CN107413321B - Preparation method of core-shell type carrier - Google Patents
Preparation method of core-shell type carrier Download PDFInfo
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- CN107413321B CN107413321B CN201710400659.XA CN201710400659A CN107413321B CN 107413321 B CN107413321 B CN 107413321B CN 201710400659 A CN201710400659 A CN 201710400659A CN 107413321 B CN107413321 B CN 107413321B
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 83
- 239000003292 glue Substances 0.000 claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 11
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 241000219782 Sesbania Species 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910006415 θ-Al2O3 Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011257 shell material Substances 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 2
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- 239000003054 catalyst Substances 0.000 description 22
- 238000009495 sugar coating Methods 0.000 description 16
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000005096 rolling process Methods 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004287 Dehydroacetic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a core-shell carrier, which comprises the following steps: mixing silica sol, aluminum sol, titanium sol, sesbania gum, sodium carboxymethylcellulose and water to obtain a gum solution; spraying the glue solution on a base material, and roasting at the temperature of 100-200 ℃ to obtain a carrier precursor; coating the shell layer slurry outside the carrier precursor, and then roasting at the temperature of 300-500 ℃. Firstly, a glue layer is prepared on the base material, so that the roughness of the surface of the base material is increased, and the phenomenon that a shell material is easy to fall off from the base material is avoided; the glue solution with a limited proportion is selected, so that the pore passage on the base material can be effectively blocked, and the mechanical strength is increased to a certain extent; the sintering temperature is controlled at 300-500 ℃, the crystal form of the shell layer is effectively ensured, and the specific surface area of the carrier is increased.
Description
Technical Field
The invention relates to the field of catalyst carriers, in particular to a preparation method of a core-shell carrier.
Background
With the continuous development of chemical industry towards environmental protection, energy conservation and high efficiency. The requirements for various properties of the catalyst are continuously improved. Supported catalysts are widely used because of their high catalytic activity and good selectivity. Among them, the supported catalyst using noble metal as active component is most widely used, especially in petrochemical industry, the noble metal supported catalyst is widely used in gas purification, raw material hydrogenation, cracking and other processes with its excellent catalytic performance. The most common method for preparing the noble metal supported catalyst is to directly load the noble metal active component on a carrier with a larger specific surface by means of dipping, spraying and the like, and then to finally obtain the noble metal supported catalyst by roasting. In the preparation method, the carrier with larger specific surface area is selected, and the carrier with larger specific surface area has more porous channels, so that a considerable part of noble metal permeates into the carrier in the loading process, the utilization rate of the noble metal in the carrier is very low in the catalysis process, the waste of the noble metal is caused, the noble metal is expensive, and the production cost is greatly increased.
Aiming at the problems, the carrier is improved, and a core-shell carrier is designed, wherein the carrier with small specific surface area is coated with a layer of material with larger specific surface area, so that the pore channels on the surface of the material with larger specific surface area are reducedDeep. gamma-Al2O3And TiO2The gamma-Al is widely applied to shell materials due to large specific surface area, low price and wide sources2O3The preparation method of the core-shell carrier as the shell material comprises the following steps: preparing aluminum sol from pseudo-boehmite, soaking a base material in the aluminum sol, and then drying and roasting, wherein the core-shell type carrier prepared by the method has the problems of uneven shell thickness and poor mechanical strength; with TiO2The preparation method of the core-shell carrier as the shell material comprises the following steps: mixing titanium chloride with water, taking titanium sol formed on the titanium chloride, putting a carrier into the titanium sol for dipping and roasting, wherein in the preparation method, the titanium chloride is subjected to violent hydrolysis immediately after meeting water, and simultaneously, a large amount of precipitates are generated, so that the amount of the generated titanium sol is very small and is only about 5-10 percent, a large amount of titanium raw materials are wasted, and a large amount of polluted gas hydrogen chloride is generated in the hydrolysis process; meanwhile, the shell layer carrier prepared by the method also has the problem of poor mechanical strength.
