CN103055947A - Preparation method of alumina support - Google Patents
Preparation method of alumina support Download PDFInfo
- Publication number
- CN103055947A CN103055947A CN2011103224481A CN201110322448A CN103055947A CN 103055947 A CN103055947 A CN 103055947A CN 2011103224481 A CN2011103224481 A CN 2011103224481A CN 201110322448 A CN201110322448 A CN 201110322448A CN 103055947 A CN103055947 A CN 103055947A
- Authority
- CN
- China
- Prior art keywords
- accordance
- nacf
- drying
- alumina support
- dry
- 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.)
- Granted
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 have the preparation method of the alumina support of large pore volume and high-specific surface area.
Background technology
Along with day by day heaviness, the in poor quality of crude oil, oil refining enterprise faces a large amount of weights, residual oil processing and utilization problem.Have organo-metallic compound and the asphalitines such as a large amount of nickel, vanadium and iron in weight, the residual oil, above-mentioned metal and asphalitine can cause the obstruction of beds hole and reduce catalyst life.A large amount of metal deposits on the catalyst tend to make catalyst poisoning or deactivation.In addition, asphalitine tends 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 with rapid deactivation and need in advance replacing.
In the catalytic hydrogenation process, the macromolecules adsorption in the heavy oil also is deposited on surface or the aperture of catalyst, and the reaction inside diffusional resistance is increased, and causes the apparent activity of catalyst to descend.Simultaneously, contain more coke precursor in weight, the residual oil, they can generate coke under certain condition and be deposited on the activated centre that causes catalyst in the hole poisons.Diffuse in the catalyst attach most importance to, the governing factor of residual oil catalytic hydrogenation process, therefore, catalytic hydrogenation heavy, residual oil needs macroporous catalyst, and has larger aperture and pore volume, in order 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 the pore-size distribution that should have the 10 ~ 20nm that comparatively concentrates, also should have an amount of macropore, especially greater than the large pore size distribution of 100nm, with the obstruction that delays large molecule aperture in catalyst with hold more carbon deposit, metal deposit etc.In addition, for satisfying the requirement of commercial Application, macropore carrier also should have enough intensity.Yet the aperture of aluminium oxide that is generally used for preparing hydrotreating catalyst is less, can not satisfy the needs of preparation heavy oil, residuum hydrogenating and metal-eliminating catalyst.Therefore must in preparation process, adopt the way of reaming to obtain macropore.Expanding method commonly used is to add various types of expanding agents in intending the forming processes such as thin water aluminum oxide dry glue powder kneading, extrusion, and the physics expanding agent of wherein using at present has the organic substances such as carbon black, charcoal fiber, carbohydrate.
US 4448896 becomes plastic and extruded moulding with it with the boehmite kneading take carbon black as expanding agent.In the carrier roasting process, expanding agent is progressively overflowed with the gaseous state thing through oxidation, burning, forms the cavity in carrier, thereby consists of macropore.But the used amounts of carbon black of the method is larger, generally reaches more than the 20wt%, and the mechanical strength of gained carrier is lower, and pore size distribution is disperse comparatively.It is that expanding agent prepares macroporous aluminium oxide that EP 0237240 adopts the charcoal fiber, but exists equally the expanding agent consumption to reach greatly the low deficiency that waits of support strength.CN 1055877C is by adding physics expanding agent such as carbon black and chemical enlargement agent such as phosphide in the boehmite dry glue powder, by the kneading method moulding, the gained carrier can several bore dias be 10 ~ 20nm, but do not form double-pore structure, and only accounting for about 5% of total pore volume greater than the pore volume that the macropore of 100nm has, the support strength that makes of method is lower thus simultaneously.Thereby when the required catalyst of reaction required carrier to have dual duct and will higher mechanical strength be arranged, this kind carrier just had been subject to certain limitation.CN 1768947A is take crops stem shell powder as expanding agent, and addition is the 10wt%～20wt% of aluminium oxide.Although the cost of used expanding agent is comparatively cheap, but because crops stem shell powder and aluminum oxide dry glue powder compatibility are relatively poor, the while large usage quantity, stem shell powder disperses inhomogeneous in plastic in the kneading and compacting process, cause the large pore size distribution in the carrier also inhomogeneous, affect the mechanical strength of macroporous aluminium oxide.
