CN103803616B - Preparation method for alumina dry gel - Google Patents
Preparation method for alumina dry gel Download PDFInfo
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- CN103803616B CN103803616B CN201210443030.0A CN201210443030A CN103803616B CN 103803616 B CN103803616 B CN 103803616B CN 201210443030 A CN201210443030 A CN 201210443030A CN 103803616 B CN103803616 B CN 103803616B
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Abstract
The invention discloses a preparation method for alumina dry gel. The method comprises the following steps: in the process of gel formation by concurrent 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 concurrent flow at the same time, controlling proper reaction conditions and carrying out gel formation, wherein the organic template agent is cellulose ethers; then adding an alkaline solution to adjust a pH value; and then carrying out filtering, washing and drying so as to obtain the alumina dry gel. The alumina dry gel 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 carrier component for a heavy oil hydrotreating catalyst, especially applicable as a carrier component for a residual oil hydrodesulfurization or hydro-conversion catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of alumina dry glue, in particular for the carrier component of heavy resid hydrotreating catalyst.
Background technology
Aluminum oxide is one of the most frequently used industrial raw material, at field important roles such as catalyzer, pottery, refractory materialss.Because aluminum oxide has good physical strength, thermostability, can the Acidity of modulation and pore structure, be therefore widely used in catalytic field as support of the catalyst.The attention of the current world to hydrogen addition technology makes the demand of catalyzer market to hydrogenation catalyst constantly increase.Current most widely used hydrogenation catalyst is generally loaded catalyst, the complex carrier that its carrier is generally aluminum oxide and is derived by it, as TiO
2-Al
2o
3, SiO
2-Al
2o
3deng, or in alumina supporter, add some auxiliary agents carry out modification, as phosphorus, boron, fluorine etc.Along with people are to the further investigation of hydrogenation catalyst, new understanding be there has also been to the importance of the carrier property of catalyzer, the pore structure (specific surface area, pore volume and pore size distribution) of carrier is not only to the dispersity important of active ingredient, and the diffusion be directly connected in reaction process and mass transfer, pore size and hole shape can affect the inner diffusing rate of reactant, product, thus affect the activity and selectivity of catalyzer.Especially for residual hydrocracking reaction process, residual oil molecule is because molecular dimension is large, viscosity high, residual oil molecule is more serious by internal diffusion restriction ratio in catalyzer duct, therefore, residual oil molecule can be spread effectively in duct, can react fully again, just need catalyzer to have suitable pore structure.
γ-A1
2o
3duct form primarily of a few part, 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 catalyzer pore volume, aperture and specific surface area, and its size depends primarily on the factor such as form of the size of pseudo-boehmite primary particle, shape and accumulation mode and offspring.And offspring hole and poly particle hole are contributed larger for the duct of hundred nano-scale.There is substantial connection in the preparation condition of these factors and pseudo-boehmite (as reacted and aging temperature, pH value, stirring velocity, the residence time and washing and drying conditions).The primary particle of pseudo-boehmite particle and the form of offspring and accumulation mode etc. greatly affect the pore structure of aluminum oxide prepared therefrom as can be seen here.
CN1257754A discloses a kind of preparation method of support of the catalyst, and wherein adopt water glass and Tai-Ace S 150 to prepare the dry glue of sial, the carrier pore volume of preparation is 0.45 ~ 0.75mL/g, and mean pore size is 5 ~ 10nm.Prepared by this one-tenth gluing method contains silicon carrier, and aperture is less, is not suitable for being used as heavy oil or catalyst for hydrotreatment of residual oil.
CN102039195A discloses a kind of carrying alumina preparation.The method adds organic expanding agent and defoamer when being and adopting carborization to prepare alumina dry glue.Although the alumina supporter that the method provides can reach 12 ~ 13nm in a few aperture, its pore volume and specific surface area are all lower.When this carrier is used for catalyst for hydroprocessing of heavy oil, more chain carrier cannot be provided.
CN102309998A discloses a kind of carrying alumina preparation.The method adopts pH value swing method to carry out plastic at a lower temperature, more at high temperature aging for some time.Although this one-tenth gluing method can prepare the alumina supporter with larger aperture, its pore distribution be less than within the scope of 15nm is less.After being prepared into catalyzer using this aluminum oxide as catalyst for hydroprocessing of heavy oil carrier, its pore structure may react favourable to demetalization, but is unfavorable for desulfurization and hydroconversion reactions.
