CN117463319B - La and B doped zinc oxide-aluminum oxide composite metal oxide carrier and preparation method and application thereof - Google Patents
La and B doped zinc oxide-aluminum oxide composite metal oxide carrier and preparation method and application thereof Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 19
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 title claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 13
- 239000001294 propane Substances 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 239000011701 zinc Substances 0.000 claims 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 25
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 17
- 239000011148 porous material Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 11
- 241000219782 Sesbania Species 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysts, and discloses a La and B doped zinc oxide-aluminum oxide composite metal oxide carrier, a preparation method and application thereof, wherein La and B are adopted to carry out doping modification on a bimetallic oxide material containing zinc oxide and active aluminum oxide, the content of zinc oxide in the bimetallic oxide material is 1-10 wt%, and the content of La and B in the metal oxide carrier prepared by modification is 0.1-5 wt%. The ZnO-Al 2O3 bimetallic oxide is doped with La and B elements, so that the catalyst has proper surface acidity and alkalinity and higher thermal stability, has the advantage of large specific surface area of active alumina, and is particularly suitable for preparing a carrier of a propane dehydrogenation catalyst.
Description
Technical Field
The invention relates to a La and B doped zinc oxide-aluminum oxide composite metal oxide carrier and a preparation method and application thereof, in particular to a La and B doped zinc oxide-aluminum oxide composite metal oxide carrier applied to a propane dehydrogenation catalyst and a preparation method and application thereof, and belongs to the technical field of catalysts.
Background
In the field of propane dehydrogenation catalysts, the carrier has multiple functions, such as being used as a heat stabilizer to avoid aggregation and sintering of catalytic active components, being used as an antitoxic agent to reduce carbon deposition and by-product generation, being used as a diluting component to reduce catalyst cost, maintaining catalyst strength and the like.
The active alumina, gamma-Al 2O3, has the advantages of large specific surface area, adjustable pore structure and pore distribution, acid centers with different properties on the surface, good mechanical strength and thermal stability, low price and the like, and is widely used as a carrier of a propane dehydrogenation catalyst. However, γ -Al 2O3 also has significant drawbacks, which can greatly affect the performance of the supported catalyst: firstly, under the high temperature condition, gamma-Al 2O3 can be converted into alpha-Al 2O3 with more stable thermodynamics, so that the specific surface area of the catalyst carrier is reduced sharply, active components on the carrier are aggregated, the catalytic activity is reduced, and the service life is shortened. Secondly, the surface properties of activated alumina, in particular the number, strength and distribution of its surface acid sites, can greatly affect the performance of the supported catalyst. The research shows that the Lewis acid center on the surface of the active alumina is favorable for adsorbing reactant gas molecules on the surface of the catalyst, so that the catalytic activity is improved; however, in the hydrocarbon dehydrogenation reaction, the too strong Lewis acid center is unfavorable for the desorption of the intermediate and the catalytic product, and easily causes carbon deposition on the surface of the catalyst, so that the activity of the catalyst is reduced or even deactivated.
In summary, the sintering resistance, phase transition resistance and carbon deposition resistance of the activated alumina are required to be further improved. Therefore, research and development of a catalyst support having proper surface acidity and basicity and high thermal stability is necessary for improving the performance of propane dehydrogenation catalyst.
