CN103055947B - Preparation method of alumina support - Google Patents
Preparation method of alumina support Download PDFInfo
- Publication number
- CN103055947B CN103055947B CN201110322448.1A CN201110322448A CN103055947B CN 103055947 B CN103055947 B CN 103055947B CN 201110322448 A CN201110322448 A CN 201110322448A CN 103055947 B CN103055947 B CN 103055947B
- Authority
- CN
- China
- Prior art keywords
- accordance
- roasting
- nacf
- dry
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an alumina support. The method comprises the steps of enabling activated carbon fibers with developed pore structures to adsorb inorganic aluminium salts through dipping and then using the activated carbon fibers as pore-enlarging agents, kneading and forming the activated carbon fibers with an alumina precursor, and then drying and roasting the product, thus obtaining the alumina support. The alumina support prepared by the method is higher in specific surface area, more concentrated in pore size distribution and high in mechanical strength, also contains part of macropores with sizes more than 100nm, is suitable for preparing heavy/residual oil hydrogenation catalysts, and is favorable for removing macromolecular impurities in heavy/residual oil and delaying the increase of diffusion resistance in heavy/residual oil hydrogenation, thus being favorable for maintaining the activities of the hydrogenation catalysts and lengthening the running period.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support, particularly there is the preparation method of the alumina support of large pore volume and high-specific surface area.
Background technology
Along with heaviness day by day, the in poor quality of crude oil, oil refining enterprise faces a large amount of weights, Residual cracking Utilizing question.There is organo-metallic compound and the asphalitines such as a large amount of nickel, vanadium and iron in weight, residual oil, above-mentioned metal and asphalitine can cause the blocking of beds hole and reduce catalyst life.A large amount of metal deposits on catalyst tend to make catalyst poisoning or deactivation.In addition, asphalitine is tended to reduce the susceptibility of hydrocarbon desulfurization, and for Hydrobon catalyst, if be applied in containing metal and bitum hydrocarbon material, so, this catalyst is by rapid deactivation and need to change in advance.
In catalytic hydrogenation, the macromolecules adsorption in heavy oil is also deposited on surface or the aperture of catalyst, reaction inside diffusional resistance is increased, causes the apparent activity of catalyst to decline.Meanwhile, containing more coke precursor in weight, residual oil, they can generate coke under certain condition and be deposited in hole and cause the activated centre of catalyst poisoning.Diffuse in catalyst attach most importance to, the governing factor of residual oil catalytic hydrogenation, therefore, catalytic hydrogenation that is heavy, residual oil needs macroporous catalyst, and has larger aperture and pore volume, to hold more carbon deposit, metal deposit etc., reduce the diffusional resistance that macromolecular reaction runs into.The large aperture of catalyst and pore volume mainly rely on the carrier of corresponding large aperture and large pore volume.
Good macropore carrier is on pore-size distribution, except should having the pore-size distribution of the 10 ~ 20nm comparatively concentrated, also should have appropriate macropore, especially be greater than the large pore size distribution of 100nm, with delay large molecule in the catalyst aperture blocking and hold more carbon deposit, metal deposit etc.In addition, for meeting the requirement of commercial Application, macropore carrier also should have enough intensity.But the aperture being generally used for the aluminium oxide preparing hydrotreating catalyst is less, the needs preparing heavy oil, residuum hydrogenating and metal-eliminating catalyst can not be met.Therefore the way of reaming must be adopted in preparation process to obtain macropore.Conventional expanding method adds various types of expanding agent in the forming processes such as plan thin Water oxidize aluminium dry glue powder kneading, extrusion, and the physics expanding agent wherein used at present has the organic substances such as carbon black, Carbon fibe, carbohydrate.
