CN103801312A - Preparation method for hydrotreatment catalyst - Google Patents
Preparation method for hydrotreatment catalyst Download PDFInfo
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- CN103801312A CN103801312A CN201210443029.8A CN201210443029A CN103801312A CN 103801312 A CN103801312 A CN 103801312A CN 201210443029 A CN201210443029 A CN 201210443029A CN 103801312 A CN103801312 A CN 103801312A
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Abstract
The invention discloses a preparation method for a hydrotreatment catalyst. The method comprises the following steps: in the process of gel formation by cocurrent flow of an alkaline solution containing aluminum and an acidic solution containing aluminum, adding an additive and an organic template agent in the manner of cocurrent flow at the same time, controlling proper reaction conditions and carrying out gel formation; then adding an alkaline solution to adjust a pH value; then carrying out filtering, washing and drying so as to obtain alumina dry gel; carrying out molding, drying and calcining so as to obtain an alumina carrier; and loading active metal components. The catalyst prepared by using the method has the advantages of a large specific surface area, a great pore volume and a reasonable pore structure and is particularly applicable as a catalyst for hydrodesulfurization or hydro-conversion of residual oil.
Description
Technical field
The present invention relates to a kind of preparation method of hydrotreating catalyst, be particularly useful for the preparation method of the hydrotreating catalyst of processing poor residuum.
Background technology
Along with aggravation and the market continuous increase to 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 remarkable to increasing the economic benefit of refinery.Hydrotreatment technology, as improving inferior heavy oil quality and one of effective technology scheme of high-quality feedstock oil being provided for downstream unit, is subject to extensive concern at present.
Residual oil (reduced crude, decompression residuum) is remaining most important part after crude oil time processing (normal, decompression distillation).With light ends oil phase ratio, residual oil composition is complicated, and mean molecule quantity is large, and viscosity is high, and density is large, and hydrogen-carbon ratio is low, and carbon residue is high, and most of sulphur, nitrogen, carbon residue and metal impurities in crude oil are enriched in residual oil.The duct of the These characteristics requirement catalyst for hydrotreatment of residual oil of residual oil more can the macromolecular diffusion of adaptive response thing.Current most widely used hydrotreating catalyst is generally loaded catalyst, and its carrier is generally aluminium oxide and by its derivative complex carrier, as TiO
2-Al
2o
3, SiO
2-Al
2o
3deng, or in alumina support, add some auxiliary agents and carry out modification, 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.Because aluminium oxide has good mechanical strength, heat endurance, Acidity and pore structure that can modulation, be therefore widely used in catalytic field as catalyst carrier.The world makes catalyst market constantly increase the demand of hydrogenation catalyst to the attention of hydrogen addition technology at present.Along with the further investigation of people to hydrogenation catalyst, the importance of the carrier property to catalyst has also had new understanding, the not only decentralization important to active component of pore structure (specific area, pore volume and pore-size distribution) of carrier, and be directly connected to diffusion and mass transfer in course of reaction, pore size and pass can affect the inner diffusing rate of reactant, product, thereby affect the activity and selectivity of catalyst.Therefore, for the activity of catalyst, selective, service life, mechanical strength and power of regeneration important.Aluminium hydroxide is the important presoma of preparing aluminium oxide, and its pore structure has certain decisive action to crystalline phase, the surface acid property etc. of aluminium oxide.Therefore the catalyst carrier for hydrgenating that, processability is good and price is suitable has important practical significance for exploitation high-performance hydrotreating catalyst.
γ-A1
2o
3duct mainly formed by several parts, comprise 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 area, and its size depends primarily on the factor such as size, shape and accumulation mode and the form of offspring of boehmite primary particle.And offspring hole and poly particle hole are larger for the duct contribution of hundred nano-scale.There is substantial connection with the preparation condition (as reacted and aging temperature, pH value, mixing speed, the time of staying and washing and drying condition) of boehmite in these factors.The primary particle of boehmite particle and form and the accumulation mode etc. of offspring greatly affect the pore structure of aluminium oxide prepared therefrom as can be seen here.