In addition, for the design of industrial catalyst, also should have higher specific area, in order to make the concentration of active sites of catalyst larger.Yet specific area and aperture usually are opposition contradiction.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 alumina support that high-specific surface area, diplopore distribute, mechanical strength is high.
The preparation process of alumina support of the present invention comprises:
(1) NACF is immersed in the inorganic aluminum salting liquid to adsorption equilibrium, after filtration, drying; Above-mentioned dipping and dry run repeat 1 ~ 5 time, are preferably 2 ~ 3 times;
(2) NACF after aluminium oxide precursor and step (1) are processed evenly mixes, and then adds peptizing agent, through kneading, and moulding;
(3) formed body drying and the roasting of step (2) gained obtain alumina support.
The specific area of the described NACF of step (1) is 600 ~ 1500m
2/ g.In the step (2), the addition of the NACF after step (1) is processed is the 5wt% ~ 30wt% of aluminium oxide precursor weight, is preferably 10wt% ~ 15wt%.The described inorganic aluminate of step (1) is one or more in aluminum nitrate, aluminum sulfate, the aluminium chloride, is preferably aluminum nitrate.The concentration of described inorganic aluminum salting liquid is 1wt% ~ 30wt%, is preferably 5wt% ~ 25wt%.
The described drying of step (1) be 50 ~ 100 ℃ lower dry 1 ~ 10 hour, preferably at room temperature dried in the shade 3 ~ 24 hours first, then lower dry 1 ~ 10 hour at 50 ~ 100 ℃.
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 aperture control of aluminium oxide.
The described aluminium oxide precursor of step (2) is the boehmite dry glue powder, it perhaps is the boehmite dry glue powder of at least a element additive modification in silicon, boron, phosphorus, titanium or zirconium etc., perhaps for other after step (3) roasting, can be converted into the gamma oxidation Aluminum Compounds, and at least a element additive modification in silicon, boron, phosphorus, titanium or zirconium etc. and through being converted into the gamma oxidation Aluminum Compounds after step (3) roasting.
The described peptizing agent of step (2) comprises in nitric acid, acetic acid, the citric acid one or more for common are machine acid and/or inorganic acid, is preferably nitric acid.
Step (2) can also add required shaping assistant raw material as required, such as the materials such as sesbania powder as extrusion aid.
The described moulding of step (2) can be adopted conventional forming method, comprises extrusion, compressing tablet or balling-up etc.
The described drying of step (3) was generally descended dry 1 ~ 4 hour at 100 ~ 120 ℃, preferentially at room temperature dried in the shade 10 ~ 24 hours, then was warming up to 100 ~ 120 ℃ of dryings 1 ~ 4 hour.Roasting process is that the heating rate of roasting process was preferably less than 30 ℃/hour 500 ~ 850 ℃ of lower roastings 2 ~ 10 hours.
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 bore dia accounts for 5% ~ 15% of total pore volume greater than the pore volume of 100nm, and crushing strength is 100 ~ 140N/mm.
The NACF that the present invention uses is a kind of efficient sorbing material, is widely used in various fields.It has great specific area, reaches 600 ~ 1500m
2/ g, bore dia mainly concentrate on 0.5 ~ 5.0nm, and adsorption capacity is 100 times of plain particles active carbon.The used NACF of the present invention is except as the expanding agent, 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 that is adsorbed in the NACF duct is converted into the aluminium oxide precursor when drying.Behind NACF and the aluminium oxide precursor kneading and compacting, gradually oxidation of NACF, decomposition, effusion in roasting process participate in the generation of macropore.Aluminium oxide precursor in the NACF duct then is converted into the aluminium oxide nano particle along with the gradually burn off of NACF; these nano particles are along with the disappearance of charcoal protective layer on every side and assemble; the final reunion in the macropore duct that is formed by NACF is offspring; these inorganic aluminates change into the aluminium oxide nano particle and the offspring that generates can form abundant pore structure; thereby form higher specific area, agglomerated particles can also play the effect of supporting large hole strength simultaneously.