In the prior art, the invention patent with publication number CN103212411A discloses a catalyst capable of efficiently catalyzing low-carbon alkane to prepare olefin and a preparation method thereof, the catalyst takes a high-temperature composite oxide containing one or more mixtures of Al 2O3, magnesia, zirconia and zinc oxide as a carrier, an active component and an auxiliary agent are once loaded on the high-temperature composite oxide carrier by using a method of forming a stable complexing solution of Pt-Sn in an acid solution, and the catalyst capable of efficiently and stably catalyzing alkane to be dehydrogenated can be obtained through drying, roasting and reducing, but the high-temperature composite oxide carrier has lower strength and is not suitable for being used as a fixed bed carrier, and the catalyst can be crushed by the weight of the high-temperature composite oxide carrier. The invention patent with publication number CN116651434A also discloses a low-carbon alkane dehydrogenation catalyst and a preparation method and application thereof, the catalyst is a Cr catalyst with a new design configuration, active alumina containing La element is used as a carrier, la-O sites in the framework can be formed due to the introduction of La element in the alumina carrier framework, la element with larger size occupying lattice sites can inhibit high-temperature migration of Al 3+ in a bulk phase, and the special electronic attribute of La-O bond is beneficial to activating H +, promoting the occurrence of dehydrogenation reaction process and improving selectivity and thermal stability, but La is +3 valence in the catalyst and is expressed as Lewis acid, so that the acidity of the carrier and the catalyst can be improved, carbon deposition is increased, and the activity is fast reduced.
Disclosure of Invention
The invention aims to provide a La and B doped zinc oxide-aluminum oxide composite metal oxide carrier, which has proper surface acidity and alkalinity and higher thermal stability by doping La and B elements into ZnO-Al 2O3 bimetallic oxide, has the advantage of large specific surface area of active aluminum oxide, and is particularly suitable for preparing a carrier of a propane dehydrogenation catalyst. For this reason, the invention also provides a method for preparing the metal oxide carrier and application thereof in preparing a propane dehydrogenation catalyst.
The invention is realized by the following technical scheme: a La and B doped zinc oxide-aluminum oxide composite metal oxide carrier is prepared by doping and modifying a bimetallic oxide material containing zinc oxide and active aluminum oxide, wherein the content of zinc oxide in the bimetallic oxide material is 1-10 wt%, and the content of La and B in the modified metal oxide carrier is 0.1-5 wt% respectively.
The preparation method of the La and B doped zinc oxide-aluminum oxide composite metal oxide carrier comprises the following steps:
s1, stirring and mixing zinc oxide, active aluminum oxide and an auxiliary agent, and extruding the mixture into strips to prepare a bimetal oxide material;
S2, preparing a mixed solution containing La (NO 3)3·6H2O、H3BO3;
S3, adding the bimetallic oxide material into the mixed solution for soaking, and drying and roasting to obtain the metal oxide carrier.
In the step S1, the auxiliary agent is selected from sesbania powder, methylcellulose, starch or cyclodextrin.
In the step S1, a single screw extruder is adopted during extrusion, and the extrusion pressure is controlled to be 2750-3450 kPa.
In the step S2, la (the mass ratio of NO 3)3·6H2 O to H 3BO3) in the mixed solution is 5:1-1:5.
In the step S3, the soaking time is 4-10 h.
In the step S3, the drying temperature is 150-200 ℃ and the drying time is 2-4 h.
In the step S3, roasting is carried out for 4-8 hours in the air atmosphere at 600-800 ℃.
The La and B doped zinc oxide-aluminum oxide composite metal oxide carrier is applied to the preparation of propane dehydrogenation catalysts.
Compared with the prior art, the invention has the following advantages:
(1) The composite metal oxide carrier provided by the invention is prepared by introducing La and B elements into ZnO-Al 2O3 bimetallic oxide, and can be used for modifying the acid position of the aluminum oxide surface by introducing La and B elements, so that the strong Lewis acid center is converted to the weak acid center, namely, the acid distribution of the carrier surface is changed, the carbon deposition resistance is enhanced, and the catalytic activity and the service life of the catalyst dehydrogenation are improved.
(2) According to the invention, zn, la, B and other elements are doped in the active alumina, and the stronger interaction formed between the doping atoms and the O atoms is utilized, so that the active alumina can be used for improving the thermal stability of the alumina crystal structure, preventing the alumina from high-temperature phase transition, promoting the better dispersion of the catalytic active components on the surface of the carrier material, and further improving the activity and thermal stability of the catalyst.