US 4448896 take carbon black as expanding agent, and it is become plastic and extruded moulding with boehmite kneading.In carrier calcination process, expanding agent, through oxidation, burning, progressively with the effusion of gaseous state thing, forms cavity in the carrier, thus forms macropore.But the method amounts of carbon black used is comparatively large, and generally reach more than 20wt%, the mechanical strength of gained carrier is lower, and pore size distribution is disperse comparatively.EP 0237240 adopts Carbon fibe to be that expanding agent prepares macroporous aluminium oxide, but it is low etc. not enough to there is the large and support strength of expanding agent consumption equally.CN 1055877C by adding physics expanding agent if carbon black and chemical enlargement agent are as phosphide in boehmite dry glue powder, shaping by kneading method, gained carrier can a few bore dia be 10 ~ 20nm, but do not form double-pore structure, and the pore volume that the macropore being greater than 100nm has only accounts for about 5% of total pore volume, the support strength that method is obtained thus is simultaneously lower.Thus, when reacting required catalyst requirement carrier and having dual duct and will have higher mechanical strength, this kind of carrier just receives a definite limitation.CN 1768947A is with crops stem shell powder for expanding agent, and addition is the 10wt% ~ 20wt% of aluminium oxide.Although the cost of expanding agent used is comparatively cheap, but due to crops stem shell powder and aluminum oxide dry glue powder compatibility poor, large usage quantity simultaneously, in kneading and compacting process, stem shell powder disperses uneven in plastic, cause the large pore size distribution in carrier also uneven, affect the mechanical strength of macroporous aluminium oxide.
In addition, for the design of industrial catalyst, also higher specific area should be had, to make the concentration of the active sites of catalyst larger.But specific area and aperture are usually the contradiction that opposes.In order to suppress deposit to the deposition in aperture, need larger hole to spread, but larger hole mean lower specific area usually.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method with high-specific surface area, diplopore distribution, alumina support that mechanical strength is high.
The preparation process of alumina support of the present invention, comprising:
(1) NACF is immersed in adsorption equilibrium in inorganic aluminum salting liquid, after filtration, dry; Above-mentioned dipping and dry run repeat 1 ~ 5 time, are preferably 2 ~ 3 times;
(2) the NACF Homogeneous phase mixing after aluminium oxide precursor and step (1) being processed, then adds peptizing agent, through kneading, shaping;
(3) the formed body drying of step (2) gained and roasting, obtain alumina support.
The specific area of the NACF described in step (1) is 600 ~ 1500m
2/ g.In step (2), the addition of the NACF after step (1) process is the 5wt% ~ 30wt% of aluminium oxide precursor weight, is preferably 10wt% ~ 15wt%.Inorganic aluminate described in step (1) is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride, is preferably aluminum nitrate.The concentration of described inorganic aluminum salting liquid is 1wt% ~ 30wt%, is preferably 5wt% ~ 25wt%.
Drying described in step (1) is at 50 ~ 100 DEG C dry 1 ~ 10 hour, preferably first at room temperature dries in the shade 3 ~ 24 hours, then at 50 ~ 100 DEG C dry 1 ~ 10 hour.
Described NACF granularity is 100 ~ 300 orders, is preferably 150 ~ 250 orders.The particle size size of NACF, its order number can be wider scope, but is preferably narrower particle size distribution, to be conducive to the pore size control of aluminium oxide.
Aluminium oxide precursor described in step (2) is boehmite dry glue powder, or be the boehmite dry glue powder of at least one element additive modification in silicon, boron, phosphorus, titanium or zirconium etc., or be other the compound that can be converted into gama-alumina after step (3) roasting, and at least one element additive modification in silicon, boron, phosphorus, titanium or zirconium etc. and the compound of gama-alumina can be converted into after step (3) roasting.
Peptizing agent described in step (2), for common are machine acid and/or inorganic acid, comprises one or more in nitric acid, acetic acid, citric acid, is preferably nitric acid.
Step (2) can also add required shaping assistant raw material as required, as materials such as the sesbania powder as extrusion aid.
The shaping forming method adopting routine described in step (2), comprises extrusion, compressing tablet or balling-up etc.
Drying described in step (3) generally at 100 ~ 120 DEG C dry 1 ~ 4 hour, preferentially at room temperature dries in the shade 10 ~ 24 hours, is then warming up to 100 ~ 120 DEG C of dryings 1 ~ 4 hour.Roasting process is roasting 2 ~ 10 hours at 500 ~ 850 DEG C, and the heating rate of roasting process is preferably less than 30 DEG C/h.