CN1257754A discloses a kind of preparation method of catalyst carrier, wherein adopts waterglass and aluminum sulfate to prepare the dry glue of sial, and the carrier pore volume of preparation is 0.45 ~ 0.75mL/g, and average pore size is 5 ~ 10nm.Prepared by this one-tenth gluing method contains silicon carrier, and aperture is less, is not suitable for as heavy oil or catalyst for hydrotreatment of residual oil.
CN102039195A discloses a kind of carrying alumina preparation.The method is while adopting carbonizatin method to prepare alumina dry glue, to add organic expanding agent and defoamer.Although the alumina support that the method provides can reach 12 ~ 13nm in several apertures, its pore volume and specific area are all lower.When this carrier is used for catalyst for hydroprocessing of heavy oil, cannot provide more chain carrier.
CN102309998A discloses a kind of preparation method of catalyst for hydroprocessing of heavy oil carrier.The method is to adopt at a lower temperature pH value swing method to carry out plastic, more aging a period of time at high temperature.Although this one-tenth gluing method can be prepared the alumina support with larger aperture, it is less that it is less than pore size distribution within the scope of 15nm.Be prepared into after catalyst as catalyst for hydroprocessing of heavy oil carrier using this aluminium oxide, its pore structure may react favourable to demetalization, but is unfavorable for desulfurization and hydroconversion reactions.
CN1768948A discloses a kind of preparation method who is applicable to Hydrodemetalation catalyst carrier, wherein take sodium metaaluminate and aluminum sulfate solution as raw material, adopts cocurrent cooling operation to prepare alumina support.Although alumina support average pore size prepared by this one-tenth gluing method is large, specific 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 invention provides a kind of preparation method of hydrotreating catalyst.Catalyst prepared by the inventive method, has that pore volume is large, specific area is moderate, reasonable pore distribution and a suitable feature of surface acid property, is particularly suitable for mink cell focus hydrotreatment process, especially residuum hydrodesulfurization and carbon residue conversion process.
The preparation method of hydrotreating catalyst of the present invention, comprising:
(1) containing the alkaline solution of aluminium with containing the acid solution of aluminium and flow in the process of plastic, simultaneously and stream add additive and organic formwork agent, regulating pH value is 6.0 ~ 8.0, reaction temperature is 50 ~ 100 ℃, the reaction time is 30 ~ 120min; Described additive is that 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) in the product of step (1) gained, add alkaline solution, regulating pH value is 7.5 ~ 10.0, and reaction temperature is 60 ℃ ~ 100 ℃, and the reaction time is 30 ~ 120min;
(3) slurries of step (2) gained are filtered, filter cake, through washing, obtains alumina dry glue after being dried;
(4) by the alumina dry gum forming of step (3) gained, through super-dry, roasting, obtain catalyst carrier,
(5) adopt impregnation method that hydrogenation active metals component is incorporated in the catalyst carrier of step (3) gained, then through super-dry, roasting, obtain hydrotreating catalyst.
In the inventive method, step (2) gained slurries are through aging step, described aging referring to makes solution keep the regular hour under stirring or inactive state, aging temperature is 60 ~ 100 ℃, preferably 80 ~ 95 ℃, more preferably 85 ~ 90 ℃, ageing time is 10 ~ 120min, preferably 15 ~ 60 min, more preferably 20 ~ 40min.