The present invention by slow control programming rate, makes step by step oxidation Decomposition of NACF in the intensification roasting process, therefore less on the impact of the mechanical strength of carrier after the roasting, can not reduce the intensity of carrier when 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, the residual oil.Alumina support of the present invention is except having the concentrated pore size distribution of 10 ~ 20nm, also contain part greater than the macropore pore volume of 100nm, this is conducive to delay the raising of inside diffusional resistance in weight, the residual hydrogenation, thereby is conducive to keep activity of hydrocatalyst and prolongs service cycle.
The specific embodiment
Specific area, pore volume and pore size distribution are to adopt the low temperature liquid nitrogen determination of adsorption method among the present invention, and crushing strength is according to HG/T 2782-1996 standard, adopt QCY-602 type catalyst strength analyzer to measure.Below in conjunction with embodiment the inventive method is described further.
Embodiment 1
The preliminary treatment of NACF.100 ~ 150 purpose NACFs, 10 grams after will grinding, its specific area is 856 m
2/ g impregnated in the aluminum nitrate solution that concentration is 5wt%, until adsorption equilibrium.Behind the active carbon fibre dimensional filter after the absorption, dry in the shade under the room temperature, then 60 ℃ were descended 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 see Table 1.
The character of table 1 NACF and pretreatment condition
| ? | The order number | Specific area *，m 2/g | Aluminum nitrate concentration, wt% | Baking temperature and time, ℃/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 gram, NACF ACF1 10 grams, sesbania powder 5 grams, after mixing under the dry state, adding gradually concentration is the rare nitric acid 140ml of 3.5wt% again, then moves in the banded extruder after abundant kneading is plastic, is extruded into stripe shape.Extrudate is at room temperature after the dried overnight, in 110 ℃ of lower oven dry 4 hours.Drying sample is placed high temperature furnace, is warming up to 550 ℃ with 10 ℃/hour speed, and under this temperature constant temperature 6 hours, cooling makes alumina support naturally.
Embodiment 3
Boehmite dry glue powder 150 gram, NACF ACF2 15 grams, sesbania powder 4 grams, after mixing under the dry state, adding gradually concentration is the rare nitric acid 140ml of 3.5wt% again, then moves in the banded extruder after abundant kneading is plastic, is extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 110 ℃ under the extrudate room temperature.Drying sample is placed high temperature furnace, is warming up to 650 ℃ with 10 ℃/hour speed, and under this temperature constant temperature 6 hours, cooling makes alumina support naturally.
Embodiment 4
Boehmite dry glue powder 150 gram, NACF ACF3 22 grams, sesbania powder 6 grams, after mixing under the dry state, adding gradually concentration is the rare nitric acid 145ml of 3.5wt% again, then moves in the banded extruder after abundant kneading is plastic, is extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 120 ℃ under the extrudate room temperature.Drying sample is placed high temperature furnace, is warming up to 750 ℃ with 10 ℃/hour speed, and under this temperature constant temperature 6 hours, cooling makes alumina support naturally.
Embodiment 5
Boehmite dry glue powder 150 gram, NACF ACF4 22 grams, sesbania powder 6 grams, after mixing under the dry state, adding gradually concentration is the rare nitric acid 145ml of 3.5wt% again, moves at last in the banded extruder after abundant kneading is plastic, is extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 120 ℃ under the extrudate room temperature.Drying sample is placed high temperature furnace, is warming up to 750 ℃ with 10 ℃/hour speed, and under this temperature constant temperature 6 hours, cooling makes alumina support naturally.
Embodiment 6
Boehmite dry glue powder 150 gram, NACF ACF5 22 grams, sesbania powder 6 grams, after mixing under the dry state, adding gradually concentration is the rare nitric acid 145ml of 3.5wt% again, moves at last in the banded extruder after abundant kneading is plastic, is extruded into stripe shape.After the dried overnight, oven dry is 4 hours under 120 ℃ under the extrudate room temperature.Drying sample is placed high temperature furnace, is warming up to 850 ℃ with 10 ℃/hour speed, and under this temperature constant temperature 4 hours, cooling makes alumina support naturally.