The character of the alumina support of the inventive method gained is as follows: pore volume is 0.6 ~ 1.5ml/g, and specific area is 200 ~ 450m
2/ g, bore dia accounts for 60% ~ 75% of total pore volume at the pore volume of 10 ~ 20nm, and the pore volume that bore dia is greater than 100nm accounts for 5% ~ 15% of total pore volume, and crushing strength is 100 ~ 140N/mm.
The NACF that the present invention uses is a kind of sorbing material efficiently, is widely used in various field.It has great specific area, reaches 600 ~ 1500m
2/ g, bore dia mainly concentrates on 0.5 ~ 5.0nm, and adsorption capacity is 100 times of plain particles active carbon.NACF used by the present invention is except as except expanding agent, and because it is rich in flourishing microcellular structure, specific area is high, has the ability of strong absorption inorganic aluminum salting liquid.The inorganic aluminate be adsorbed in NACF duct is converted into aluminium oxide precursor when drying.After NACF and aluminium oxide precursor kneading and compacting, in roasting process, NACF is oxidized gradually, decomposes, overflows, and participates in the generation of macropore.Aluminium oxide precursor in NACF duct is then converted into alumina nanoparticles along with the burn off gradually of NACF; these nano particles along with around charcoal protective layer disappearance and assemble; final reunion in the macropore duct formed by NACF is offspring; these inorganic aluminates change into alumina nanoparticles and the offspring that generates can form abundant pore structure; thus forming higher specific area, agglomerated particles can also play the effect supporting large hole strength simultaneously.
The present invention by slowly controlling programming rate, makes NACF oxidation Decomposition step by step in intensification roasting process, therefore less on the impact of the mechanical strength of carrier after roasting, can not reduce the intensity of carrier while obtaining macropore.
The specific area of the alumina support of the inventive method gained is higher, and bore dia accounts for 60% ~ 75% of total pore volume at the pore volume of 10 ~ 20nm, distributes comparatively concentrated, for the preparation of heavy, residual oil hydrocatalyst, is very beneficial for removing large molecular impurity in weight, residual oil.Alumina support of the present invention is except having the concentrated pore size distribution of 10 ~ 20nm, the macropore pore volume of 100nm is also greater than containing part, this is conducive to the raising delaying inside diffusional resistance in weight, residual hydrogenation, thus is conducive to keeping activity of hydrocatalyst and extending service cycle.
Detailed description of the invention
In the present invention, specific area, pore volume and pore size distribution adopt low temperature liquid nitrogen determination of adsorption method, and crushing strength is according to HG/T 2782-1996 standard, adopts QCY-602 type catalyst strength analyzer to measure.Below in conjunction with embodiment, the inventive method is described further.
Embodiment 1
The pretreatment of NACF.100 ~ 150 object NACF 10 grams after grinding, its specific area is 856 m
2/ g, impregnated in concentration is in the aluminum nitrate solution of 5wt%, until adsorption equilibrium.After the active carbon fibre dimensional filter after absorption, dry in the shade under room temperature, then at 60 DEG C dry 10 hours.Dry complete, above-mentioned dipping absorption and dry run are repeated 3 times.The NACF of gained is designated as ACF1;
In like manner, the character of NACF and pretreatment condition are in table 1.
The character of table 1 NACF and pretreatment condition
| Order number | Specific area *，m 2/g | Aluminum nitrate concentration, wt% | Baking temperature and time, DEG C/h | Number of repetition | |
| ACF1 | 100~150 | 856 | 5 | 60/10 | 3 |
| ACF2 | 150~200 | 930 | 15 | 60/10 | 3 |
| ACF3 | 200~300 | 1087 | 20 | 80/8 | 2 |
| ACF4 | 200~300 | 894 | 25 | 80/8 | 2 |
| ACF5 | 250~300 | 1340 | 25 | 100/2 | 2 |
* the specific area of undressed NACF
Embodiment 2
Boehmite dry glue powder 100 grams, NACF ACF1 10 grams, 5 grams, sesbania powder, after mixing under dry state, then to add concentration be gradually 3.5wt% dust technology 140ml, and then moving in banded extruder through abundant kneading is after plastic, is extruded into stripe shape.Extrudate, at room temperature after dried overnight, is dried 4 hours at 110 DEG C.Drying sample is placed in high temperature furnace, is warming up to 550 DEG C with the speed of 10 DEG C/h, and constant temperature 6 hours, the naturally obtained alumina support of cooling at such a temperature.