For this purpose, chinese patent CN101491778A discloses a thin shell type noble metal catalyst, which uses alumina as the core and gamma-Al as the carrier2O3The powder is used as a coating material, the coating material is mixed with water, glue solution and surfactant to prepare slurry, then the slurry is sprayed on the surface of the base material, and the base material is roasted at the temperature of 700-1200 ℃ to obtain the layered composite carrier. In the technical scheme, the gamma-Al is directly adopted2O3The powder glue solution is mixed to be used as a shell material, and for the adhesion strength, the powder glue solution can only be roasted at a very high temperature, the existence temperature of the gamma-phase alumina crystal form is 400-plus 600 ℃, if the temperature is too high, the crystal form is changed, and at 700-plus 1200 ℃, the gamma-phase alumina crystal form is converted into a delta phase or/and a theta phase with a very small specific surface area, so that the specific surface area of the carrier is greatly reduced; meanwhile, the technical scheme disclosed in the patent does not improve the mechanical strength of the carrier;
meanwhile, in the technical scheme disclosed in the patent, the disclosed base material is α -Al with smaller specific surface area2O3、θ-Al2O3Spinel, quartz, etc. as the base material, the surface of the above-mentioned material is smooth, in the course of rubberizing, often will produce the situation that the glue solution can't be loaded on the base material.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to overcome the defects of the prior art that the thickness of the shell layer is not uniform, when the shell layer carries an active component, the active component is easy to permeate into the base material, the mechanical strength is low, and the shell layer material is not easy to coat on the base material, thereby providing a preparation method of the core-shell carrier.
A preparation method of a core-shell carrier comprises the following steps:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, sodium carboxymethylcellulose and water to obtain a gum solution;
(2) spraying the glue solution on a base material, and roasting at the temperature of 100-200 ℃ to obtain a carrier precursor;
(3) coating the shell layer slurry outside the carrier precursor, and then roasting at the temperature of 300-500 ℃ to obtain the core-shell carrier.
Preferably, in the preparation method, the shell layer slurry is an aluminum sol or a titanium sol.
Preferably, in the preparation method, SiO is contained in the glue solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the sodium carboxymethylcellulose to the water is as follows: (0.1-10): (0.1-10): (0.1-10): (0.1-1): (0.1-1): 100.
preferably, in the preparation method, SiO is contained in the glue solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the sodium carboxymethylcellulose to the water is as follows: 0.1:1:1:0.1:0.2: 100.
preferably, in the preparation method, the mass ratio of the glue solution to the base material is as follows: (1-13): 25.
preferably, in the preparation method, the base material is α -Al2O3、δ-Al2O3、θ-Al2O3Or α -SiO2。
Preferably, in the preparation method, the base material is spherical and has a diameter of 2-5 mm.
Preferably, in the preparation method,
in the step 2, the roasting time is 0.5-1 h;
in the step 3, the roasting time is 0.5-3 h.
The technical scheme of the invention has the following advantages:
the invention provides a preparation method of a core-shell carrier, which comprises the following steps: mixing silica sol, aluminum sol, titanium sol, sesbania gum, sodium carboxymethylcellulose and water to obtain a gum solution; spraying the glue solution on a base material, and roasting at the temperature of 100-200 ℃ to obtain a carrier precursor; coating the shell layer slurry outside the carrier precursor, and then roasting at the temperature of 300-500 ℃ to obtain the core-shell carrier. Firstly, a glue layer is prepared on a base material, so that the roughness of the surface of the base material is increased, and the falling of a shell material from the base material is avoided; secondly, the glue solution with a limited proportion is selected, so that the pore passages on the base material can be effectively blocked, the mechanical strength is increased to a certain degree, and the test proves that the mechanical strength can reach 170N/particle; thirdly, the sintering temperature is controlled to be 300-500 ℃, the crystal form of the shell layer is effectively ensured, and the specific surface area of the carrier is increased.
Meanwhile, the catalyst prepared by the core-shell carrier prepared by the method disclosed by the invention also has higher catalytic activity.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
In the inventionThe aluminum sol and the titanium sol can be prepared by any method for preparing the aluminum sol and the titanium sol in the prior art, or can be purchased as finished products on the market, and for comparison, the preparation method of the aluminum sol in the embodiments 1 to 3 is as follows: uniformly mixing pseudo-boehmite powder with water, dropwise adding a nitric acid solution at 80 ℃ while stirring, and cooling to room temperature to obtain an alumina sol with the solid content of 10%; the preparation method of the titanium sol in examples 4 to 6 was: mixing TiCl3Mixing with water, stirring, standing for 5-10min, and collecting the upper layer glue solution, i.e. titanium sol with solid content of 10%.