CN1768948A discloses a kind of carrying alumina preparation, wherein with sodium metaaluminate and alum liquor for raw material, adopt cocurrent cooling operation to prepare alumina dry glue.Although alumina supporter mean pore size prepared by this one-tenth gluing method is large, specific surface area is little, is unfavorable for mink cell focus hydrogenating desulfurization and hydroconversion reactions using it as support of the catalyst.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of alumina dry glue.The alumina ratio surface-area of the method gained is large, pore volume is large, pore structure is reasonable, is especially suitable for use as the carrier component of catalyst for hydroprocessing of heavy oil, is particularly useful for the carrier component of residuum hydrodesulfurization or hydrogenation conversion catalyst.
The preparation method of alumina dry glue of the present invention, comprising:
(1) containing the basic solution of aluminium and containing the acidic solution of aluminium and flow in plastic process, also stream adds additive and organic formwork agent simultaneously, and adjust ph is 6.0 ~ 8.0, and temperature of reaction is 50 ~ 100 DEG C, and the reaction times is 30 ~ 120min; Described additive is one or more in sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight, described organic formwork agent is ether of cellulose compounds, and add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight;
(2) in the product of step (1) gained, add basic solution, adjust ph is 7.5 ~ 10.0, and temperature of reaction is 60 DEG C ~ 100 DEG C, and the reaction times is 30 ~ 120min;
(3) filtered by the slurries of step (2) gained, filter cake, through washing, obtains alumina dry glue after drying.
In the inventive method, step (2) gained slurries are through Aging Step, described aging referring to is being stirred or is being made solution keep the regular hour under stationary state, aging temperature is 60 ~ 100 DEG C, preferably 80 ~ 95 DEG C, more preferably 85 ~ 90 DEG C, digestion time is 10 ~ 120min, preferably 15 ~ 60 min, more preferably 20 ~ 40min.
In step (1), the basic solution containing aluminium, the acidic solution containing aluminium, additive and template are carried out and are flowed plastic reaction, and adjust ph is preferably 6.5 ~ 8.0, control gelling temperature at least 50 DEG C, preferably 50 ~ 95 DEG C, the reaction times is preferably 40 ~ 100min, more preferably 60 ~ 80min.Wherein, additive and organic formwork agent can individually add, and add, also both can be added in the basic solution containing aluminium or the acidic solution containing aluminium and add after also both can being mixed, and preferably add after additive and organic formwork agent mixing; Additive and organic formwork agent individually add or add fashionable after both mixing, and preferably add in form of an aqueous solutions, 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 acidic solution containing aluminium, the solution of one or more of preferably sulfuric acid aluminium, aluminum nitrate, aluminum chloride etc., more preferably sulfuric acid aluminum solutions.Concentration containing the acidic solution of aluminium is 20 ~ 80gAl
2o
3/ L.The described basic solution containing aluminium, the solution of preferred sodium metaaluminate, potassium metaaluminate or their mixture, more preferred sodium aluminate solution.Concentration containing the basic solution of aluminium is 100 ~ 200gAl
2o
3/ L.Described additive is one or more in sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, preferably sodium dodecyl sulfate.Described template is ether of cellulose compounds, comprise one or more in methylcellulose gum (MC), ethyl cellulose (EC), Walocel MT 20.000PV (HMC), Natvosol (HEC), hydroxypropylcellulose (HPC), ethylmethylcellulose (EMC), hydroxyethylmethyl-cellulose (HEMC), Vltra tears (HPMC), carboxymethyl Walocel MT 20.000PV (CMHMC), preferable methyl Mierocrystalline cellulose and Vltra tears.
In step (2), described basic solution is one or more the solution in sodium hydroxide, sodium carbonate, sodium bicarbonate, volatile salt, bicarbonate of ammonia, potassium hydroxide, ammoniacal liquor, preferred sodium carbonate solution.Step (2) adjust ph is 7.5 ~ 10.0, and temperature of reaction is 60 DEG C ~ 100 DEG C, pH value preferably 8.0 ~ 9.0, more preferably 8.2 ~ 8.8, temperature of reaction preferably 70 ~ 95 DEG C, more preferably 80 ~ 90 DEG C, reaction times is 30 ~ 120min, preferably 50 ~ 90min, more preferably 60 ~ 80min.