Embodiment 3
Boehmite dry glue powder 150 grams, NACF ACF2 15 grams, 4 grams, sesbania powder, after mixing under dry state, then to add concentration be gradually 3.5wt% dust technology 140ml, and then moving in banded extruder through abundant kneading is after plastic, is extruded into stripe shape.After extrudate dry at room temperature over night, dry 4 hours at 110 DEG C.Drying sample is placed in high temperature furnace, is warming up to 650 DEG C with the speed of 10 DEG C/h, and constant temperature 6 hours, the naturally obtained alumina support of cooling at such a temperature.
Embodiment 4
Boehmite dry glue powder 150 grams, NACF ACF3 22 grams, 6 grams, sesbania powder, after mixing under dry state, then to add concentration be gradually 3.5wt% dust technology 145ml, and then moving in banded extruder through abundant kneading is after plastic, is extruded into stripe shape.After extrudate dry at room temperature over night, dry 4 hours at 120 DEG C.Drying sample is placed in high temperature furnace, is warming up to 750 DEG C with the speed of 10 DEG C/h, and constant temperature 6 hours, the naturally obtained alumina support of cooling at such a temperature.
Embodiment 5
Boehmite dry glue powder 150 grams, NACF ACF4 22 grams, 6 grams, sesbania powder, after mixing under dry state, then to add concentration be gradually 3.5wt% dust technology 145ml, and finally moving in banded extruder through abundant kneading is after plastic, is extruded into stripe shape.After extrudate dry at room temperature over night, dry 4 hours at 120 DEG C.Drying sample is placed in high temperature furnace, is warming up to 750 DEG C with the speed of 10 DEG C/h, and constant temperature 6 hours, the naturally obtained alumina support of cooling at such a temperature.
Embodiment 6
Boehmite dry glue powder 150 grams, NACF ACF5 22 grams, 6 grams, sesbania powder, after mixing under dry state, then to add concentration be gradually 3.5wt% dust technology 145ml, and finally moving in banded extruder through abundant kneading is after plastic, is extruded into stripe shape.After extrudate dry at room temperature over night, dry 4 hours at 120 DEG C.Drying sample is placed in high temperature furnace, is warming up to 850 DEG C with the speed of 10 DEG C/h, and constant temperature 4 hours, the naturally obtained alumina support of cooling at such a temperature.
Comparative example 1
Boehmite dry glue powder 100 grams, 100 ~ 150 order NACFs 10 grams, 5 grams, sesbania powder, after mixing under dry state, then to add concentration be gradually 3.5wt% dust technology 140ml, and then moving in banded extruder through abundant kneading is after plastic, is extruded into stripe shape.Extrudate, at room temperature after dried overnight, is dried 4 hours at 110 DEG C.Drying sample is placed in high temperature furnace, is warming up to 550 DEG C with the speed of 10 DEG C/h, and constant temperature 6 hours, the naturally obtained alumina support of cooling at such a temperature.
Comparative example 1 is compared with embodiment 2, and when activated carbon fiber is without pretreatment, specific surface and the pore volume of products therefrom decline all to some extent.In pore size distribution, the micropore being less than 10nm and the pore size distribution being greater than 100nm improve, but the pore size distribution of 10-20nm declines to a great extent, therefore for being unfavorable for the raising of catalyst activity during catalyst carrier.