Drawings
FIG. 1 is a NH 3 -TPD diagram of materials A1, B3, B5.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the present invention, but are merely illustrative of the present invention. The experimental methods used in the following examples are not specifically described, but the experimental methods in which specific conditions are not specified in the examples are generally carried out under conventional conditions, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
Example 1:
Mixing ZnO and activated alumina powder with a proper amount of sesbania powder according to the mass ratio of 5:100, fully stirring, extruding into strips in a single screw extruder, and obtaining ZnO-Al 2O3 bimetallic oxide under the extrusion pressure of 2750 kPa.
Adding 0.31g of La (NO 3)3·6H2 O and 0.57g H 3BO3) into 10ml of water, uniformly mixing to form a mixed solution, adding 99.8g of ZnO-Al 2O3 bimetallic oxide into the mixed solution, soaking for 4 hours, placing the soaked mixture into an oven, drying at a constant temperature of 200 ℃ for 2 hours, and roasting the dried solid in an air atmosphere at 800 ℃ for 4 hours to obtain the mixed metal oxide, wherein the mixed metal oxide is marked as a material B1.
Example 2:
Mixing ZnO and activated alumina powder with proper amount of methylcellulose according to the mass ratio of 1:99, extruding into strips in a single screw extruder after fully stirring, wherein the extrusion pressure is 3250kPa, and obtaining ZnO-Al 2O3 bimetallic oxide.
1.56G of La (NO 3)3·6H2 O and 2.866g H 3BO3) is taken and added into 50ml of water, mixed solution is formed after uniform mixing, 99g of ZnO-Al 2O3 bimetallic oxide is added into the mixed solution, the mixed solution is immersed for 6 hours, the immersed mixture is placed into an oven to be dried for 4 hours at the constant temperature of 150 ℃, and the dried solid is baked for 5 hours in the air atmosphere at the temperature of 800 ℃ to obtain mixed metal oxide, and the mixed metal oxide is marked as a material B2.
Example 3:
Mixing ZnO and activated alumina powder with a proper amount of sesbania powder according to the mass ratio of 5:95, fully stirring, extruding into strips in a single screw extruder, and obtaining ZnO-Al 2O3 bimetallic oxide under the extrusion pressure of 2850 kPa.
3.12G of La (NO 3)3·6H2 O and 5.72g H 3BO3) are taken and added into 100ml of water, mixed solution is formed after uniform mixing, 98g of ZnO-Al 2O3 bimetallic oxide is added into the mixed solution, the mixed solution is immersed for 8 hours, the immersed mixture is placed into an oven for constant temperature drying at 180 ℃ for 3 hours, the dried solid is baked for 6 hours in air atmosphere at 600 ℃ to obtain mixed metal oxide, and the mixed metal oxide is marked as a material B3.
Example 4:
Mixing ZnO and activated alumina powder with proper amount of starch according to the mass ratio of 10:90, extruding into strips in a single screw extruder after fully stirring, wherein the extrusion pressure is 3450kPa, and obtaining ZnO-Al 2O3 bimetallic oxide.
6.23G of La (NO 3)3·6H2 O and 11.44g H 3BO3) are taken and added into 200ml of water, mixed solution is formed after uniform mixing, 96g of ZnO-Al 2O3 bimetallic oxide is added into the mixed solution, the mixed solution is immersed for 10 hours, the immersed mixture is placed into an oven for constant temperature drying for 4 hours at 200 ℃, the dried solid is baked for 5 hours in air atmosphere at 750 ℃ to obtain mixed metal oxide, and the mixed metal oxide is marked as a material B4.
Example 5:
Mixing ZnO and active alumina powder with a proper amount of cyclodextrin according to the mass ratio of 6:94, extruding into strips in a single screw extruder after fully stirring, and obtaining ZnO-Al 2O3 bimetallic oxide under the extrusion pressure of 3200 kPa.
