CN105582952A - Preparation method of rare-earth-containing hydrodemetallization catalyst - Google Patents
Preparation method of rare-earth-containing hydrodemetallization catalyst Download PDFInfo
- Publication number
- CN105582952A CN105582952A CN201410563745.9A CN201410563745A CN105582952A CN 105582952 A CN105582952 A CN 105582952A CN 201410563745 A CN201410563745 A CN 201410563745A CN 105582952 A CN105582952 A CN 105582952A
- Authority
- CN
- China
- Prior art keywords
- accordance
- catalyst
- carbon black
- weight
- roasting
- 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 a rare-earth-containing hydrodemetallization catalyst. The preparation method includes the following steps: 1) respectively impregnating carbon black powder with a part of an active component impregnation solution and a solution containing rare earth metal elements, and drying the carbon black powder for later use; 2) performing mix-kneading to the impregnated carbon black powder in the step 1) with pseudo-boehmite dry glue powder, a chemical pore-enlarging agent, an extrusion additive and a peptizer to form a plastic body, and bar-extruding, drying and roasting the plastic body to obtain a modified alumina carrier containing the active components and rare earths; and 3) supporting the rest of active component onto the modified alumina carrier, and drying and roasting the modified alumina carrier to prepare the hydrodemetallization catalyst. In the catalyst, active metals are high in content at macro pores and are low in content at micro pores, and the thermal stability of the macro pores is significantly improved, so that the hydrodemetallization catalyst is high in activity and has long-period operation stability.
Description
Technical field
The present invention relates to a kind of preparation method containing rare earth Hydrodemetalation catalyst.
Background technology
Along with the raising that raw material deep processing in world wide requires, main energy sources structure is gradually to large molecule and high-carbon future development, all the more so for China of the general heaviness of crude oil. The problem such as catalyst activity reduction or inactivation that heavy oil component is excessive at catalyst duct inside diffusional resistance in order effectively to solve, beavy metal impurity deposition and coking cause, an urgent demand possesses large pore volume and wide-aperture characteristic at the widely used alumina support of the industries such as petrochemical industry. Large aperture is conducive to macromolecular compound to catalyst granules diffusion inside, and macropore volume is conducive to improve metal or the coke ability held.
CN1206037A discloses a kind of residuum hydrogenating and metal-eliminating catalyst, the method adds physics expanding agent and chemical enlargement agent in alumina support preparation process simultaneously, again with the mode of spray dipping by active constituent loading to carrier, the pore volume of this catalyst is 0.80-1.20ml/g, and specific area is 110-200m2/ g, can several apertures be 15-20nm, and bulk density is 0.50-0.60g/ml.
CN1289640A discloses a kind of preparation method of carried catalyst for hydrogenation and demetalation. In the method, adopted the unsaturated technology that sprays, the catalyst after spraying does not do dry processing, directly puts into roaster. The method effectively prevented metal salt solution in follow-up dry run by material lower floor to upper strata or the migration on surface, reduced production cost.
US4,448,896 disclose the catalyst of a kind of hydrodesulfurization and heavy metal, and the preparation method of this catalyst is to be 100-350m by active constituent loading to specific area2/ g, on the alumina support that the pore volume that pore radius is 3.75-7500nm is 0.5-1.5ml/g, the preparation method of this carrier be by activated alumina or activated alumina precursor mix with carbon black, moulding, roasting.
Residuum hydrogenating and metal-eliminating catalyst active metal component prepared by said method is evenly distributed at macropore and the aperture place of carrier, causes the utilization rate of macropore lower, and in addition, the heat endurance of carrier needs further to be improved.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method containing rare earth Hydrodemetalation catalyst. Catalyst activity metal prepared by the method is relatively high at macropore place content, and aperture place content is relatively low, and the heat endurance of macropore obviously improves, and this Hydrodemetalation catalyst has high activity and long-term operation stability.