The physico-chemical property of table 2 alumina support
| Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | |
| Pore volume, ml/g | 0.71 | 0.85 | 1.12 | 1.36 | 1.55 | 0.60 |
| Specific area, m 2/g | 213 | 245 | 439 | 269 | 245 | 190 |
| Crushing strength, N/mm | 135 | 132 | 121 | 113 | 112 | 119 |
| Pore size distribution % | ||||||
| <10nm | 13 | 15 | 14 | 16 | 15 | 18 |
| 10~20nm | 63 | 65 | 70 | 72 | 69 | 45 |
| >100nm | 5 | 6 | 8 | 9 | 12 | 17 |
Claims (12)
1. a preparation process for alumina support, comprising:
(1) NACF is immersed in adsorption equilibrium in inorganic aluminum salting liquid, after filtration, dry; Above-mentioned dipping and dry run repeat 1 ~ 5 time; The specific area of described NACF is 600 ~ 1500m
2/ g, granularity is 100 ~ 300 orders;
(2) the NACF Homogeneous phase mixing after alumina precursor and step (1) being processed, then adds peptizing agent, through kneading, shaping; The addition of the NACF after step (1) process is the 5wt% ~ 30wt% of aluminum oxide precursor body weight;
(3) the formed body drying of step (2) gained and roasting, obtain alumina support.
2. the drying that in accordance with the method for claim 1, it is characterized in that described in step (1) is at 50 ~ 100 DEG C dry 1 ~ 10 hour.
3. in accordance with the method for claim 1, it is characterized in that drying described in step (1) is first at room temperature dried in the shade 3 ~ 24 hours, and then at being warmed up to 50 ~ 100 DEG C dry 1 ~ 10 hour.
4. in accordance with the method for claim 1, it is characterized in that in step (2), the addition of the NACF after step (1) process is the 10wt% ~ 15wt% of aluminum oxide precursor body weight.
5. the inorganic aluminate that in accordance with the method for claim 1, it is characterized in that described in step (1) is one or more in aluminum nitrate, aluminum sulfate, aluminium chloride; The concentration of described inorganic aluminum salting liquid is 1 wt% ~ 30wt%.
6. in accordance with the method for claim 1, it is characterized in that the alumina precursor described in step (2) is boehmite dry glue powder, or be the boehmite dry glue powder of at least one element additive modification in silicon, boron, phosphorus, titanium, zirconium, or be other the compound that can be converted into gama-alumina after step (3) roasting, and through at least one element additive modification in silicon, boron, phosphorus, titanium, zirconium and the compound of gama-alumina can be converted into after step (3) roasting.
7. in accordance with the method for claim 1, it is characterized in that the peptizing agent described in step (2) is organic acid and/or inorganic acid.
8. the peptizing agent that in accordance with the method for claim 1, it is characterized in that described in step (2) is one or more in nitric acid, acetic acid, citric acid.
9. in accordance with the method for claim 1, it is characterized in that step (2) adds required shaping assistant raw material as required.
10. in accordance with the method for claim 1, it is characterized in that drying described in step (3) at 100 ~ 120 DEG C dry 1 ~ 4 hour, roasting process is roasting 2 ~ 10 hours at 500 ~ 850 DEG C.
11. in accordance with the method for claim 1, it is characterized in that the drying described in step (3) is at room temperature dried in the shade 10 ~ 24 hours, be then warming up to 100 ~ 120 DEG C of dryings 1 ~ 4 hour, and roasting process is roasting 2 ~ 10 hours at 500 ~ 850 DEG C.