In step (3), described washing generally adopts deionized water wash to neutral, described drying conditions: 100 ~ 150 DEG C of dryings 2 ~ 6 hours, preferably 110 ~ 130 DEG C, dry 4 ~ 6 hours.
Alumina dry glue prepared by the inventive method obtains aluminum oxide in 2 ~ 6 hours through 500 ~ 950 DEG C of roastings, and its character is as follows: pore volume is 0.75 ~ 1.10mL/g, and specific surface area is 200 ~ 400m
2/ g, pore distribution is as follows: the pore volume in the hole of bore dia < 8nm accounts for less than 15% of total pore volume, bore dia is that the pore volume in the hole of 8 ~ 15nm accounts for 40% ~ 60% of total pore volume, the pore volume in the hole of bore dia > 15nm accounts for more than 30% of total pore volume, be generally 30% ~ 45%, the pore volume in the hole of its median pore diameter > 100 nm accounts for 5% ~ 20% of total pore volume.
The inventive method preferably adopts continuous process to prepare alumina dry glue, and wherein step (1) and step (2) are preferably carried out in two reactors separated.
The inventive method is at the basic solution containing aluminium and add suitable appropriate additive and template containing in aluminium acidic solution plastic reaction process, and control plastic reaction conditions, by improving plastic temperature of reaction, solution degree of supersaturation declines, molecular motion velocities is accelerated, accelerate dissolution-crystallization process, be conducive to the growth of crystal grain.The additive added can match with template, and the hydrophobic part in strengthening template molecule and the effect of water molecules, cause the gelling temp of template raise and can be in more stable state in reaction system.Under the cooperatively interacting of additive and organic formwork agent, pseudo-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 length-to-diameter ratio of pseudo-boehmite can be promoted, as bar-shaped or chain pattern, make the connectivity in formed duct good, be conducive to the diffusion of reactant, and improving the utilization ratio in duct, settling is not easy to deposit in duct, the work-ing life of extending catalyst.The inventive method is by effectively controlling the process of growth of pseudo-boehmite crystal grain, and the alumina dry glue grain size obtained, accumulation mode are even.The aluminum oxide prepared thus has the feature of large pore volume, high-ratio surface and reasonable pore distribution, thus be conducive to the diffusion of macromolecular reaction thing in catalyzer 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, alumina supporter prepared by the inventive method, just can meet Production requirement without the need to additionally adding expanding agent.
Aluminum oxide prepared by the inventive method is suitable for the carrier component of heavy oil or residuum hydrodesulfurization or hydrogenation conversion catalyst, and catalyzer prepared therefrom is more stable in the mink cell focus hydrogenation process of height reaction severity.
The inventive method technological process is simple, and do not have the discharge of pollutent, non-environmental-pollution, cost is low, is especially suitable for industrial continuous production alumina dry glue.
Central hole structure of the present invention and specific surface area adopt mercury penetration method analysis.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that embodiment 1 prepares aluminum oxide;
Fig. 2 is the scanning electron microscope (SEM) photograph that comparative example 1 prepares aluminum oxide.
Embodiment
State technical characteristic of the present invention further below by embodiment, but be not limited to embodiment.
Embodiment 1
Preparation sodium aluminate solution concentration is 140gAl
2o
3/ L, amounts to 2.5L; Alum liquor concentration is 40gAl
2o
3/ L amounts to 5.0L; In sodium lauryl sulphate and Vltra tears (HPMC) mixing solutions, sodium lauryl sulphate concentration is 1.0g/L, HPMC concentration is 1.0g/L, amounts to 1.0L.
In retort, pre-interpolation end water, arranges 75 DEG C by retort temperature, opens and stir.By the sodium aluminate solution prepared and alum liquor according to certain flow rate and stream adds in retort process, simultaneously and stream adds sodium lauryl sulphate and Vltra tears (HPMC) mixing solutions, adjust ph is 6.5.After material adds, in the product of gained, add basic solution, adjust ph is 8.8, and temperature of reaction is 90 DEG C, and the reaction times is 30min.Enter the aging step after reaction terminates, temperature of reaction is 90 DEG C, and digestion time is 20min.Filtered by the slurries of gained, filter cake, through washing, obtains alumina dry glue after drying.650 DEG C of roastings obtain aluminum oxide A in 3 hours.
