, it is characterised in that described additive and organic formwork agent are added separately to, or add after both mixing, or both are added in the alkaline solution containing aluminum or the acid solution containing aluminum and add.
5. in accordance with the method for claim 1, it is characterised in that described additive and organic formwork agent add after mixing in form of an aqueous solutions, and in aqueous solution, the concentration of additive is 0.5 ~ 60g/L, and the concentration of organic formwork agent is 0.5 ~ 60g/L.
6. in accordance with the method for claim 1, it is characterised in that the described acid solution containing aluminum is the solution of one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, and the concentration of the acid solution containing aluminum is 20 ~ 80gAl2O3/L；The described alkaline solution containing aluminum is the solution of sodium metaaluminate, potassium metaaluminate or their mixture, and the concentration of the alkaline solution containing aluminum is 100 ~ 200gAl2O3/L。
7. in accordance with the method for claim 1, it is characterised in that described additive is one or more in ethanol, isopropanol, propanol, propylene glycol.
8. in accordance with the method for claim 1, it is characterised in that described template is cellulose ether compounds is one or more in methylcellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethylmethylcellulose, hydroxyethylmethyl-cellulose, hydroxypropyl methyl cellulose, carboxymethyl hydroxymethyl cellulose.
9. in accordance with the method for claim 1, it is characterised in that described template is methylcellulose and/or hydroxypropyl methyl cellulose.
10. in accordance with the method for claim 1, it is characterised in that in step (2), described alkaline solution is one or more the solution in sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate, potassium hydroxide, ammonia.
11. in accordance with the method for claim 1, it is characterised in that it is 8.0 ~ 9.0 that step (2) regulates pH value, and reaction temperature 80 ~ 90 DEG C, the response time is 50 ~ 90min.
12. in accordance with the method for claim 1, it is characterised in that the drying condition described in step (3): 100 ~ 150 DEG C dry 2 ~ 6 hours.
13. in accordance with the method for claim 1, it is characterized in that: in carrier preparation process, add in shaping assistant, expanding agent as required one or more, described shaping assistant is one or more in peptization acid, extrusion aid, binding agent, and described expanding agent is one or more in white carbon black, ammonium phosphate, ammonium carbonate, Polyethylene Glycol, polyvinyl alcohol, methylcellulose, polyacrylamide.
14. in accordance with the method for claim 1, it is characterised in that the drying condition of step (4) is dry 2 ~ 20 hours at 80 DEG C ~ 200 DEG C, and roasting condition is roasting 1 ~ 8 hour at 450 DEG C ~ 1000 DEG C.
15. in accordance with the method for claim 1, it is characterized in that described hydrogenation active metals is group VIII and vib metal, group viii metal is Ni or/and Co, vib metal is W or/and Mo, with the weight of catalyst for benchmark, group viii metal is calculated as 0.5wt% ~ 9.0wt% with oxide, and vib metal is calculated as 10.0wt% ~ 30.0wt% with oxide.
16. in accordance with the method for claim 1, it is characterised in that the baking temperature described in step (5) is room temperature～120 DEG C, drying time 0.5～24h, sintering temperature 400～550 DEG C, roasting time 1 ~ 6h.
17. in accordance with the method for claim 1, it is characterized in that in described hydrotreating catalyst containing one or more in auxiliary agent P, B, F, Ti, Zr, auxiliary agent adds in plastic or carrier preparation process, or adds when impregnating hydrogenation active metals component.
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| CN110935461B (en) * | 2018-09-25 | 2022-07-08 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| CN113559891B (en) * | 2020-04-28 | 2023-03-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN111774048A (en) * | 2020-07-13 | 2020-10-16 | 沈阳三聚凯特催化剂有限公司 | Method for preparing alumina carrier, reforming protective agent and preparation method thereof |
| CN115518663B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrocracking catalyst |
| CN115518644B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
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| CN101240190A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Boiling bed hydrogenation treatment catalyst and its preparing process |
| CN102039138A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Heavy oil or residual oil hydrogenation catalyst and preparation method thereof |
| CN102765737A (en) * | 2011-05-06 | 2012-11-07 | 北京化工大学 | Mesoporous spherical alumina prepared by guiding of template and preparation method thereof |
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