Preparation method containing rare earth Hydrodemetalation catalyst of the present invention, comprises following content:
(1) flood respectively carbon black powder, then drying for standby with part activity component impregnation liquid with containing the solution of thulium;
(2) carbon black powder after the dipping of step (1) gained is become to plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid, peptizing agent kneading, extrusion, dry, roasting, make containing active component and rare earth modified alumina support;
(3) load residual activity component on modified aluminium oxide supports then, drying, roasting, make Hydrodemetalation catalyst.
In the inventive method, described activity component impregnation liquid is group vib metallic compound and/or group VIII metal compound solution, can, for containing acid solution, the aqueous solution or the ammonia solution of active component, be preferably ammonia solution, the manner of formulation of above maceration extract is known for those skilled in the art; Wherein group vib metallic compound is selected from one or more in ammonium molybdate, ammonium tungstate, ammonium metatungstate or ethyl ammonium tungstate, and group VIII metallic compound is selected from one or more in nickel nitrate, cobalt nitrate, nickel chloride, cobalt chloride, nickel acetate, cobalt acetate or metatungstic acid nickel; In maceration extract, the concentration of group vib metallic compound is 0.1-100g/100ml, and the concentration of group VIII metallic compound is 0.01-10g/100ml; The impregnation method of step (1) adopts incipient impregnation.
In the inventive method, the described part activity component impregnation immersion of step (1) is steeped the weight of active component, count the 0.01wt%-1wt% of final catalyst weight with oxide, the 0.1wt%-0.8wt% that preferably group vib weight metal content is final catalyst weight, the 0.01wt%-0.05wt% that group VIII weight metal content is final catalyst weight.
In the inventive method, the described thulium of step (1) be selected from lanthanum, cerium, praseodymium, ytterbium or samarium one or more, be generally water and/or the ethanolic solution of rare earth element soluble-salt containing the solution of thulium, soluble-salt is generally nitrate or chloride, as lanthanum nitrate, cerous nitrate, praseodymium nitrate, ytterbium nitrate, samaric nitrate etc., the consumption of solution is the saturated water adsorptive value of carbon black powder, after dipping, the content of carbon black powder rare earth elements, in oxide, accounts for 0.01% ~ 0.05% of catalyst weight.
In the inventive method, the described drying condition of step (1) is that nature dries in the shade or in 50-120 DEG C of dry 1-10 hour.
In the inventive method, the described boehmite dry glue powder of step (2) can be the boehmite dry glue powder that adopts any one method to prepare.
In the inventive method, the addition of the carbon black powder in step (2) after dipping is the 5%-10% of boehmite dry glue powder weight.
In the inventive method, in kneading process described in step (2), preferably adding mass concentration is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of polyethylene glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
In the inventive method, the described chemical enlargement agent of step (2) is one or more in phosphoric acid, phosphate or boric acid, preferably phosphate, wherein phosphate is selected from one or more in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP), and chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the described extrusion aid of step (2) is one or more in sesbania powder, starch or methylcellulose, is preferably sesbania powder, and extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
In the inventive method, the described peptizing agent of step (2) is one or more mixing in formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the inventive method, the described drying condition of step (2) is dry 1-10 hour at 100-130 DEG C; Roasting process is at 500-650 DEG C of roasting 2-4 hour.
In the inventive method, the load of the surplus active component described in step (3) adopts infusion process, can adopt volume dipping, incipient impregnation or spray impregnating mode, dip time is 1-5 hour, and the concrete concentration of maceration extract can be determined according to the tenor on final catalyst.
In the inventive method, the described drying condition of step (3) is dry 6-10 hour at 80-120 DEG C; Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
The inventive method is impregnated into appropriate thulium and active metal element on carbon black powder, and makes modified aluminium oxide supports with boehmite kneading, moulding, dry, roasting, and dipping active component finally makes catalyst. In roasting process, carbon powder is removed formation macropore through oxidation, in carbon powder, the active metal component of institute's load and thulium are loaded on corresponding macropore, and the active component content at macropore place in final catalyst and thulium content are obviously increased. Thulium covers alumina surface, has protected part of hydroxyl and has stoped aluminum ions migration, has greatly improved the heat endurance of macropore, prevents caving in of macropore, and the ability that catalyst holds metal and volume carbon strengthens. The active metallic content at macropore place is higher simultaneously, and active increasing, has improved the utilization rate of macropore. When kneading, make carbon black powder mix with boehmite adding of polyethylene glycol, improved the uniformity coefficient of macropore.