12. in accordance with the method for claim 1, it is characterized in that, in step (3), the heating rate of roasting process is less than 30 DEG C/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110322448.1A CN103055947B (en) | 2011-10-21 | 2011-10-21 | Preparation method of alumina support |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110322448.1A CN103055947B (en) | 2011-10-21 | 2011-10-21 | Preparation method of alumina support |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103055947A CN103055947A (en) | 2013-04-24 |
| CN103055947B true CN103055947B (en) | 2015-04-15 |
Family
ID=48099014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110322448.1A Active CN103055947B (en) | 2011-10-21 | 2011-10-21 | Preparation method of alumina support |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103055947B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437664B (en) * | 2013-09-16 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of method preparing alpha-alumina supports |
| CN103818939B (en) * | 2014-01-14 | 2016-06-08 | 杜云峰 | Hydrogen peroxide fluid bed special aluminium oxide and production technology |
| CN103818938B (en) * | 2014-02-27 | 2016-05-04 | 昆明铂生金属材料加工有限公司 | A kind of preparation method of high thermal stability modified aluminium oxide supports |
| CN105709852B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of preparation method of alumina supporter with high specific surface area |
| CN104874383B (en) * | 2015-04-30 | 2017-07-11 | 大连理工大学 | It is a kind of to be used to catalyze and synthesize difunction catalyst of methyl acrylate and preparation method thereof |
| WO2018069772A1 (en) * | 2016-10-12 | 2018-04-19 | The Hong Kong University Of Science And Technology | Lightweight and highly tough aluminum composite with ceramic matrix |
| CN110935430B (en) * | 2018-09-25 | 2023-01-10 | 中国石油化工股份有限公司 | Titanium modified macroporous alumina and preparation method thereof |
| CN110860281B (en) * | 2019-11-22 | 2021-05-18 | 大连理工大学 | Preparation method of rod-shaped alumina carrier and alumina carrier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62201643A (en) * | 1986-02-28 | 1987-09-05 | Nippon Oil Co Ltd | Production of hydrogenation catalyst |
| US4923843A (en) * | 1986-09-25 | 1990-05-08 | Aluminum Company Of America | Peptized activated carbon/alumina composite |
| CN1103009A (en) * | 1993-11-23 | 1995-05-31 | 中国石油化工总公司 | Preparing method for aluminium oxide carrier with double-hole |
| CN101462074A (en) * | 2007-12-19 | 2009-06-24 | 中国石油化工股份有限公司 | Alumina supporter and preparation method thereof |
-
2011
- 2011-10-21 CN CN201110322448.1A patent/CN103055947B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62201643A (en) * | 1986-02-28 | 1987-09-05 | Nippon Oil Co Ltd | Production of hydrogenation catalyst |
| US4923843A (en) * | 1986-09-25 | 1990-05-08 | Aluminum Company Of America | Peptized activated carbon/alumina composite |
| CN1103009A (en) * | 1993-11-23 | 1995-05-31 | 中国石油化工总公司 | Preparing method for aluminium oxide carrier with double-hole |
| CN101462074A (en) * | 2007-12-19 | 2009-06-24 | 中国石油化工股份有限公司 | Alumina supporter and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103055947A (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055947B (en) | Preparation method of alumina support | |
| CN102441368B (en) | Method for preparing hydro-demetalization catalyst for heavy oil | |
| CN102847541B (en) | Coal tar hydrodemetalization catalyst and preparation method thereof | |
| TWI745434B (en) | Porous carbon material,method for producing the same,and catalyst for synthesis reaction | |
| CN103785401B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN102921473A (en) | Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof | |
| CN101362072A (en) | Absorbent for removing trace benzene in carbon dioxide and preparation method thereof | |
| Pan et al. | New composite aerogel-like adsorbents for thiophene based on π-complexation | |
| KR20150028301A (en) | Improved resid hydrotreating catalyst containing titania | |
| CN108671934B (en) | Preparation method of hydrofining catalyst with high mechanical strength | |
| CN103769179A (en) | Preparation method of residual oil hydro-treatment catalyst | |
| CN102728335A (en) | Preparation method of boron-modified alumina carrier | |
| CN113042109A (en) | Ozone catalyst carrier and preparation method thereof | |
| CN103316675B (en) | Preparation method of Pt-Sn reforming catalyst | |
| CN103240117A (en) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method | |
| CN103055949B (en) | Preparation method of macroporous alumina support | |
| CN102049270A (en) | Selective hydrogenation catalyst for gasoline and preparation method thereof | |
| CN102861588B (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
| CN101913912A (en) | Method for coating cordierite honeycomb | |
| CN108927146B (en) | Inferior heavy oil hydrogenation catalyst and preparation method thereof | |
| CN104549345A (en) | Active hydrocracking proppant and preparation method thereof | |
| CN112642486B (en) | MOF-253 encapsulated metal nanoparticle catalyst and preparation method and application thereof | |
| JP2016050132A (en) | Alumina particle | |
| CN104028215B (en) | A kind of gasoline high-selectivity adsorption desulfurizing agent and its preparation method and application | |
| CN104275198A (en) | Preparation method of multi-metal reforming catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |