CN114749184A - Metal carrier catalyst, preparation method and application thereof - Google Patents
Metal carrier catalyst, preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 154
- 239000002184 metal Substances 0.000 title claims abstract description 154
- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 66
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 238000000975 co-precipitation Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000002041 carbon nanotube Substances 0.000 claims description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 239000013078 crystal Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 238000009827 uniform distribution Methods 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000014509 gene expression Effects 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 oxygen ions Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- B01J35/615—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
Abstract
The application relates to the technical field of catalysts, in particular to a metal carrier catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: preparing metal salt and carrier raw materials into a mixed dispersion liquid; carrying out solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the solid-phase reaction treatment comprises hydrothermal method solid-phase reaction treatment or coprecipitation method solid-phase reaction treatment; and sintering the precursor, and then reducing and activating to obtain the metal carrier catalyst. The hydrothermal method solid phase reaction or the coprecipitation method solid phase reaction is adopted to enable the metal salt and the carrier to react well, the obtained metal carrier catalyst is ensured to have complete crystal grain development, small particle size, uniform distribution and light particle aggregation, and the sintering treatment is further carried out to remove impurities on the surface of the metal carrier catalyst, so that the metal carrier catalyst has uniform particle size and increased specific surface area, and further the catalytic efficiency of the material is improved.
Description
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a metal carrier catalyst and a preparation method and application thereof.
Background
The carbon nano tube is a one-dimensional quantum material with a special structure (the carbon nano tube mainly comprises carbon atoms arranged in a hexagon to form a coaxial circular tube with a plurality of layers to dozens of layers, a fixed distance is kept between every two layers, the distance is about 0.34nm, the diameter is generally 2-20 nm, and the carbon nano tube can be divided into a sawtooth shape, an arm chair shape and a spiral shape according to different axial orientations of the carbon hexagon.
The preparation method of the carbon nano tube mainly comprises the following steps: arc discharge, laser ablation, chemical vapor deposition (hydrocarbon gas pyrolysis), solid phase pyrolysis, glow discharge, gas combustion, and polymerization synthesis. Among them, the chemical vapor deposition method has high efficiency, and thus, the application is wider. However, when the carbon nanotubes are synthesized using chemical vapor deposition, the catalyst plays a very important role because the growth of the carbon nanotubes varies with the type and composition ratio of the transition metal and the size of the metal particles, and thus in order to improve the synthesis efficiency of the carbon nanotubes, it is required to improve the catalytic efficiency of the metal-supported catalyst.
At present, the preparation method of the metal carrier catalyst is very simple, and the metal carrier catalyst is usually prepared by adopting an impregnation method, and the preparation method is simple, so that the obtained carrier catalyst has uneven particle size and poor catalytic efficiency, and is not beneficial to being applied to the preparation of carbon nano tubes.
Disclosure of Invention
The application aims to provide a metal carrier catalyst, and a preparation method and application thereof, and aims to solve the problems of uneven particle size and poor catalytic efficiency of the carrier catalyst obtained by the preparation method in the prior art.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a method for preparing a metal supported catalyst, comprising the steps of:
preparing metal salt and carrier raw materials into a mixed dispersion liquid;
carrying out solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the solid-phase reaction treatment comprises a hydrothermal method solid-phase reaction treatment or a coprecipitation method solid-phase reaction treatment;
sintering the precursor, and then reducing and activating to obtain the metal carrier catalyst.
In a second aspect, the present application provides a metal supported catalyst, wherein the metal supported catalyst is prepared by a preparation method of the metal supported catalyst, the metal supported catalyst is a porous spherical catalyst, the particle size of the porous spherical catalyst is 125-300 μm, and the specific surface area of the porous spherical catalyst is 200-400m 2The pore diameter is 3-20 nm.
In a third aspect, the present application provides a metal supported catalyst for use in the preparation of carbon nanotubes.
According to the preparation method of the metal carrier catalyst provided by the first aspect of the application, firstly, metal salt and carrier raw materials are prepared into mixed dispersion liquid, then the mixed dispersion liquid is subjected to hydrothermal solid-phase reaction or coprecipitation solid-phase reaction, the hydrothermal solid-phase reaction or coprecipitation solid-phase reaction can be adopted to enable the metal salt and the carrier to better react, the obtained metal carrier catalyst is ensured to have complete crystal grain development, small granularity, uniform distribution and light particle agglomeration, sintering treatment is carried out to enable the metal salt and the carrier to be tightly connected and remove impurities on the surface of the metal carrier catalyst, and then reduction activation is carried out to obtain a metal simple substance, so that the metal carrier catalyst is uniform in grain size and increased in specific surface area, and further the catalytic efficiency of the material is improved; meanwhile, the preparation method is simple and easy to operate, and is beneficial to industrial mass production.
The metal carrier catalyst provided by the second aspect of the application has the advantages that the crystal grain of the metal carrier catalyst is completely developed and is in a porous spherical shape, the obtained catalyst is moderate in particle size, high in purity, good in dispersity, uniform, free of agglomeration, controllable in shape, increased in specific surface area and high in catalytic efficiency, and the wide application of the metal carrier catalyst is facilitated.
The metal carrier catalyst provided by the third aspect of the application is applied to the preparation of the carbon nano tube, and the obtained metal carrier catalyst has the advantages of controllable shape, uniform particle size and high catalytic efficiency, and is applied to the preparation of the carbon nano tube, thereby being beneficial to improving the production efficiency of the carbon nano tube and being easy to carry out industrial mass production.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
In this application, the term "and/or" describes an association relationship of associated objects, which means that there may be three relationships, for example, a and/or B, which may mean: a alone, A and B together, and B alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In this application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
A first aspect of an embodiment of the present application provides a method for preparing a metal supported catalyst, including the steps of:
s01, preparing a mixed dispersion liquid from metal salt and a carrier raw material;
s02, carrying out first solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the first solid-phase reaction treatment comprises a hydrothermal method solid-phase reaction treatment or a coprecipitation method solid-phase reaction treatment;
and S03, sintering the precursor, and then reducing and activating to obtain the metal carrier catalyst.
Because the prior art generally adopts an impregnation method for preparation, the preparation method is simple, so that the obtained carrier catalyst has uneven particle size and poorer catalytic efficiency; according to the preparation method of the metal carrier catalyst provided by the first aspect of the embodiment of the application, firstly, the metal salt and the carrier raw material are prepared into the mixed dispersion liquid, then the mixed dispersion liquid is subjected to hydrothermal solid-phase reaction or coprecipitation solid-phase reaction, the hydrothermal solid-phase reaction or coprecipitation solid-phase reaction can be adopted to enable the metal salt and the carrier to better react, and the obtained metal carrier catalyst is ensured to have complete crystal grain development, small particle size, uniform distribution and light particle agglomeration, is subjected to sintering treatment and then is subjected to reduction activation to remove impurities on the surface of the metal carrier catalyst, so that the metal carrier catalyst is uniform in particle size and increased in specific surface area, and further the catalytic efficiency of the material is improved; meanwhile, the preparation method is simple and easy to operate, and is beneficial to industrial mass production.
In step S01, a mixed dispersion is prepared from the metal salt and the carrier raw material.
In some embodiments, the metal salt comprises at least one of an iron salt, a molybdenum salt; in some embodiments, the iron salt comprises at least one of ferric nitrate, ferric acetate, ferric chloride, ferric bromide, ferric oxide; the molybdenum salt comprises at least one of molybdenum nitrate, molybdenum acetate and molybdenum oxide. And providing iron salt and molybdenum salt as reactants for reaction to finally obtain metallic iron and metallic molybdenum elementary substance loaded on the surface of the carrier. Preferably, iron nitrate and molybdenum nitrate are selected, and the inventor finds in research that the coprecipitation method can maintain higher dispersity of the iron nitrate and molybdenum nitrate components at a larger loading amount compared with the conventional impregnation method, thereby improving the catalytic efficiency.
In some embodiments, the support material comprises alpha-alumina, which is the most stable phase of all aluminas, since alpha-alumina is trigonal a2B3The compound has the structure that oxygen ions are approximately packed in a close-packed hexagonal mode, and aluminum atoms are filled in octahedral gaps of the compound. Since the ratio of aluminum atoms to oxygen atoms is 2:3, the aluminum atoms do not fill all the octahedral voids, filling only 2/3, and thus reducing the symmetry of the alpha-alumina crystal. In the crystal structure of alpha-alumina, the plane composed of 3 oxygen atoms is shared by two adjacent octahedra, and the whole crystal can be seen as countless octahedra [ AlO ] 6]The large 'molecule' formed by coplanar combination ensures that the stability of the selected alpha-alumina is large, the metal particles loaded on the carrier after reaction are stable, and the metal carrier catalyst has high stability, thereby being more beneficial to large-scale preparation and use in industry.
In some embodiments, the alpha-alumina has a specific surface area of 50 to 80m2The specific surface area of the provided alpha-alumina is larger, which is beneficial to the loading of the metal simple substance, improves the loading amount of the metal simple substance, and simultaneously improves the specific surface area of the obtained metal carrier catalyst, so that the catalytic efficiency is higher. In some embodiments, the alpha-alumina has a specific surface area of 50m2/g、55m2/g、60m2/g、65m2/g、70m2/g、75m2/g、80m2/g。
In some embodiments, the molar ratio of metal salt to support material is 15 to 45: 30-85; the molar ratio of the metal salt to the carrier raw material is controlled, so that the obtained metal carrier catalyst is high in catalytic efficiency, and the synthesis of the carbon nano tube is facilitated when the metal carrier catalyst is applied to the preparation process of the carbon nano tube.
In some embodiments, the molar ratio of metal salt to support starting material includes, but is not limited to, 15: 85. 20: 80. 25: 75. 30: 70. 35: 65. 40: 60. 45, and (2) 45: 65.
in some embodiments, in the obtained metal carrier catalyst, the mass ratio of the metal simple substance to the total mass of the metal carrier catalyst is 17.04-63.51%, and the control of the mass ratio of the metal simple substance can ensure that the obtained metal carrier catalyst has higher catalytic efficiency. In some embodiments, the mass ratio of the elemental metal in the metal supported catalyst to the total mass of the metal supported catalyst as a whole includes, but is not limited to, 17%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, 47%, 50%, 52%, 55%, 57%, 60%, 63%.
In step S02, performing a solid-phase reaction on the mixed dispersion to obtain a precursor; wherein the solid-phase reaction treatment comprises hydrothermal method solid-phase reaction treatment or coprecipitation method solid-phase reaction treatment. The hydrothermal method solid phase reaction or the coprecipitation method solid phase reaction can enable the metal salt and the carrier to react well, and ensure that the obtained metal carrier catalyst has complete crystal grain development, small particle size, uniform distribution and light particle agglomeration, and is sintered to remove impurities on the surface of the metal carrier catalyst, so that the metal carrier catalyst has uniform particle size and increased specific surface area, and further the catalytic efficiency of the material is improved; meanwhile, the preparation method is simple and convenient to operate, and industrial mass production is facilitated.
In some embodiments, in the step of subjecting the mixed dispersion to a solid-phase reaction treatment to obtain a precursor, the solid-phase reaction treatment is selected from a hydrothermal solid-phase reaction treatment; wherein in the step of hydrothermal solid-phase reaction treatment, the pressure of the hydrothermal solid-phase reaction treatment is 0.1-3.0 MPa, the temperature is 250-600 ℃, and the time is 2-10 hours. In the hydrothermal reaction process, the treatment pressure and temperature of the reaction are mainly controlled, the crystal structure of the obtained material is controlled to be complete through the pressure and temperature of the reaction, the crystal grain purity is high, and the particle size of the obtained material is ensured to be uniform. The diameter of the metal carrier catalyst prepared by adopting the condition is 125-300 mu m.
In some embodiments, in the step of hydrothermal solid-phase reaction treatment, the pressure of the hydrothermal solid-phase reaction treatment is 2.5 to 3.0MPa, the temperature is 350 to 600 ℃, and the time is 4 to 6 hours. The treatment under the condition is a high-temperature high-pressure hydrothermal reaction treatment, the reaction time can be controlled to be short, the reaction rate is high, and the metal carrier catalyst can be quickly formed.
In some embodiments, in the step of subjecting the mixed dispersion to a solid-phase reaction treatment to obtain a precursor, the solid-phase reaction treatment is selected from a coprecipitation method solid-phase reaction treatment; and (2) adopting a coprecipitation method for treatment, enabling cations in the solution to exist in the solution in a homogeneous phase, adding a precipitator, and obtaining uniform precipitates of various components after precipitation reaction to obtain the metal carrier catalyst.
Wherein, in the step of solid phase reaction treatment by coprecipitation method, the method comprises the following steps: mixing a precipitator and a dispersion liquid, and then carrying out coprecipitation solid-phase reaction treatment, wherein the pressure of the coprecipitation solid-phase reaction treatment is 0.3-0.6MPa, the temperature is 40-80 ℃, and the time is 1-5 hours; and, the precipitant comprises an alkaline precipitant. The coprecipitation solid-phase reaction is further acted by adding the alkaline precipitator, so that the reaction pressure and temperature are low, and the reaction condition is mild.
In some embodiments, an alkaline precipitant, including but not limited to sodium hydroxide, is added to rapidly combine with the metal cation to form a precipitate, thereby increasing the rate of production.
In some embodiments, the molar ratio of the basic precipitant to the metal salt is 1.2-2: 1, in order to completely precipitate the metal salt, a slight excess of the basic precipitant is provided to facilitate the binding with the metal salt in the mixed solution. In some embodiments, the molar ratio of the basic precipitant to the metal salt includes, but is not limited to, 1.2: 1. 1.3: 1. 1.4: 1. 1.5: 1. 1.6: 1. 1.7: 1. 1.8: 1. 1.9: 1. 2.0: 1.
in some specific embodiments, the pressure of the coprecipitation method solid-phase reaction treatment is 0.3-0.4MPa, the temperature is 60-80 ℃, and the time is 2-3 hours, and the metal carrier catalyst obtained by the reaction under the coprecipitation method solid-phase reaction condition has uniform particle size and good dispersion.
In step S03, the precursor is sintered, and then reduced and activated to obtain the metal supported catalyst.
In some embodiments, the precursor is subjected to a sintering treatment at a temperature of 400-1200 ℃ for 1-6 hours. The spherical particles are cleaved by further combining a sintering process, thereby significantly increasing the surface area of the spherical particles.
In some embodiments, the temperature of the sintering process includes, but is not limited to, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C, 1100 deg.C, 1200 deg.C.
In some embodiments, the time of the sintering process includes, but is not limited to, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours.
In some embodiments, the reduction activation comprises introducing 80-120L/min hydrogen and inert gas into a reduction furnace to reduce the sintered catalyst for 8-20min at a reduction temperature of 300-400 ℃. The sintered catalyst is subjected to reduction activation treatment, process parameters such as air flow velocity, reduction temperature, time and the like are optimized, and the metal oxide is reduced into metal nano particles, so that the catalytic activity of the catalyst is improved.
In some embodiments, hydrogen and inert gas are introduced to ensure that the hydrogen performs a better reduction treatment, and under the protection of the inert gas, no other reaction occurs during the reduction treatment, thereby avoiding the generation of other impurities. In some embodiments, the hydrogen and inert gases are introduced at a rate including, but not limited to, 80L/min, 90L/min, 100L/min, 110L/min, 120L/min.
In some embodiments, the inert gas comprises at least one of helium, neon, argon, krypton, xenon, radon, nitrogen.
In some embodiments, the time of the reduction treatment is 8-20min, and the temperature of the reduction treatment is 300-400 ℃; if the time for the reduction treatment is too short or the reduction temperature is too low, the reduction treatment is incomplete, and the effect of the reduction treatment is impaired.
In some embodiments, the time of the reduction treatment includes, but is not limited to, 8min, 10min, 12min, 14min, 16min, 18min, 20 min.
In some embodiments, the temperature of the reduction treatment includes, but is not limited to, 300 deg.C, 320 deg.C, 340 deg.C, 360 deg.C, 380 deg.C, 400 deg.C.
In a second aspect, the present application provides a metal supported catalyst, wherein the metal supported catalyst is prepared by a preparation method of the metal supported catalyst, the metal supported catalyst is a porous spherical catalyst, the particle size of the porous spherical catalyst is 125-300 μm, and the specific surface area of the porous spherical catalyst is 200-400m2G, the pore diameter is 3-20 nm.
The metal carrier catalyst provided by the second aspect of the application has the advantages that the crystal grain of the metal carrier catalyst is completely developed and is in a porous spherical shape, the obtained catalyst is moderate in particle size, high in purity, good in dispersity, uniform, free of agglomeration, controllable in shape, increased in specific surface area and high in catalytic efficiency, and the wide application of the metal carrier catalyst is facilitated.
In some embodiments, the metal supported catalyst comprises at least one metal catalyst of iron and molybdenum supported on the surface of an alpha alumina support.
In some embodiments, the metal supported catalyst is a porous spherical catalyst.
In some embodiments, in the metal supported catalyst, the ratio of Fe: mo: z, wherein x is more than or equal to 15 and less than or equal to 40; y is more than or equal to 0 and less than or equal to 3; z is more than or equal to 30 and less than or equal to 80, and after conversion: fe and Mo in the total mass (Fe, Mo, and Al)2O3) The mass ratio of (A) is in the range of 17.04-63.51%. Ensure to obtainThe obtained metal carrier catalyst has high catalytic efficiency.
In some embodiments, the metal supported catalyst has a surface area of 200 to 400m2The specific surface area of the provided carrier raw material is large, and the carrier raw material is subjected to corresponding solid-phase reaction treatment and sintering treatment, so that the surface area of the obtained metal carrier catalyst is 200-400 m2/And g, the increase of the specific surface area is beneficial to improving the catalytic efficiency of the catalyst. The larger the specific area of the catalyst, the higher the catalytic activity.
In some embodiments, the surface area of the metal supported catalyst includes, but is not limited to, 200m2/g、220m2/g、240m2/g、260m2/g、270m2/g、300m2/g、320m2/g、340m2/g、360m2/g、380m2/g、400m2/g，
In some embodiments, the resulting metal supported catalyst is spherical and the diameter of the metal supported catalyst is 125-300 μm. In some embodiments, the diameter of the metal supported catalyst includes, but is not limited to, 125 μm, 130 μm, 135 μm, 140 μm, 145 μm, 155 μm, 160 μm, 165 μm, 170 μm, 175 μm, 180 μm, 185 μm, 190 μm, 195 μm, 200 μm, 205 μm, 210 μm, 215 μm, 220 μm, 225 μm, 230 μm, 235 μm, 240 μm, 245 μm, 250 μm, 255 μm, 260 μm, 265 μm, 270 μm, 275 μm, 280 μm, 285 μm, 290 μm, 295 μm, 300 μm.
In a third aspect, the present application provides a metal supported catalyst for use in the preparation of carbon nanotubes.
The metal carrier catalyst provided by the third aspect of the embodiment of the present application is applied to the preparation of carbon nanotubes, and the obtained metal carrier catalyst has a controllable shape, a uniform particle size and high catalytic efficiency, and is applied to the preparation of carbon nanotubes, thereby facilitating the improvement of the production efficiency of carbon nanotubes and facilitating industrial mass production.
The following description is given with reference to specific examples.
Example 1
Preparation method of metal carrier catalyst
The preparation method comprises the following steps:
providing ferric nitrate, molybdenum nitrate and alpha-alumina to prepare a mixed dispersion liquid; the molar ratio of the metal salt to the carrier raw material is 15: 85 parts by weight;
carrying out hydrothermal solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the pressure of the hydrothermal method solid-phase reaction treatment is 2.5MPa, the temperature is 350 ℃, and the time is 4 hours;
sintering the precursor, and then reducing and activating, wherein the sintering temperature is 400 ℃ and the time is 6 hours; the reduction activation comprises the steps of introducing 80L/min of hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 10min at the reduction temperature of 300 ℃ to obtain the metal carrier catalyst.
Example 2
Preparation method of metal carrier catalyst
The preparation method comprises the following steps:
providing iron acetate, molybdenum acetate and alpha-alumina to prepare a mixed dispersion liquid; the molar ratio of the metal salt to the carrier raw material is 30: 70;
carrying out hydrothermal solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the pressure of the hydrothermal method solid-phase reaction treatment is 2.8MPa, the temperature is 500 ℃, and the time is 5 hours;
sintering the precursor, and then reducing and activating, wherein the sintering temperature is 800 ℃, and the time is 3 hours; the reduction activation comprises the steps of introducing 90L/min of hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 12min, wherein the reduction temperature is 320 ℃, and the metal carrier catalyst is obtained.
Example 3
Preparation method of metal carrier catalyst
The preparation method comprises the following steps:
providing iron oxide, molybdenum oxide and alpha-alumina to prepare a mixed dispersion liquid; the molar ratio of the metal salt to the carrier raw material is 45: 55;
carrying out hydrothermal solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the pressure of the hydrothermal method solid-phase reaction treatment is 3MPa, the temperature is 600 ℃, and the time is 6 hours;
sintering the precursor, and then reducing and activating, wherein the sintering temperature is 1200 ℃, and the time is 1 hour; the reduction activation comprises the steps of introducing 100L/min hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 14min, wherein the reduction temperature is 340 ℃, and the metal carrier catalyst is obtained.
Example 4
Preparation method of metal carrier catalyst
The preparation method comprises the following steps:
providing ferric nitrate, molybdenum nitrate, alpha-alumina and sodium hydroxide to prepare a mixed dispersion liquid; the molar ratio of the metal salt to the carrier raw material is 15: 85 parts by weight; the molar ratio of sodium hydroxide to metal salt is 1.2: 1;
carrying out coprecipitation solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the pressure of the coprecipitation solid-phase reaction treatment is 0.3MPa, the temperature is 40 ℃, and the time is 5 hours;
sintering the precursor, and then reducing and activating, wherein the sintering temperature is 400 ℃ and the time is 6 hours; the reduction activation comprises the steps of introducing 110L/min hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 16min, wherein the reduction temperature is 360 ℃, and the metal carrier catalyst is obtained.
Example 5
Preparation method of metal carrier catalyst
The preparation method comprises the following steps:
providing iron acetate, molybdenum acetate, alpha-alumina and sodium hydroxide to prepare a mixed dispersion liquid; the molar ratio of the metal salt to the carrier raw material is 30: 70; the molar ratio of sodium hydroxide to metal salt is 1.5: 1;
carrying out coprecipitation solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the pressure of the coprecipitation solid-phase reaction treatment is 0.5MPa, the temperature is 60 ℃, and the time is 3 hours;
Sintering the precursor, and then reducing and activating, wherein the sintering temperature is 800 ℃, and the time is 3 hours; the reduction activation comprises the steps of introducing 120L/min hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 18min, wherein the reduction temperature is 360 ℃, and thus the metal carrier catalyst is obtained.
Example 6
Preparation method of metal carrier catalyst
The preparation method comprises the following steps:
providing iron oxide, molybdenum oxide, alpha-aluminum oxide and sodium hydroxide to prepare a mixed dispersion liquid; the molar ratio of the metal salt to the carrier raw material is 45: 55; the molar ratio of sodium hydroxide to metal salt is 1.8: 1;
carrying out coprecipitation solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the pressure of the coprecipitation solid-phase reaction treatment is 0.6MPa, the temperature is 80 ℃, and the time is 5 hours;
sintering the precursor, and then reducing and activating, wherein the sintering temperature is 1200 ℃, and the time is 1 hour; the reduction activation comprises the steps of introducing 120L/min of hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 20min, wherein the reduction temperature is 400 ℃, and thus the metal carrier catalyst is obtained.
Comparative example 1
The preparation method of the metal carrier catalyst by adopting the conventional impregnation method in the field comprises the following specific steps:
Pretreating alpha-alumina, and then preparing a steeping liquor containing ferric nitrate, molybdenum nitrate and oxalic acid; the molar ratio of the metal salt to the carrier raw material is 15: 85; the molar ratio of oxalic acid to metal salt is 0.5: 1, the concentration of the impregnation liquid is 1.0 mol per liter of the metal salt content;
soaking the pretreated alpha-alumina in the soaking solution for 6 hours, and then taking out and naturally drying;
sintering the precursor, and then reducing and activating, wherein the sintering temperature is 400 ℃, and the time is 6 hours; the reduction activation comprises the steps of introducing 80L/min of hydrogen and inert gas into a reduction furnace to carry out reduction treatment on the sintered catalyst for 10min at the reduction temperature of 300 ℃ to obtain the metal carrier catalyst.
Performance testing and results analysis
The metal-supported catalysts prepared in examples 1 to 6 and comparative example 1 were analyzed by N-N using a specific surface area and pore size analyzer (3H-2000PS4 model, Bechard instruments technologies (Beijing) Ltd.)2Characterization of the specific surface area (m) of the catalyst2Per g) and pore size (nm). The results are shown in Table 1.
TABLE 1 analysis of specific surface area and pore diameter of metal carrier catalyst
| Item | Specific surface area (m)2/g) | Pore size (nm) |
| Example 1 | 278.568 | 4.58 |
| Example 2 | 305.563 | 4.12 |
| Example 3 | 292.521 | 4.35 |
| Example 4 | 298.654 | 4.25 |
| Example 5 | 312.214 | 4.10 |
| Example 6 | 291.365 | 4.56 |
| Comparative example 1 | 245.254 | 5.23 |
As can be seen from Table 1, the metal supported catalyst prepared by the invention has high specific surface area and small pore diameter, and can improve the catalytic efficiency of carbon nanotube preparation. This is because the hydrothermal method and the coprecipitation method can maintain a high degree of dispersion of the metal salt component at a high loading, thereby improving the catalytic efficiency. The metal carrier catalyst prepared by adopting the conventional impregnation method in the field is not easy to be uniformly distributed in the carrier because the active component metal salt enters the inside of the carrier in the impregnation process, and the loading capacity is not high, so that the prepared catalyst has larger particle aperture and reduced specific surface area, and the catalytic activity of the carbon nano tube is influenced.
The non-reduction activated catalysts prepared in example 1 and comparative example 1 were subjected to hydrogen temperature programmed reduction detection, and H was performed using a high performance full-automatic chemical adsorption apparatus (AutoChem II 2920 type)2TPR test, which characterizes the reduction characteristics of the catalyst, with a heating rate of 10 ℃/min and a gas mixture of 5% H2Ar, sample mass 50 mg. Since the alumina as the carrier material is not reduced by hydrogen, the reduction peak formed in the test process is the reduction peak of the metal salt, and the test finds that the hydrogen consumption area of the reduction peak of example 1 is obviously larger than that of comparative example 1, which shows that the content of the metal salt loaded on the metal carrier catalyst of example 1 is obviously higher than that of the metal salt loaded on the metal carrier catalyst of comparative example 1, so that the metal carrier catalyst of example 1 has more catalytic sites and higher catalytic activity.
The metal supported catalysts prepared in examples 1 to 6 and comparative example 1 were used for the preparation of carbon nanotubes under the same reaction conditions. The metal carrier catalyst disclosed in the embodiments 1-6 of the invention is found to be applied to the preparation of carbon nanotubes, so that the catalytic activity is higher, the specific surface area of the obtained carbon nanotubes is larger, and the ash content is less.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A preparation method of a metal carrier catalyst is characterized by comprising the following steps:
preparing metal salt and carrier raw materials into a mixed dispersion liquid;
carrying out solid-phase reaction treatment on the mixed dispersion liquid to obtain a precursor; wherein the solid-phase reaction treatment comprises a hydrothermal method solid-phase reaction treatment or a coprecipitation method solid-phase reaction treatment;
and sintering the precursor, and then reducing and activating to obtain the metal carrier catalyst.
2. The method of claim 1, wherein in the step of hydrothermal solid-phase reaction treatment, the pressure of the hydrothermal solid-phase reaction treatment is 0.1-3.0 MPa, the temperature is 250-600 ℃, and the time is 2-10 hours.
3. The method for preparing a metal supported catalyst according to claim 1, wherein the step of the coprecipitation solid-phase reaction treatment comprises: providing a precipitator and mixing the precipitator with the dispersion liquid, and then carrying out coprecipitation solid-phase reaction treatment, wherein the pressure of the coprecipitation solid-phase reaction treatment is 0.3-0.6MPa, the temperature is 40-80 ℃, and the time is 1-5 hours; and, the precipitating agent comprises an alkaline precipitating agent.
4. The method for preparing a metal supported catalyst according to any one of claims 1 to 3, wherein the metal salt comprises at least one of an iron salt and a molybdenum salt; and/or
The support raw material comprises alpha-alumina;
the molar ratio of the metal salt to the carrier raw material is 15-45: 30-85.
5. The method for preparing the metal supported catalyst according to any one of claims 1 to 3, wherein the reduction activation comprises introducing 80 to 120L/min of hydrogen and inert gas into a reduction furnace to perform reduction treatment on the sintered catalyst for 8 to 20min at a reduction temperature of 300 ℃ to 400 ℃.
6. The method for producing a metal supported catalyst according to claim 5,
the inert gas comprises at least one of helium, neon, argon, krypton, xenon, radon and nitrogen.
7. The method for preparing a metal supported catalyst according to any one of claims 1 to 3, wherein the sintering treatment is carried out at a temperature of 400 to 1200 ℃ for 1 to 6 hours.
8. The metal supported catalyst is characterized in that the metal supported catalyst is prepared by the preparation method of the metal supported catalyst as claimed in any one of claims 1 to 7, the metal supported catalyst is a porous spherical catalyst with the particle size of 125-300 μm and the specific surface area of 200-400m2G, the pore diameter is 3-20 nm.
9. The metal supported catalyst of claim 8, wherein the metal supported catalyst comprises at least one metal catalyst selected from the group consisting of iron and molybdenum supported on the surface of an α -alumina support.
10. The metal supported catalyst of claim 8 is applied to the preparation of carbon nanotubes.
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