Detailed description of the invention
Further illustrate effect of the present invention below in conjunction with embodiment, but be not limited to following examples.
Embodiment 1
Get industrial ammonium heptamolybdate 55g and be placed in ammoniacal liquor, stir, till insoluble matter, then add industrial basic nickel carbonate 25g, stir, till insoluble matter, make containing MoO310 grams/100 milliliters, molybdenum-nickel-ammonia active metal salting liquid of NiO1.2 gram/100 milliliters. Can regulate as required the maceration extract of the addition preparation variable concentrations of ammonium heptamolybdate and basic nickel carbonate.
Taking 7.2 grams of carbon black powders is placed in spray and rolls pot, under rotary state, spray containing 0.3 gram of molybdenum oxide in the saturated mode spraying to the carbon black powder rolling in pot with atomizing type, the active metal maceration extract that nickel oxide is 0.03 gram, the carbon black powder after dipping is dried 3 hours in 110 DEG C. Dried carbon black powder is placed in to spray again and rolls pot, under rotary state, spray lanthanum nitrate ethanolic solution containing lanthana 0.02 gram to the carbon black powder rolling in pot in the saturated mode spraying with atomizing type, the carbon black powder after dipping in 110 DEG C dry 3 hours for subsequent use.
Take 143 grams of boehmite dry glue powders (aluminium oxide butt content 70%) and above-mentioned steps carbon black powder, 7.5 grams of sesbania powder, 3 grams of ammonium phosphate mix, adding mass concentration is 3%, mean molecule quantity is 43 grams of kneadings of Aqueous Solutions of Polyethylene Glycol of 4000, then adds to be dissolved with in right amount 5 grams of nitre aqueous acids to continue kneadings even, and on screw rod banded extruder, being extruded into diameter is the cloverleaf pattern bar of 1.8mm, dry 3 hours in 120 DEG C, by dried article shaped in the roasting temperature of 550 DEG C 4 hours.
Above-mentioned material is placed in to beaker, with 150 milliliters containing MoO310 grams/100 milliliters, molybdenum-nickel-ammonia active metal salt solution impregnated carrier of NiO1.2 gram/100 milliliters 5 hours, elimination redundant solution, dry 2 hours for 120 DEG C, then at 550 DEG C, roasting makes catalyst C1 for 5 hours, this catalyst MoO3Quality percentage composition is 10.2wt%, and NiO quality percentage composition is 1.22wt%, and lanthana quality percentage composition is 0.02wt%.
Embodiment 2
With embodiment 1, just the consumption of carbon black powder is 12 grams, in carbon black powder containing 0.1 gram of molybdenum oxide, 0.01 gram of nickel oxide, 0.03 gram of cerium oxide, the addition of polyglycol solution is 43 to restrain to obtain catalyst C2 of the present invention, this catalyst MoO3Quality percentage composition is 10wt%, and NiO quality percentage composition is 1.2wt%, and cerium oxide quality percentage composition is 0.03wt%.
Embodiment 3
With embodiment 1, just the consumption of carbon black powder is 9 grams, in carbon black powder containing 0.5 gram of molybdenum oxide, 0.02 gram of nickel oxide, 0.01 gram of praseodymium oxide, the addition of polyglycol solution is 100 to restrain to obtain catalyst C3 of the present invention, this catalyst MoO3Quality percentage composition is 10.5wt%, and NiO quality percentage composition is 1.22wt%, and praseodymium oxide quality percentage composition is 0.01wt%.
Embodiment 4
With embodiment 1, just the consumption of carbon black powder is 14.3 grams, in carbon black powder containing 0.7 gram of molybdenum oxide, 0.05 gram of nickel oxide, 0.05 gram of ytterbium oxide, the addition of polyglycol solution is 100 to restrain to obtain catalyst C3 of the present invention, this catalyst MoO3Quality percentage composition is 10.5wt%, and NiO quality percentage composition is 1.22wt%, and ytterbium oxide quality percentage composition is 0.05wt%.