In step (1), contain the alkaline solution of aluminium, carry out and flow plastic reaction containing acid solution, additive and the template of aluminium, regulate pH value to be preferably 6.5 ~ 8.0, control at least 50 ℃ of plastic temperature, preferably 50 ~ 95 ℃, the reaction time is preferably 40 ~ 100min, more preferably 60 ~ 80min.Wherein, additive and organic formwork agent can add separately respectively, after also both can being mixed, add, and also both can be added to containing the alkaline solution of aluminium or containing in the acid solution of aluminium and add, and preferably will after additive and organic formwork agent mixing, add; Additive and organic formwork agent add separately respectively or both add fashionablely after mixing, and preferably add with the form of the aqueous solution, and in the 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 aluminium, the solution of one or more of preferably sulfuric acid aluminium, aluminum nitrate, aluminium chloride etc., more preferably sulfuric acid aluminum solutions.The concentration that contains the acid solution of aluminium is 20 ~ 80gAl
2o
3/ L.The described alkaline solution containing aluminium, the preferably solution of sodium metaaluminate, potassium metaaluminate or their mixture, more preferred sodium aluminate solution.The concentration that contains the alkaline solution of aluminium is 100 ~ 200gAl
2o
3/ L.Described additive is hydroxyl small molecule alcohol as one or more in ethanol, isopropyl alcohol, propyl alcohol, propane diols, preferred alcohol and isopropyl alcohol.Described template is cellulose ether compounds, comprise one or more in methylcellulose (MC), ethyl cellulose (EC), CMC (HMC), hydroxyethylcellulose (HEC), hydroxypropyl cellulose (HPC), ethylmethylcellulose (EMC), HEMC (HEMC), hydroxypropyl methylcellulose (HPMC), carboxymethyl CMC (CMHMC), preferable methyl cellulose and hydroxypropyl methylcellulose.
In step (2), described alkaline solution is one or more the solution in NaOH, sodium carbonate, sodium acid carbonate, ammonium carbonate, carbonic hydroammonium, potassium hydroxide, ammoniacal liquor, preferably sodium carbonate liquor.It is 7.5 ~ 10.0 that step (2) regulates pH value, and reaction temperature is 60 ℃ ~ 100 ℃, pH value preferably 8.0 ~ 9.0, more preferably 8.2 ~ 8.8, preferably 70 ~ 95 ℃ of reaction temperatures, more preferably 80 ~ 90 ℃, reaction time is 30 ~ 120min, preferably 50 ~ 90min, more preferably 60 ~ 80min.
In step (3), described washing generally adopts deionized water washing to neutral, described drying condition: 100 ~ 150 ℃ are dried 2 ~ 6 hours, and preferably 110 ~ 130 ℃, dry 4 ~ 6 hours.
In the inventive method, in carrier preparation process, can add as required shaping assistant and expanding agent etc.Described shaping assistant can be peptization acid, extrusion aid, adhesive etc.Described expanding agent is one or more of carbon black, ammonium phosphate, ammonium carbonate, polyethylene glycol, polyvinyl alcohol, methylcellulose, polyacrylamide etc.The addition of described expanding agent accounts for 2% ~ 10% of raw mixture weight.
In the inventive method, the drying condition of step (4) is at 80 ℃ ~ 200 ℃ dry 2 ~ 20 hours, and roasting condition is roasting 1 ~ 8 hour at 450 ℃ ~ 1000 ℃.Described moulding can adopt existing conventional method, as extrusion molding or rolling ball method etc.
In hydrotreating catalyst of the present invention, the hydrogenation active metals of employing comprises group VIII and vib metal, and VIII metal is generally Ni or/and Co, and vib metal is that W is or/and Mo.Take the weight of catalyst as benchmark, VIII metal is counted 0.5wt% ~ 9.0wt% with oxide, and vib metal is counted 10.0wt% ~ 30.0wt% with oxide.In the inventive method, adopt infusion process that hydrogenation metal component is introduced in catalyst.Described dipping can adopt conventional dipping method, preferably adopts saturated infusion process.Dipping solution adopts conventional method preparation.After dipping active metal component, drying and roasting, obtain hydrotreating catalyst.Wherein baking temperature is normal temperature～120 ℃, drying time 0.5～24h, 400～550 ℃ of sintering temperatures, 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 ~ 280m
2/ 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, bore dia be the pore volume in the hole of 6 ~ 15nm account for total pore volume 35% ~ 55%, the pore volume in the hole of bore dia > 15nm accounts for the more than 25% of total pore volume, be generally 25% ~ 40%, the pore volume in the hole of its median pore diameter > 100 nm accounts for 5% ~ 20% of total pore volume; Meleic acid amount 0.250 ~ 0.550mmol/g.