Example 1
A method of preparing a core-shell support comprising:
(1) mixing silica sol, alumina sol, titanium sol, sesbania gum, CMC (sodium carboxymethylcellulose) and water at room temperature, and stirring to obtain a gum solution, wherein SiO in the gum solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the CMC to the water is 0.1:0.1:10:1:0.1: 100;
(2) selecting spherical α -Al with the diameter of 2mm2O3Putting the base material into a sugar-coating machine, spraying the glue solution on the base material according to the mass ratio of the glue solution to the base material of 1:25, rolling the base material in the sugar-coating machine for 0.5h to ensure that the glue solution is uniformly coated outside the base material, and roasting the base material at the temperature of 100 ℃ for 0.5h to obtain a carrier precursor;
(3) spraying the aluminum sol on the obtained carrier precursor according to the mass ratio of the aluminum sol to the base material of 1:25, and roasting at 300 ℃ for 3h to obtain a carrier A;
example 2
A method of preparing a core-shell support comprising:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, CMC and water at room temperature, and stirring to obtain a gum solution, wherein SiO in the gum solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the CMC to the water is 10:10:0.1:0.1:1: 100;
(2) selecting spherical delta-Al with the diameter of 5mm2O3As a base material in a sugar-coating machineSpraying the glue solution on a base material according to the mass ratio of the glue solution to the base material of 13:25, rolling in a sugar coating machine for 1h to enable the glue solution to be uniformly coated outside the base material, and roasting at the temperature of 150 ℃ for 1h to obtain a carrier precursor;
(3) spraying the aluminum sol on the obtained carrier precursor according to the mass ratio of the aluminum sol to the base material of 13:25, and roasting at 500 ℃ for 0.5h to obtain a carrier B;
example 3
A method of preparing a core-shell support comprising:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, CMC and water at room temperature, and stirring to obtain a gum solution, wherein SiO in the gum solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the CMC to the water is 1:1:1:1:1: 100;
(2) selecting spherical theta-Al with the diameter of 3mm2O3Putting the base material into a sugar-coating machine, spraying the glue solution onto the base material according to the mass ratio of the glue solution to the base material of 7:25, rolling the base material in the sugar-coating machine for 1 hour to ensure that the glue solution is uniformly coated outside the base material, and roasting the base material at the temperature of 200 ℃ for 1 hour to obtain a carrier precursor;
(3) and spraying the aluminum sol on the obtained carrier precursor according to the mass ratio of the aluminum sol to the base material of 7:25, and roasting for 2 hours at 400 ℃ to obtain the carrier C.
Example 4
A method of preparing a core-shell support comprising:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, CMC and water at room temperature, and stirring to obtain a gum solution, wherein SiO in the gum solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the CMC to the water is 0.1:1:1:0.1:0.2: 100;
(2) selecting spherical α -Al with the diameter of 4mm2O3Putting the base material in a sugar-coating machine, spraying the glue solution onto the base material according to the mass ratio of the glue solution to the base material of 9:25, rolling in the sugar-coating machine for 1h to uniformly coat the glue solution on the outside of the base material, and heating at a certain temperatureRoasting for 1h at 130 ℃ to obtain a carrier precursor;
(3) and spraying the titanium sol on the obtained carrier precursor according to the mass ratio of the titanium sol to the base material of 9:25, and roasting for 2 hours at 400 ℃ to obtain the carrier D.
Example 5
A method of preparing a core-shell support comprising:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, CMC and water at room temperature, and stirring to obtain a gum solution, wherein SiO in the gum solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the CMC to the water is 5:4:6:0.5:0.7: 100;
(2) selecting spherical α -SiO with the diameter of 4mm2Putting the base material into a sugar-coating machine, spraying the glue solution on the base material according to the mass ratio of the glue solution to the base material of 10:25, rolling the base material in the sugar-coating machine for 1 hour to ensure that the glue solution is uniformly coated outside the base material, and roasting the base material at the temperature of 180 ℃ for 1 hour to obtain a carrier precursor;
(3) and spraying the titanium sol on the obtained carrier precursor according to the mass ratio of the titanium sol to the base material of 10:25, and roasting for 3 hours at 500 ℃ to obtain the carrier E.