Embodiment 5
With embodiment 1, just the consumption of carbon black powder is 13 grams, contains 0.8 gram of molybdenum oxide in carbon black powder, 0.04 gram of nickel oxide, and 0.04 gram of samarium oxide, the addition of polyglycol solution is 86 grams, when dipping, contains MoO with 150 milliliters38 grams/100 milliliters, molybdenum-nickel-ammonia active metal salt solution impregnated carrier of NiO0.9 gram/100 milliliters makes catalyst C5 of the present invention, this catalyst MoO3Quality percentage composition is 8.7wt%, and NiO quality percentage composition is 0.93wt%, and samarium oxide quality percentage composition is 0.04wt%.
Embodiment 6
With embodiment 1, when just boehmite mixes with carbon black powder, do not add polyglycol solution to make catalyst C6 of the present invention, this catalyst MoO3Quality percentage composition is 10.2wt%, and NiO quality percentage composition is 1.21wt%, and lanthana quality percentage composition is 0.02wt%.
Comparative example 1
With example 1, just active metal does not load on carbon black powder, but adds in kneading, and preparation has the comparative catalyst C7 with embodiment 1 same composition.
Comparative example 2
With example 1, just rare earth metal does not load on carbon black powder, but adds when kneading, and preparation has the catalyst C8 with embodiment 1 same composition.
Comparative example 3
With example 1, just active metal and rare earth metal do not load on carbon black powder, but add when kneading, and preparation has the catalyst C9 with embodiment 1 same composition.
Embodiment 7
The heat endurance of catalyst prepared by the present embodiment investigation embodiment 1,2 and comparative example 2, concrete operations are as follows:
Embodiment 1,2 and comparative example 2 gained catalyst are placed in to Muffle furnace, in 1000 DEG C of roastings 12 hours, naturally cool to room temperature, measure respectively pore structure and the specific surface of above-mentioned catalyst and high-temperature roasting procatalyst, result is as shown in table 1.
Table 1 catalyst heat endurance is investigated.
The heat endurance of introducing as can be seen from Table 1 rare earth element rear catalyst obviously improves, and still has higher specific area and pore volume 1000 DEG C of roastings after 12 hours.
Catalyst prepared by above-mentioned example and comparative example carries out activity rating, more above-mentioned each catalyst activity and stability. Feedstock oil character and evaluation process conditions are in table 2 and table 3, the activity rating of running 200h the results are shown in Table 4, along with the increase of the duration of runs, the activity decreased of catalyst, in order to keep the activity of catalyst to meet production requirement, need to be to beds temperature raising, the temperature rise of 5000 hours rear catalyst beds of running is in table 5.
Table 2.
Table 3.
Table 4.
| Project | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| De-(nickel+vanadium) rate, % | 80 | 78 | 84 | 88 | 73 | 74 | 53 | 70 | 41 |
Table 5.
Can be found out by table 4 data, catalyst provided by the invention has higher HDM activity compared with reference catalyst. Find out from the result of table 5, react after 5000 hours, adopt Hydrodemetalation catalyst provided by the invention to there is higher activity stability.
Claims (14)
1. containing a preparation method for rare earth Hydrodemetalation catalyst, it is characterized in that comprising following content: (1) floods respectively carbon black powder, then drying for standby with part activity component impregnation liquid with containing the solution of thulium; (2) carbon black powder after the dipping of step (1) gained is become to plastic with boehmite dry glue powder, chemical enlargement agent, extrusion aid and peptizing agent kneading, extrusion, dry, roasting, make containing active component and rare earth modified alumina support; (3) load residual activity component on modified aluminium oxide supports then, drying, roasting, make Hydrodemetalation catalyst.
2. in accordance with the method for claim 1, it is characterized in that: described activity component impregnation liquid is group vib metallic compound and/or group VIII metal compound solution, be selected from acid solution, the aqueous solution or ammonia solution containing active component; Wherein group vib metallic compound is selected from one or more in ammonium molybdate, ammonium tungstate, ammonium metatungstate or ethyl ammonium tungstate, and group VIII metallic compound is selected from one or more in nickel nitrate, cobalt nitrate, nickel chloride, cobalt chloride, nickel acetate, cobalt acetate or metatungstic acid nickel; In maceration extract, the concentration of group vib metallic compound is 0.1-100g/100ml, and the concentration of group VIII metallic compound is 0.01-10g/100ml.
3. in accordance with the method for claim 1, it is characterized in that: the described part activity component impregnation immersion of step (1) is steeped the weight of active component, count the 0.01wt%-1wt% of final catalyst weight with oxide.
4. according to the method described in claim 1 or 2, it is characterized in that: the described part activity component impregnation immersion of step (1) is steeped the weight of active component, in oxide, the 0.1wt%-0.8wt% that group vib weight metal content is final catalyst weight, the 0.01wt%-0.05wt% that group VIII weight metal content is final catalyst weight.
5. in accordance with the method for claim 1, it is characterized in that: the described thulium of step (1) be selected from lanthanum, cerium, praseodymium, ytterbium or samarium one or more, solution containing thulium is water and/or the ethanolic solution of rare earth element soluble-salt, the consumption of solution is the saturated water adsorptive value of carbon black powder, ree content, in oxide, accounts for 0.01% ~ 0.05% of catalyst weight.
6. it is characterized in that in accordance with the method for claim 1: the described drying condition of step (1) is that nature dries in the shade or in 50-120 DEG C of dry 1-10 hour.
7. it is characterized in that in accordance with the method for claim 1: the addition of the carbon black powder in step (2) after dipping is the 5%-10% of boehmite dry glue powder weight.
8. in accordance with the method for claim 1, it is characterized in that: in the kneading process described in step (2), adding mass concentration is 1%-5% Aqueous Solutions of Polyethylene Glycol, wherein the mean molecule quantity of polyethylene glycol is 1000-4000, and the addition of Aqueous Solutions of Polyethylene Glycol is 30-70 gram/100 grams boehmite dry glue powders.
9. in accordance with the method for claim 1, it is characterized in that: the described chemical enlargement agent of step (2) is one or more in phosphoric acid, phosphate or boric acid, wherein phosphate is selected from one or more in ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP), and chemical enlargement agent addition is the 3%-5% of boehmite dry glue powder weight.
10. in accordance with the method for claim 1, it is characterized in that: the described extrusion aid of step (2) is one or more in sesbania powder, starch or methylcellulose, and extrusion aid addition is the 3%-5% of boehmite dry glue powder weight.
11. 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 formic acid, acetic acid, citric acid or nitric acid, and addition is the 3%-10% of boehmite dry glue powder weight.
12. in accordance with the method for claim 1, it is characterized in that: the described drying condition of step (2) is dry 1-10 hour at 100-130 DEG C; Roasting process is at 500-650 DEG C of roasting 2-4 hour.
13. in accordance with the method for claim 1, it is characterized in that: the load of the surplus active component described in step (3) adopts infusion process, was selected from the one in volume dipping, incipient impregnation or spray impregnation method, and dip time is 1-5 hour.