In hydrotreating catalyst of the present invention, can comprise suitable auxiliary agent, as one or more in P, B, F, Ti, Zr etc.Auxiliary agent can add in plastic or carrier preparation process, also can in the time of dipping active metal component, add.
Catalyst prepared by the inventive method can be for processes such as the hydrodesulfurization of heavy oil, hydrodenitrogeneration, hydro-conversions.Operating condition is generally: reaction pressure is 5 ~ 25MPa, and temperature is 300 ~ 500 ℃, and when liquid, volume space velocity is 0.1 ~ 5.0h
-1, hydrogen to oil volume ratio is 100 ~ 5000.
In the inventive method, in the time of Kaolinite Preparation of Catalyst carrier, under the cooperatively interacting of low mass molecule alcohol class 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 can promote boehmite crystal grain to form the particle shape with certain draw ratio, as bar-shaped or chain pattern, make the connectivity in formed duct good, be conducive to the diffusion of reactant, and improving the utilization rate in duct, deposit is not easy to deposit in duct, the service life of extending 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 even.The catalyst of preparation has the feature of large pore volume, high-ratio surface and reasonable pore distribution thus, thereby be conducive to the diffusion of macromolecular reaction thing in catalyst duct in mink cell focus or residual oil, be conducive to again especially the carrying out of desulfurization and denitrification reaction of macromolecular reaction thing removing impurities matter.Therefore, catalyst prepared by the inventive method, just can meet Production requirement without the extra expanding agent that adds.
Catalyst prepared by the inventive method is suitable for heavy oil or residuum hydrodesulfurization or hydrogenation conversion catalyst, more stable at the mink cell focus hydrogenation process performance of height reaction severity.
The inventive method technical process is simple, there is no the discharge of pollutant, non-environmental-pollution, and cost is low.
Central hole structure of the present invention and specific 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 is prepared aluminium oxide.
The specific embodiment
Below by further statement technical characterictic of the present invention of embodiment, but be not limited to embodiment.Wt% is mass fraction.
Embodiment 1
(1) alumina dry glue preparation
Preparation sodium aluminate solution concentration is 140gAl
2o
3/ L, amounts to 2.5L; Aluminum sulfate solution concentration is 40gAl
2o
3/ L amounts to 5.0L; In ethanol and hydroxypropyl methylcellulose (HPMC) mixed solution, concentration of alcohol is 1.0g/L, and HPMC concentration is 1.0g/L, amounts to 1.0L.
In retort, the pre-end water that adds, arranges 75 ℃ by retort temperature, opens and stirs.The sodium aluminate solution preparing and aluminum sulfate solution are added in retort process according to certain flow rate stream, simultaneously and stream add ethanol and hydroxypropyl methylcellulose (HPMC) mixed solution, adjusting pH value is 6.5.After material adds, in the product of gained, add alkaline solution, regulating pH value is 8.8, and reaction temperature is 90 ℃, and the reaction time is 30min.After reaction finishes, enter the ageing step, reaction temperature is 90 ℃, and ageing time is 20min.The slurries of gained are filtered, and filter cake, through washing, obtains alumina dry glue after being dried.650 ℃ of roastings obtain aluminium oxide for 3 hours.
(2) catalyst preparation
Take alumina dry glue 1000g prepared by step (1), add 25g sesbania powder and mix, dissolving 26g nitric acid (67wt%) with the dilution of 900g deionized water and join in mixture, kneading extruded moulding, dry 2h at 120 ℃, at 700 ℃, roasting 3h obtains A-1 carrier.
Take A-1 carrier 100g.Take molybdenum oxide 20.5g, basic nickel carbonate 7.0g, phosphoric acid 5.6g, adds deionized water dissolving to be cooled to constant volume 85mL after room temperature, obtains dipping solution.Adopt spray mode that above-mentioned maceration extract is immersed on carrier A-1, at room temperature place after 2.0 hours and be dried 2 hours at 120 ℃, finally at 450 ℃, roasting makes catalyst A C-1 for 3 hours.