Example 6
gamma-Al alloy2O3The preparation method of the core-shell carrier serving as the shell layer comprises the following steps:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, CMC and water at room temperature, and stirring to obtain a gum solution, wherein SiO in the gum solution2、Al2O3、TiO2The mass ratio of the sesbania gum to the CMC to the water is 9:8:10:0.7:0.3: 100;
(2) selecting spherical theta-Al with the diameter of 5mm2O3Putting the base material into a sugar-coating machine, spraying the glue solution onto the base material according to the mass ratio of the glue solution to the base material of 12:25, rolling the base material in the sugar-coating machine for 2 hours to ensure that the glue solution is uniformly coated outside the base material, and roasting the base material at the temperature of 110 ℃ for 1 hour to obtain a carrier precursor;
(3) and spraying the titanium sol on the obtained carrier precursor according to the mass ratio of the titanium sol to the base material of 12:25, and roasting for 3 hours at 500 ℃ to obtain the carrier F.
Comparative example 1
A method of preparing a core-shell support comprising:
(1) mixing silica sol, CMC and water at room temperature, and stirring to obtain a glue solution, wherein SiO is contained in the glue solution2And the mass ratio of CMC to water is 0.5: 0.5: 100, respectively;
(2) selecting spherical α -Al with the diameter of 4mm2O3Putting the base material into a sugar-coating machine, spraying the glue solution onto the base material according to the mass ratio of the glue solution to the base material of 9:25, rolling the base material in the sugar-coating machine for 1 hour to ensure that the glue solution is uniformly coated outside the base material, and roasting the base material at the temperature of 130 ℃ for 1 hour to obtain a carrier precursor;
(3) and spraying the titanium sol on the obtained carrier precursor according to the mass ratio of the titanium sol to the base material of 9:25, and roasting for 2 hours at 400 ℃ to obtain the carrier G.
Comparative example 2
A preparation method of a shell-layer core-shell carrier comprises the following steps:
(1) selecting spherical α -Al with the diameter of 4mm2O3Putting the base material into a sugar-coating machine, spraying the glue solution onto the base material according to the mass ratio of the glue solution to the base material of 9:25, rolling the base material in the sugar-coating machine for 1 hour to ensure that the glue solution is uniformly coated outside the base material, and roasting the base material at the temperature of 130 ℃ for 1 hour to obtain a carrier precursor;
(2) and spraying the titanium sol on the obtained carrier precursor according to the mass ratio of the titanium sol to the base material of 9:25, and roasting for 2 hours at 400 ℃ to obtain the carrier H.
Effect verification:
the core-shell type carriers prepared according to the present invention can be prepared into any one of catalysts according to the preparation methods in the prior art, and for comparison, the carriers a to H prepared in examples 1 to 6 and comparative examples 1 to 2 were prepared into deoxygenation catalysts a to H according to the following methods.
A method of preparing a deoxygenation catalyst comprising:
preparing a chloroplatinic acid aqueous solution with the mass percentage of 10%, soaking the carrier in the chloroplatinic acid aqueous solution for 1.5h according to the amount of soaking 1g of the carrier in 100mL of the chloroplatinic acid aqueous solution, drying at 70 ℃ for 2h, and roasting at 500 ℃ for 2h to obtain the deoxygenation catalyst.
1. Penetration detection of active ingredient platinum
The amount of platinum supported on the substrate of the catalyst a-H carrier was measured by evaluating the amount of the metal active component supported on the catalysts a-H using an electron probe, and the results are shown in table 1.
TABLE 1 Metal content of internal substrate of core-shell type Carrier
As can be seen from Table 1, the deoxygenation catalysts A-F prepared using the supports A-F of examples 1-6 exhibited substantially no detection of platinum metal on the substrate (core portion); while the deoxidation catalysts G and H prepared using the carriers G and H of comparative examples 1-2 had platinum metal active components detected on the substrates.
2. Deoxygenation efficiency detection
The deoxidation catalyst A-H is used for deoxidation of raw material gas, wherein the raw material gas is nitrogen, the normal temperature and the normal pressure are realized, and the space velocity is 5000H-1The deoxidation performance of the catalyst was measured by adding hydrogen gas using a mass flow meter control system under the conditions of (1), and the results are shown in table 2.