15.58G of La (NO 3)3·6H2 O and 28.60g H 3BO3) are taken and added into 500ml of water, mixed solution is formed after uniform mixing, 90g of ZnO-Al 2O3 bimetallic oxide is added into the mixed solution, the mixed solution is immersed for 8 hours, the immersed mixture is placed into an oven for constant temperature drying at 160 ℃ for 3 hours, and the dried solid is baked for 8 hours in air atmosphere at 650 ℃ to obtain mixed metal oxide, and the mixed metal oxide is marked as a material B5.
Comparative example 1:
100g of active alumina powder is taken and mixed with a proper amount of sesbania powder, and after full stirring, the mixture is extruded into strips by a single screw extruder, the extrusion pressure is properly adjusted, and the material A1 is marked.
Comparative example 2:
1g ZnO, 99g active alumina powder and a proper amount of sesbania powder are mixed, fully stirred and extruded into strips in a single screw extruder, the extrusion pressure is properly adjusted, and the material A2 is marked.
Comparative example 3:
2g ZnO, 98g active alumina powder and a proper amount of sesbania powder are mixed, fully stirred and extruded into strips in a single screw extruder, the extrusion pressure is properly adjusted, and the material A3 is marked.
Comparative example 4:
5g ZnO, 95g active alumina powder and a proper amount of sesbania powder are mixed, fully stirred and extruded into strips in a single screw extruder, the extrusion pressure is properly adjusted, and the material A4 is marked.
Comparative example 5:
8g ZnO, 92g active alumina powder and a proper amount of sesbania powder are mixed, fully stirred and extruded into strips in a single screw extruder, the extrusion pressure is properly adjusted, and the material A5 is marked.
Comparative example 6:
10g ZnO, 90g active alumina powder and a proper amount of sesbania powder are mixed, fully stirred and extruded into strips in a single screw extruder, the extrusion pressure is properly adjusted, and the material A6 is marked.
Comparative example 7:
The same procedure as in example 1 was used, except that: 0.16g of La (NO 3)3·6H2 O and 0.29g H 3BO3) was added to 5ml of water, and mixed solution was formed after mixing uniformly, and 99.9g of ZnO-Al 2O3 bimetallic oxide was added to the mixed solution, and the obtained mixed metal oxide was labeled as material A7.
Comparative example 8:
The same procedure as in example 1 was used, except that: 18.70g La (NO 3)3·6H2 O and 34.32g H 3BO3) was added to 600ml water, and mixed uniformly to form a mixed solution, 88g ZnO-Al 2O3 bimetallic oxide was added to the mixed solution, and the obtained mixed metal oxide was labeled as material A8.
The following material property experiments were conducted using the materials A1 to A8 of the above comparative examples 1 to 8 and the materials B1 to B5 of examples 1 to 5 as experimental samples.
Nitrogen adsorption and desorption experiments
Pore structure parameter analysis of the samples in the experiments was performed on a JW-TB series specific surface and pore size analyzer purchased from beijing micro-advanced high-bos scientific technology limited. The sample was vacuum degassed at 350 ℃ for 4 hours before measurement, the specific surface area of the sample was calculated by BET method, the pore volume was calculated by BJH model, and the pore size distribution was analyzed by DFT method. Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The nitrogen adsorption and desorption experiments are carried out on the materials A1-8 and B1-5, and the obtained results are shown in Table 1:
TABLE 1
| Numbering device | Material | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Average pore diameter (nm) |
| Comparative example 1 | A1 | 325.1 | 0.55 | 4.8 |
| Comparative example 2 | A2 | 322.6 | 0.55 | 4.8 |
| Comparative example 3 | A3 | 319.4 | 0.55 | 4.8 |
| Comparative example 4 | A4 | 310.7 | 0.56 | 4.9 |
| Comparative example 5 | A5 | 301.5 | 0.56 | 4.9 |
| Comparative example 6 | A6 | 295.1 | 0.57 | 5.0 |
| Comparative example 7 | A7 | 314.9 | 0.56 | 4.9 |
| Comparative example 8 | A8 | 311.4 | 0.57 | 5.0 |
| Example 1 | B1 | 317.6 | 0.56 | 4.8 |
| Example 2 | B2 | 320.5 | 0.54 | 4.7 |
| Example 3 | B3 | 325.8 | 0.55 | 4.6 |
| Example 4 | B4 | 324.2 | 0.55 | 4.7 |
| Example 5 | B5 | 319.1 | 0.54 | 4.8 |
As can be seen from Table 1, the specific surface area of the ZnO-Al 2O3 bimetallic oxide prepared by the method of the present invention decreases with the doping amount of zinc oxide, because the specific surface area of zinc oxide itself is slightly smaller than that of activated alumina. Compared with the bimetallic oxide, the mixed metal oxide material with the same ZnO/Al 2O3 ratio has the advantages that the specific surface area and the pore channel structure are changed: along with the increase of the doping amount of La and B in the bimetallic oxide, the specific surface area of the mixed oxide is slightly increased, because the doping of proper amounts of La and B optimizes the pore canal structure of the ZnO-Al 2O3 bimetallic oxide, so that the specific surface areas of ZnO and Al 2O3 are increased; however, excessive La and B doping tends to cause plugging of the channels of the bimetallic oxide.
To examine the thermal stability of the above mixed metal oxide materials, materials A1 to 8 and materials B1 to 5 were calcined at 900℃for 2 hours, and then subjected to a nitrogen adsorption/desorption experiment, and the results are shown in Table 2.
TABLE 2
| Numbering device | Material | Specific surface area (m 2/g) | Pore volume (cm 3/g) | Average pore diameter (nm) |
| Comparative example 1 | A1 | 177.9 | 0.89 | 8.6 |
| Comparative example 2 | A2 | 189.1 | 0.87 | 8.5 |
| Comparative example 3 | A3 | 233.7 | 0.75 | 7.6 |
| Comparative example 4 | A4 | 268.0 | 0.72 | 6.3 |
| Comparative example 5 | A5 | 261.5 | 0.72 | 6.5 |
| Comparative example 6 | A6 | 259.1 | 0.72 | 6.5 |
| Comparative example 7 | A7 | 274.9 | 0.70 | 6.1 |
| Comparative example 8 | A8 | 308.4 | 0.58 | 5.1 |
| Example 1 | B1 | 313.8 | 0.57 | 4.9 |
| Example 2 | B2 | 318.5 | 0.54 | 4.8 |
| Example 3 | B3 | 321.0 | 0.55 | 4.7 |
| Example 4 | B4 | 320.3 | 0.55 | 4.7 |
| Example 5 | B5 | 317.1 | 0.54 | 4.8 |
As can be seen from table 2, after the pure activated alumina material A1 is calcined at 900 ℃ for 2 hours, the specific surface area becomes significantly smaller, and the pore volume and the average pore diameter become larger; after the bimetallic oxide material A2-6 is roasted for 2 hours at 900 ℃, the specific surface area is also reduced, and the degree of reduction of the specific surface area is reduced along with the increase of the doping amount of zinc oxide, which shows that the thermal stability of the bimetallic oxide is obviously higher than that of pure aluminum oxide; after the mixed metal oxide materials A7-8 and B1-5 are roasted for 2 hours at 900 ℃, the change of specific surface area and the change of pore channel structure are smaller, which shows that the thermal stability of the mixed metal oxide materials A and B is increased along with the increase of the doping amount of La and B in the bimetallic oxide.
Therefore, compared with undoped active alumina material, the mixed metal oxide carrier prepared by the method has better thermal stability, and the material used as a catalyst carrier is more beneficial to improving the stability of the catalyst.
(II) surface acidity characterization experiment of Material
The characterization experiment of the surface acidity of the sample adopts an NH 3 -TPD method.