Embodiment 2
Other condition, with embodiment 1, just replaces with isopropyl alcohol ethanol, and the isopropyl alcohol concentration of preparation changes 35g/L into, and HPMC replaces with MC, and the MC concentration of preparation changes 20g/L into, prepares A-2 carrier and catalyst A C-2.
Embodiment 3
Other condition, with embodiment 1, just changes concentration of alcohol as 55g/L into, and HPMC concentration changes 50g/L into, prepares A-3 carrier and catalyst A C-3.
Embodiment 4
Other condition, with embodiment 1, is just set to 80 ℃ retort temperature setting, prepares A-4 carrier and catalyst A C-4.
Embodiment 5
Other condition is with embodiment 1, and just ageing time is set as 40min, prepares A-5 carrier and catalyst A C-5.
Embodiment 6
Other condition is with embodiment 1, and just the sodium aluminate solution concentration of preparation is 180gAl
2o
3/ L, aluminum sulfate solution concentration is 60gAl
2o
3/ L, prepares A-6 carrier and catalyst A C-6.
Comparative example 1
Other condition, with embodiment 1, does not just add additive and template, prepares aluminium oxide, A-7 carrier and catalyst A C-7.
The catalyst physicochemical property that obtained is above listed in to table 1.
Table 1 catalyst physicochemical property
| Numbering | AC-1 | AC-2 | AC-3 | AC-4 | AC-5 | AC-6 | AC-7 |
| Character | |||||||
| Specific area/m 2·g -1 | 221 | 216 | 225 | 210 | 215 | 208 | 193 |
| Pore volume/mLg -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 | |||||||
| MoO 3/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 to activity rating with fixed bed small hydrogenation device, and the physicochemical property of raw material used is in table 2, and appreciation condition is in table 3, and take the activity of comparative example A C-7 catalyst as 100, other and the comparative example specific activity evaluation result after is in table 4.
Table 2 feedstock oil character
| Project | Feedstock oil |
| Density (20 ℃), kg/m 3 | 959 |
| Sulphur, wt% | 2.13 |
| Carbon residue, wt% | 9.58 |
| Nickel+vanadium, μ g/g | 49.8 |
Table 3 fixed bed is evaluated process conditions
| Condition | |
| Reaction temperature, ℃ | 385 |
| Reaction pressure, MPa | 14.7 |
| Volume space velocity when 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 |
| Removal efficiency relatively | |||||||
| 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 oxide shows, in embodiment 1, evenly, the particle of state of aggregation around exists with " bar-shaped " or " chain " particle shape and piles up each other alumina grain size, forms the duct of a large amount of hundred nano-scales.And aluminium oxide particles size in comparative example is inhomogeneous, between state of aggregation particle, exists mainly with " sheet " 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, comprising:
(1) containing the alkaline solution of aluminium with containing the acid solution of aluminium and flow in the process of plastic, simultaneously and stream add additive and organic formwork agent, regulating pH value is 6.0 ~ 8.0, reaction temperature is 50 ~ 100 ℃, the reaction time is 30 ~ 120min; Described additive is that 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) in the product of step (1) gained, add alkaline solution, regulating pH value is 7.5 ~ 10.0, and reaction temperature is 60 ℃ ~ 100 ℃, and the reaction time is 30 ~ 120min;
(3) slurries of step (2) gained are filtered, filter cake, through washing, obtains alumina dry glue after being dried;
(4) by the alumina dry gum forming of step (3) gained, through super-dry, roasting, obtain catalyst carrier,
(5) adopt impregnation method that hydrogenation active metals component is incorporated in the catalyst carrier of step (3) gained, then through super-dry, roasting, obtain hydrotreating catalyst.
2. in accordance with the method for claim 1, it is characterized in that step (2) gained slurries are through aging step, aging temperature is 60 ~ 100 ℃, and ageing time is 10 ~ 120min.