Comparative example 1
Boehmite dry glue powder 100 gram, 100 ~ 150 order NACFs, 10 grams, sesbania powder 5 grams, after mixing under the dry state, adding gradually concentration is the rare nitric acid 140ml of 3.5wt% again, then moves in the banded extruder after abundant kneading is plastic, is extruded into stripe shape.Extrudate is at room temperature after the dried overnight, in 110 ℃ of lower oven dry 4 hours.Drying sample is placed high temperature furnace, is warming up to 550 ℃ with 10 ℃/hour speed, and under this temperature constant temperature 6 hours, cooling makes alumina support naturally.
Comparative example 1 is compared with embodiment 2, and activated carbon fiber is during without preliminary treatment, and the specific surface of products therefrom and pore volume all descend to some extent.In pore size distribution, improve less than the micropore of 10nm with greater than the pore size distribution of 100nm, but the pore size distribution of 10-20nm declines to a great extent, be unfavorable for the raising of catalyst activity when therefore being used for 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 (14)
1. the preparation process of an alumina support comprises:
(1) NACF is immersed in the inorganic aluminum salting liquid to adsorption equilibrium, after filtration, drying; Above-mentioned dipping and dry run repeat 1 ~ 5 time;
(2) NACF after aluminium oxide precursor and step (1) are processed evenly mixes, and then adds peptizing agent, through kneading, and moulding;
(3) formed body drying and the roasting of step (2) gained obtain alumina support.
2. the specific area that in accordance with the method for claim 1, it is characterized in that the described NACF of step (1) is 600 ~ 1500m
2/ g, granularity is 100 ~ 300 orders.
3. in accordance with the method for claim 1, it is characterized in that the described drying of step (1) is lower dry 1 ~ 10 hour at 50 ~ 100 ℃.
4. in accordance with the method for claim 1, it is characterized in that described dry at room temperature the drying in the shade 3 ~ 24 hours first of step (1), and then be warmed up to 50 ~ 100 ℃ of lower dryings 1 ~ 10 hour.
5. in accordance with the method for claim 1, it is characterized in that in the step (2), the addition of the NACF after step (1) is processed is the 5wt% ~ 30wt% of aluminium oxide precursor weight.
6. in accordance with the method for claim 1, it is characterized in that in the step (2), the addition of the NACF after step (1) is processed is the 10wt% ~ 15wt% of aluminium oxide precursor weight.
7. in accordance with the method for claim 1, it is characterized in that the described inorganic aluminate of step (1) is one or more in aluminum nitrate, aluminum sulfate, the aluminium chloride; The concentration of described inorganic aluminum salting liquid is 1 wt% ~ 30wt%.
8. in accordance with the method for claim 1, it is characterized in that the described aluminium oxide precursor of step (2) is the boehmite dry glue powder, it perhaps is the boehmite dry glue powder of at least a element additive modification in silicon, boron, phosphorus, titanium, zirconium, perhaps for other after step (3) roasting, can be converted into the gamma oxidation Aluminum Compounds, and at least a element additive modification in silicon, boron, phosphorus, titanium, zirconium and through being converted into the gamma oxidation Aluminum Compounds after step (3) roasting.
9. in accordance with the method for claim 1, it is characterized in that the described peptizing agent of step (2) is organic acid and/or inorganic acid.
10. in accordance with the method for claim 1, it is characterized in that the described peptizing agent of step (2) is one or more in nitric acid, acetic acid, the citric acid.
11. in accordance with the method for claim 1, it is characterized in that step (2) adds required shaping assistant raw material as required.
12. in accordance with the method for claim 1, it is characterized in that the described drying of step (3) at 100 ~ 120 ℃ times dry 1 ~ 4 hour, roasting process is 500 ~ 850 ℃ of lower roastings 2 ~ 10 hours.
13. in accordance with the method for claim 1, it is characterized in that the described drying of step (3) at room temperature dried in the shade 10 ~ 24 hours, then be warming up to 100 ~ 120 ℃ of dryings 1 ~ 4 hour, roasting process is 500 ~ 850 ℃ of lower roastings 2 ~ 10 hours.
14. in accordance with the method for claim 1, it is characterized in that the heating rate of roasting process is less than 30 ℃/hour in the step (3).