Embodiment 2
Other condition, with embodiment 1, just replaces with sodium stearyl sulfate sodium lauryl sulphate, and the sodium stearyl sulfate concentration of preparation changes 30g/L into, and HPMC replaces with MC, and the MC concentration of preparation changes 20g/L into, prepares aluminum oxide B.
Embodiment 3
Other condition is with embodiment 1, and just sodium lauryl sulphate concentration is changed into 50g/L, HPMC concentration changes 50g/L into, prepares aluminum oxide C.
Embodiment 4
Other condition, with embodiment 1, is just set to 80 DEG C retort temperature, prepares aluminum oxide D.
Embodiment 5
Other condition is with embodiment 1, and just digestion time is set as 40min, prepares aluminum oxide E.
Embodiment 6
Other condition is with embodiment 1, and the sodium aluminate solution concentration of just preparation is 180gAl
2o
3/ L, alum liquor concentration is 60gAl
2o
3/ L, prepares aluminum oxide F.
Comparative example 1
Other condition, with embodiment 1, does not just add additive and template, prepares alumina G.
The physico-chemical property of aluminum oxide obtained above is listed in table 1.
Table 1 aluminum oxide physico-chemical property
| Numbering | A | B | C | D | E | F | G |
| Specific surface area/m 2·g -1 | 368 | 360 | 371 | 337 | 361 | 334 | 309 |
| Pore volume/cm 3·g -1 | 1.03 | 1.02 | 1.04 | 1.06 | 1.04 | 1.05 | 1.00 |
| Pore distribution/% | |||||||
| <8nm | 10.1 | 9.2 | 10.3 | 9.1 | 9.0 | 7.9 | 6.6 |
| 8~15nm | 50.7 | 56.3 | 49.1 | 50.0 | 51.9 | 49.8 | 32.3 |
| 15~100nm | 21.1 | 17.8 | 22.4 | 23.7 | 23.4 | 31.8 | 59.3 |
| >100nm | 18.1 | 16.7 | 18.2 | 17.2 | 15.7 | 10.5 | 1.8 |
Data as can be seen from table 1: when adding tensio-active agent and template in plastic reaction process, in high reaction temperatures, prepared aluminum oxide pore volume and specific surface area still have higher level, and after increasing sodium metaaluminate and Tai-Ace S 150 concentration, specific surface area reduces slightly, and pore volume does not reduce, the existence of pattern of descriptive parts agent makes the pseudo-boehmite crystal grain generated can slewing grow at a higher temperature.And when not adding additive and template, higher plastic temperature of reaction causes pseudo-boehmite grain growing too fast, the uneven specific surface area that also causes of grain size declines.
The scanning electron microscope image display of two kinds of aluminum oxide in Fig. 1 and Fig. 2, in embodiment 1, alumina grain size is even, and the particle periphery of state of aggregation exists with " bar-shaped " or " chain " particle shape and piles up each other, thus can form the duct of hundred nano-scale.And aluminium oxide particles size in comparative example 1 is uneven, exists between state of aggregation particle mainly with " sheet " particle shape.Therefore, the alumina supporter adopting the inventive method to provide is applicable to being used as the carrier component of the catalyzer such as residuum hydrogenating and metal-eliminating, hydrogenating desulfurization and hydrocracking.
Claims (13)
1. a preparation method for alumina dry glue, comprising:
(1) containing the basic solution of aluminium and containing the acidic solution of aluminium and flow in plastic process, also stream adds additive and organic formwork agent simultaneously, and adjust ph is 6.0 ~ 8.0, and temperature of reaction is 50 ~ 100 DEG C, and the reaction times is 30 ~ 120min; Described additive is one or more in sodium lauryl sulphate, Sodium palmityl sulfate, sodium stearyl sulfate, add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight, described organic formwork agent is ether of cellulose compounds, and add-on is the 0.1wt% ~ 5.0wt% of alumina dry glue butt weight;
(2) in the product of step (1) gained, add basic solution, adjust ph is 7.5 ~ 10.0, and temperature of reaction is 60 DEG C ~ 100 DEG C, and the reaction times is 30 ~ 120min;
(3) filtered by the slurries of step (2) gained, filter cake, through washing, obtains alumina dry glue after drying.
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 DEG C, and digestion time is 10 ~ 120min.