3. in accordance with the method for claim 1, it is characterized in that in step (1), contain the alkaline solution of aluminium, carry out and flow plastic reaction containing acid solution, additive and the template of aluminium, regulating pH value is 6.5 ~ 8.0, controlling plastic temperature is 50 ~ 95 ℃, and the reaction time is 40 ~ 100min.
4. in accordance with the method for claim 1, it is characterized in that described additive and organic formwork agent add separately respectively, or add after both are mixed, or both are added to containing the alkaline solution of aluminium or containing in the acid solution of aluminium and are added.
5. in accordance with the method for claim 1, it is characterized in that adding with the form of the aqueous solution after described additive and organic formwork agent mix, in the 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 characterized in that the described acid solution containing aluminium is one or more solution of aluminum sulfate, aluminum nitrate, aluminium chloride, is 20 ~ 80gAl containing the concentration of the acid solution of aluminium
2o
3/ L; The described alkaline solution containing aluminium is the solution of sodium metaaluminate, potassium metaaluminate or their mixture, and the concentration that contains the alkaline solution of aluminium is 100 ~ 200gAl
2o
3/ L.
7. in accordance with the method for claim 1, it is characterized in that described additive is one or more in ethanol, isopropyl alcohol, propyl alcohol, propane diols.
8. in accordance with the method for claim 1, it is characterized in that described template is that cellulose ether compounds is one or more in methylcellulose, ethyl cellulose, CMC, hydroxyethylcellulose, hydroxypropyl cellulose, ethylmethylcellulose, HEMC, hydroxypropyl methylcellulose, carboxymethyl CMC.
9. in accordance with the method for claim 1, it is characterized in that described template is methylcellulose and/or hydroxypropyl methylcellulose.
10. in accordance with the method for claim 1, it is characterized in that in step (2), described alkaline solution is one or more the solution in NaOH, sodium carbonate, sodium acid carbonate, ammonium carbonate, carbonic hydroammonium, potassium hydroxide, ammoniacal liquor.
11. in accordance with the method for claim 1, it is characterized in that it is 8.0 ~ 9.0 that step (2) regulates pH value, 80 ~ 90 ℃ of reaction temperatures, and the reaction time is 50 ~ 90min.
12. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (3): 100 ~ 150 ℃ are dried 2 ~ 6 hours.
13. in accordance with the method for claim 1, it is characterized in that: in carrier preparation process, add as required one or more in shaping assistant, expanding agent, described shaping assistant is one or more in peptization acid, extrusion aid, adhesive, and described expanding agent is one or more of carbon black, ammonium phosphate, ammonium carbonate, polyethylene glycol, polyvinyl alcohol, methylcellulose, polyacrylamide etc.
14. in accordance with the method for claim 1, and the drying condition that it is characterized in that step (4) is at 80 ℃ ~ 200 ℃ dry 2 ~ 20 hours, and roasting condition is roasting 1 ~ 8 hour at 450 ℃ ~ 1000 ℃.
15. in accordance with the method for claim 1, it is characterized in that described hydrogenation active metals is group VIII and vib metal, VIII metal is that Ni is or/and Co, vib metal is that W is or/and Mo, take the weight of catalyst as benchmark, VIII metal is counted 0.5wt% ~ 9.0wt% with oxide, and vib metal is counted 10.0wt% ~ 30.0wt% with oxide.
16. in accordance with the method for claim 1, it is characterized in that the described baking temperature of step (5) is normal temperature～120 ℃, drying time 0.5～24h, 400～550 ℃ of sintering temperatures, roasting time 1 ~ 6h.
17. in accordance with the method for claim 1, it is characterized in that containing one or more in auxiliary agent P, B, F, Ti, Zr in described hydrotreating catalyst, auxiliary agent adds in plastic or carrier preparation process, or adds in the time of dipping hydrogenation active metals component.
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Cited By (5)
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| CN110935461A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Preparation method of heavy oil hydrodemetallization catalyst |
| 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 |
| CN113559891A (en) * | 2020-04-28 | 2021-10-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN115518663A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrocracking catalyst |
| CN115518644A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Preparation method of residual oil hydrodemetallization catalyst |
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