TABLE 2 deoxygenation Performance of the catalyst
As can be seen from Table 2, the deoxidation performances of the deoxidation catalysts prepared using the supports of examples 1 to 8 are significantly better than those of the deoxidation catalysts prepared using the supports of comparative examples 1 to 2.
3. Detection of mechanical Strength of Carrier A-H
The mechanical strength of the supports A to H prepared in examples 1 to 6 and comparative examples 1 to 2 was measured using a pressure particle tester, and the results are shown in Table 3.
TABLE 3 mechanical Strength of Carrier
| Mechanical Strength (N/grain) | ||
| Example 1 | Carrier A | 150 |
| Example 2 | Carrier B | 152 |
| Example 3 | Carrier C | 162 |
| Example 4 | Carrier D | 170 |
| Example 5 | Carrier E | 159 |
| Example 6 | Vector F | 155 |
| Comparative example 1 | Vector G | 113 |
| Comparative example 2 | Carrier H | 94 |
As can be seen from Table 3, the mechanical strength of the supports A to F prepared in examples 1 to 6 was significantly superior to that of the supports G to H prepared in comparative examples 1 to 2.
4. Detection of specific surface area of Carrier A-K
The specific surface areas of the carriers A to H were measured by the BET specific surface area measurement method, and the measurement results are shown in Table 4.
TABLE 4 specific surface area of the support
| Specific surface area (g/m)2) | ||
| Example 1 | Carrier A | 350 |
| Example 2 | Carrier B | 320 |
| Example 3 | Carrier C | 340 |
| Example 4 | Carrier D | 280 |
| Example 5 | Carrier E | 265 |
| Example 6 | Vector F | 249 |
| Comparative example 1 | Vector G | 200 |
| Comparative example 2 | Carrier H | 155 |
As can be seen from Table 4, the specific surface areas of the supports A to F prepared by examples 1 to 6 were significantly larger than those of the supports G to H prepared by comparative examples 1 to 2.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. A preparation method of a core-shell carrier comprises the following steps:
(1) mixing silica sol, aluminum sol, titanium sol, sesbania gum, sodium carboxymethylcellulose and water to obtain a gum solution;
(2) spraying the glue solution on a base material, and roasting at the temperature of 100-200 ℃ to obtain a carrier precursor;
(3) coating the shell layer slurry outside the carrier precursor, and then roasting at the temperature of 300-500 ℃ to obtain the core-shell carrier;
wherein the base material is α -Al2O3、δ-Al2O3、θ-Al2O3Or α -SiO2；
The shell layer slurry is aluminum sol or titanium sol;
in the glue solution, SiO2、Al2O3、TiO2The mass ratio of the sesbania gum to the sodium carboxymethylcellulose to the water is as follows: (0.1-10): (0.1-10): (0.1-10): (0.1-1): (0.1-1): 100.
2. the method according to claim 1, wherein the glue solution is SiO2、Al2O3、TiO2The mass ratio of the sesbania gum to the sodium carboxymethylcellulose to the water is as follows: 0.1:1:1:0.1:0.2: 100.
3. the preparation method according to claim 1 or 2, wherein the mass ratio of the glue solution to the base material is as follows: (1-13): 25.
4. the method of claim 1, wherein the substrate is spherical and has a diameter of 2 to 5 mm.
5. The production method according to claim 1,
in the step 2, the roasting time is 0.5-1 h;
in the step 3, the roasting time is 0.5-3 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101485974A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for supporting nano titanic oxide on surface of carrier material |
| CN101491778A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of thin shell shaped noble metal catalyst |
| CN101992112A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Titanium oxide coating/ceramic structural catalyst carrier and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | Method for preparing catalyst and application thereof |
| CN101491778A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of thin shell shaped noble metal catalyst |
| CN101485974A (en) * | 2009-02-23 | 2009-07-22 | 东南大学 | Method for supporting nano titanic oxide on surface of carrier material |
| CN101992112A (en) * | 2009-08-27 | 2011-03-30 | 中国科学院金属研究所 | Titanium oxide coating/ceramic structural catalyst carrier and preparation method thereof |
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