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 true CN103055947A (en) | 2013-04-24 |
| CN103055947B 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) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103818939A (en) * | 2014-01-14 | 2014-05-28 | 淄博贝格工贸有限公司 | Aluminum oxide specially used for hydrogen peroxide fluidized bed and production technology for aluminum oxide |
| CN103818938A (en) * | 2014-02-27 | 2014-05-28 | 昆明铂生金属材料加工有限公司 | Preparation method for modified alumina supporter with high thermal stability |
| CN104437664A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for preparing alpha-alumina carrier |
| CN104874383A (en) * | 2015-04-30 | 2015-09-02 | 大连理工大学 | Acid-base bifunctional catalyst used for catalytic synthesis of methyl acrylate and preparation method thereof |
| CN105709852A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for alumina carrier with high specific surface area |
| 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 |
| CN110860281A (en) * | 2019-11-22 | 2020-03-06 | 大连理工大学 | Preparation method of rod-shaped alumina carrier and alumina carrier |
| CN110935430A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Titanium modified macroporous alumina and preparation method thereof |
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 |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437664A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for preparing alpha-alumina carrier |
| 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 |
| CN103818939A (en) * | 2014-01-14 | 2014-05-28 | 淄博贝格工贸有限公司 | Aluminum oxide specially used for hydrogen peroxide fluidized bed and production technology for aluminum oxide |
| CN103818939B (en) * | 2014-01-14 | 2016-06-08 | 杜云峰 | Hydrogen peroxide fluid bed special aluminium oxide and production technology |
| CN103818938A (en) * | 2014-02-27 | 2014-05-28 | 昆明铂生金属材料加工有限公司 | Preparation method for modified alumina supporter with high thermal stability |
| CN105709852A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method for alumina carrier with high specific surface area |
| 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 |
| CN104874383A (en) * | 2015-04-30 | 2015-09-02 | 大连理工大学 | Acid-base bifunctional catalyst used for catalytic synthesis 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 |
| CN110935430A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Titanium modified macroporous alumina and preparation method thereof |
| 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 |
| CN110860281A (en) * | 2019-11-22 | 2020-03-06 | 大连理工大学 | Preparation method of rod-shaped alumina carrier and alumina carrier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103055947B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103055947B (en) | Preparation method of alumina support | |
| Samiyammal et al. | Adsorption of brilliant green dye onto activated carbon prepared from cashew nut shell by KOH activation: Studies on equilibrium isotherm | |
| CN102441368B (en) | Method for preparing hydro-demetalization catalyst for heavy oil | |
| CN102847541B (en) | Coal tar hydrodemetalization catalyst and preparation method thereof | |
| CN110639466B (en) | A kind of dearsenic adsorbent and preparation method thereof | |
| CN102441436B (en) | Preparation method for alumina carrier | |
| CN103785401B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating catalyst | |
| CN106140182B (en) | A kind of preparation method of heavy oil hydrogenating treatment catalyst | |
| CN101041436A (en) | Special activated charcoal for gasoline vapor adsorption and preparation method thereof | |
| CN102921473A (en) | Novel nitrogen-modified carbon catalyst carrier and preparation method and use thereof | |
| CN1853785A (en) | Silicon and boron contained alumina carrier and production thereof | |
| CN113042109A (en) | Ozone catalyst carrier and preparation method thereof | |
| CN103240117B (en) | Gasoline desulfurization catalyst and preparation method thereof and gasoline desulfurization method | |
| CN103657667A (en) | Preparation method for novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures | |
| CN102861618A (en) | Preparation method of alumina supporter | |
| CN106925214A (en) | FCC gasoline adsorption dearsenic agent and preparation method thereof | |
| CN103769179A (en) | Preparation method of residual oil hydro-treatment catalyst | |
| CN103041870B (en) | Alumina supporter, and preparation method and application thereof | |
| CN102861615A (en) | Preparation method of macroporous alumina carrier | |
| CN102728335A (en) | Preparation method of boron-modified alumina carrier | |
| CN108671934B (en) | A kind of preparation method of high mechanical strength hydrotreating catalyst | |
| CN105833879B (en) | Hydrotreating catalyst and preparation method and application thereof | |
| CN103316675A (en) | Preparation method of Pt-Sn reforming catalyst | |
| CN103055949B (en) | Preparation method of macroporous alumina support | |
| CN112619609A (en) | Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof |
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 |