3. in accordance with the method for claim 1, it is characterized in that in step (1), the basic solution containing aluminium, the acidic solution containing aluminium, additive and template are carried out and are flowed plastic reaction, and adjust ph is 6.5 ~ 8.0, controlling gelling temperature is 50 ~ 95 DEG C, and the reaction times is 40 ~ 100min.
4. in accordance with the method for claim 1, it is characterized in that described additive and organic formwork agent individually add, or add after both are mixed.
5. in accordance with the method for claim 1, it is characterized in that: add after additive and organic formwork agent mix and add in form of an aqueous solutions, 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 acidic solution containing aluminium is the solution of one or more of Tai-Ace S 150, aluminum nitrate, aluminum chloride etc., the concentration containing the acidic solution of aluminium is 20 ~ 80gAl
2o
3/ L; The described basic solution containing aluminium is the solution of sodium metaaluminate, potassium metaaluminate or their mixture, and the concentration containing the basic solution of aluminium is 100 ~ 200gAl
2o
3/ L.
7. in accordance with the method for claim 1, it is characterized in that described template to be ether of cellulose compounds be in methylcellulose gum, ethyl cellulose, Walocel MT 20.000PV, Natvosol, hydroxypropylcellulose, ethylmethylcellulose, hydroxyethylmethyl-cellulose, Vltra tears, carboxymethyl Walocel MT 20.000PV one or more.
8. in accordance with the method for claim 1, it is characterized in that described template be ether of cellulose compounds is methylcellulose gum and/or Vltra tears.
9. in accordance with the method for claim 1, it is characterized in that in step (2), described basic solution is one or more the solution in sodium hydroxide, sodium carbonate, sodium bicarbonate, volatile salt, bicarbonate of ammonia, potassium hydroxide, ammoniacal liquor.
10. in accordance with the method for claim 1, it is characterized in that step (2) adjust ph is 8.0 ~ 9.0, temperature of reaction is 80 ~ 90 DEG C, and the reaction times is for being 50 ~ 90min.
11. in accordance with the method for claim 1, it is characterized in that described drying conditions: 100 ~ 150 DEG C of dryings 2 ~ 6 hours.
12. in accordance with the method for claim 1, it is characterized in that described drying conditions: 110 ~ 130 DEG C of dryings 4 ~ 6 hours.
13. 1 kinds of aluminum oxide, is characterized in that the arbitrary described alumina dry glue of claim 1 ~ 12 obtains aluminum oxide in 2 ~ 6 hours through 500 ~ 950 DEG C of roastings.
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| CN106669645B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of alumina support and preparation method thereof |
| CN106673032B (en) * | 2015-11-11 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of peracidity low-crystallinity alumina dry glue and preparation method thereof |
| CN107055580A (en) * | 2017-04-13 | 2017-08-18 | 山东公泉化工股份有限公司 | The preparation method of alumina dry glue |
| CN111099646B (en) * | 2018-10-26 | 2022-11-22 | 中国石油化工股份有限公司 | Continuous preparation method of large-pore-volume alumina carrier |
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| WO2008147519A1 (en) * | 2007-05-22 | 2008-12-04 | W . R . Grace & Co . - Conn. | Alumina particles and methods of making the same |
| CN101993102A (en) * | 2009-08-20 | 2011-03-30 | 中国科学院过程工程研究所 | Method for inorganically synthesizing organized mesoporous alumina |
| CN102234124A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Pseudoboehmite containing transition metal components and aluminum oxide prepared from same |
| CN102424411A (en) * | 2011-09-15 | 2012-04-25 | 暨南大学 | Preparation method for ordered mesoporous gamma-Al2O3 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008147519A1 (en) * | 2007-05-22 | 2008-12-04 | W . R . Grace & Co . - Conn. | Alumina particles and methods of making the same |
| CN101993102A (en) * | 2009-08-20 | 2011-03-30 | 中国科学院过程工程研究所 | Method for inorganically synthesizing organized mesoporous alumina |
| CN102234124A (en) * | 2010-04-30 | 2011-11-09 | 中国石油化工股份有限公司 | Pseudoboehmite containing transition metal components and aluminum oxide prepared from same |
| CN102424411A (en) * | 2011-09-15 | 2012-04-25 | 暨南大学 | Preparation method for ordered mesoporous gamma-Al2O3 |
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