The NH 3 -TPD experiment was performed on a temperature programmed chemisorber model TP-5080: firstly, pretreating a sample at 600 ℃ in He gas (30 ml/min) for 1 h; after the temperature is reduced to 100 ℃, the NH 3 -He mixed gas is switched, ammonia gas is adsorbed to be saturated, and then the temperature is programmed to be increased to 600 ℃ at the heating rate of 10 ℃/min for desorption; the desorbed NH 3 is detected by a Thermal Conductivity Detector (TCD).
The NH 3 -TPD test was performed on the above materials A1, B3, and B5, and the results are shown in FIG. 1.
As can be seen from FIG. 1, as the doping amount of La and B increases, the high Wen Tuowei shoulder peak in the TPD spectrogram is less and less obvious after the sample adsorbs ammonia, the peak temperature of the TPD spectrogram is also shifted to the low temperature direction, but the total area of the TPD spectrogram is slightly reduced, which indicates that the number of acid centers on the surface of the material is not greatly changed, but the number of strong acid centers is reduced and the acidity is gradually weakened.
The data show that the doping of La and B can influence the strong acid center of the alumina surface to make the alumina surface transition to the weak acid center, so that the acidity distribution of the material surface is changed.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation, etc. of the above embodiment according to the technical matter of the present invention fall within the scope of the present invention.
Claims (5)
1. A preparation method of a La and B doped zinc oxide-aluminum oxide composite metal oxide carrier with thermal stability is characterized by comprising the following steps: the method comprises the following steps of:
S1, stirring and mixing zinc oxide, active aluminum oxide and an auxiliary agent, extruding the mixture into strips, and preparing a bimetal oxide material, wherein the content of zinc oxide in the bimetal oxide material is 1-10wt%,
S2, preparing a mixed solution containing La (NO 3)3·6H2O、H3BO3, wherein the mass ratio of La (NO 3)3·6H2 O to H 3BO3 is 5:1-1:5;
s3, adding the bimetallic oxide material into the mixed solution, soaking for 4-10 hours, drying for 2-4 hours at 150-200 ℃, and roasting to obtain a metal oxide carrier, wherein the contents of La and B in the metal oxide carrier are respectively 0.1-5 wt%.
2. The method of manufacturing according to claim 1, characterized in that: in the step S1, the auxiliary agent is selected from sesbania powder, methylcellulose, starch or cyclodextrin.
3. The method of manufacturing according to claim 1, characterized in that: in the step S1, a single screw extruder is adopted during extrusion, and the extrusion pressure is controlled to be 2750-3450 kPa.
4. A La, B doped zinc oxide-alumina composite metal oxide support prepared by the preparation method of any one of claims 1 to 3.
5. Use of a La, B doped zinc oxide-alumina composite metal oxide support according to claim 4 for the preparation of a propane dehydrogenation catalyst.
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| KR20170045189A (en) * | 2017-04-19 | 2017-04-26 | 롯데케미칼 주식회사 | Dehydrogenation catalyst and manufacturing method same |
| CN106660015A (en) * | 2014-07-28 | 2017-05-10 | 乐天化学株式会社 | Dehydrogenation catalyst, and preparation method therefor |
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| CN113441129A (en) * | 2021-08-06 | 2021-09-28 | 西南化工研究设计院有限公司 | Composite metal oxide type alkane dehydrogenation catalyst and preparation method thereof |
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| CN106660015A (en) * | 2014-07-28 | 2017-05-10 | 乐天化学株式会社 | Dehydrogenation catalyst, and preparation method therefor |
| KR20170045189A (en) * | 2017-04-19 | 2017-04-26 | 롯데케미칼 주식회사 | Dehydrogenation catalyst and manufacturing method same |
| CN111659415A (en) * | 2019-03-05 | 2020-09-15 | 绍兴胜迹新材料科技有限公司 | Preparation method of coupled nano composite noble metal catalyst of active alumina carrier |
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