14. in accordance with the method for claim 1, it is characterized in that: the described drying condition of step (3) is dry 6-10 hour at 80-120 DEG C; Described roasting condition is roasting 3-6 hour at 400-600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410563745.9A CN105582952B (en) | 2014-10-22 | 2014-10-22 | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410563745.9A CN105582952B (en) | 2014-10-22 | 2014-10-22 | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105582952A true CN105582952A (en) | 2016-05-18 |
| CN105582952B CN105582952B (en) | 2017-11-24 |
Family
ID=55923073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410563745.9A Active CN105582952B (en) | 2014-10-22 | 2014-10-22 | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105582952B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774278A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of preparation method of flue gas reduction and desulfurization catalyst |
| CN110090636A (en) * | 2018-01-30 | 2019-08-06 | 中国石油化工股份有限公司 | Powder of aluminum hydroxide solid elastomer containing cerium and preparation method thereof and alumina support and its application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103480390A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Catalyst having hydrogenation catalysis function, and preparation method and application thereof, and method for hydrogenation treatment of hydrocarbon oil |
| CN103657670A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Pyrolysis gasoline nickel system selective hydrogenation catalyst and preparation method thereof |
| CN103785396A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodemetalization catalyst for heavy oil |
| CN103962165A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Transition metal phosphide hydrogenation catalyst and preparation method thereof |
-
2014
- 2014-10-22 CN CN201410563745.9A patent/CN105582952B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103480390A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Catalyst having hydrogenation catalysis function, and preparation method and application thereof, and method for hydrogenation treatment of hydrocarbon oil |
| CN103657670A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Pyrolysis gasoline nickel system selective hydrogenation catalyst and preparation method thereof |
| CN103785396A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Preparation method of hydrodemetalization catalyst for heavy oil |
| CN103962165A (en) * | 2013-01-30 | 2014-08-06 | 中国石油天然气股份有限公司 | Transition metal phosphide hydrogenation catalyst and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774278A (en) * | 2016-08-31 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of preparation method of flue gas reduction and desulfurization catalyst |
| CN107774278B (en) * | 2016-08-31 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of flue gas reduction and desulfurization catalyst |
| CN110090636A (en) * | 2018-01-30 | 2019-08-06 | 中国石油化工股份有限公司 | Powder of aluminum hydroxide solid elastomer containing cerium and preparation method thereof and alumina support and its application |
| CN110090636B (en) * | 2018-01-30 | 2021-11-12 | 中国石油化工股份有限公司 | Cerium-containing aluminum hydroxide dry glue powder and preparation method thereof, and alumina carrier and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105582952B (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106140187A (en) | A kind of preparation method of Hydrodemetalation catalyst | |
| CN105582951A (en) | Preparation method of hydrodemetallization catalyst containing alkaline earth metals | |
| WO2018161952A1 (en) | Method for preparing hydrotreating catalyst by impregnation method | |
| CN106140181A (en) | A kind of preparation method of siliceous Hydrodemetalation catalyst | |
| CN106140182B (en) | A kind of preparation method of heavy oil hydrogenating treatment catalyst | |
| CN107961795B (en) | Hydrodesulfurization catalyst, preparation method thereof and preparation method of vulcanized hydrodesulfurization catalyst | |
| CN105521793A (en) | Method for preparing hydrodemetallization catalyst | |
| CN102451722B (en) | Preparation method of eggshell-type hydrogenation catalyst | |
| CN101590433A (en) | Modified aluminium oxide supports and the hydrogenation catalyst and the preparation method that make by this carrier | |
| CN105582952A (en) | Preparation method of rare-earth-containing hydrodemetallization catalyst | |
| CN106140122A (en) | A kind of preparation method of boracic Hydrodemetalation catalyst | |
| CN111250103B (en) | Supported hydrogenation catalyst and preparation method thereof | |
| CN102861588A (en) | Residual oil hydrogenation demetalization catalyst and preparation method thereof | |
| CN106140183A (en) | A kind of preparation method containing zirconium Hydrodemetalation catalyst | |
| CN103785399A (en) | Preparation method of hydrodemetalization catalyst | |
| CN100509158C (en) | Alumina support with dual apertures and preparation method thereof | |
| CN106140208B (en) | A kind of preparation method of hydrogenation catalyst | |
| CN104549332B (en) | A kind of catalyst for demetalation and preparation method thereof | |
| CN103785433B (en) | A kind of hydrotreating catalyst and preparation method thereof | |
| CN111250101B (en) | Non-noble metal supported hydrogenation catalyst and preparation method thereof | |
| CN103785432B (en) | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof | |
| CN105582947A (en) | Preparation method of carbon-containing residual oil hydrodemetallization catalyst | |
| CN103785402B (en) | A kind of preparation method of long-life hydrotreating catalyst | |
| CN105521794B (en) | A kind of preparation method of high activity residuum hydrogenating and metal-eliminating catalyst | |
| CN103785398B (en) | A kind of preparation method of residuum hydrogenating and metal-eliminating 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |