CN117797821A - Copper-indium catalyst with broken shell hollow sphere morphology, and preparation method and application thereof - Google Patents
Copper-indium catalyst with broken shell hollow sphere morphology, and preparation method and application thereof Download PDFInfo
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- CN117797821A CN117797821A CN202311636143.7A CN202311636143A CN117797821A CN 117797821 A CN117797821 A CN 117797821A CN 202311636143 A CN202311636143 A CN 202311636143A CN 117797821 A CN117797821 A CN 117797821A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000003223 protective agent Substances 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000000889 atomisation Methods 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003595 mist Substances 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000005118 spray pyrolysis Methods 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 7
- 239000006004 Quartz sand Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000003075 superhydrophobic effect Effects 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- LKRFCKCBYVZXTC-UHFFFAOYSA-N dinitrooxyindiganyl nitrate Chemical compound [In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LKRFCKCBYVZXTC-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005406 washing Methods 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
- B01J23/825—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 gallium, indium or thallium
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a copper-indium catalyst with a broken shell hollow sphere morphology, a preparation method and application thereof, wherein a copper source and an indium source are used as raw materials, a protective agent, a surfactant and a reducing agent are added, the copper-indium catalyst is synthesized through a spray pyrolysis method, and collected precursor powder is subjected to vacuum drying, roasting and reduction treatment to obtain the copper-indium catalyst; the copper-indium catalyst prepared by the method has special morphology, is in a shell-breaking hollow sphere shape, has the diameter of 1-2 mu m, and has the pore-forming broken shell, the diameter of 100-500nm, large specific surface area, small density, low cost and small pollution, and the obtained sample is used for gas-solid phase catalytic reaction and shows excellent catalytic performance, so that the copper-indium catalyst has good research value and application prospect.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a copper-indium catalyst with a shell-broken hollow sphere morphology, and a preparation method and application thereof.
Background
Copper-indium materials have good application potential in middle-high-end industry, new energy technology and catalytic reaction, and are therefore receiving wide attention. The copper indium material is used as one of basic targets of CIG (copper indium gallium) and CIGS (copper indium gallium selenium) thin film solar materials, has the advantages of small pollution, no decay, good dim light performance, high photoelectric conversion efficiency and the like, is widely applied to the field of solar cells, and is technically applied to catalytic reaction due to excellent product conversion rate and selectivity.
However, the conventional preparation method of the copper-indium catalyst with the special structure adopts a hard template method and a soft template method to obtain the copper-indium catalyst, wherein the template agent needs to be removed in the preparation process of the hard template method, the operation is complex, and collapse and damage of a product structure can be caused. The soft template method has the advantages of poor structural stability and low efficiency, and the two methods have high price and long reaction time, and are not suitable for large-scale and wide popularization and application.
The patent with publication number CN 114029064A published in 2/11/2022 discloses a preparation method and application of a super-hydrophobic porous copper indium catalyst, wherein the preparation method comprises the following steps: (1) Mixing ammonium fluoride, a silicon-based molecular sieve and water, stirring, performing hydrothermal treatment, filtering, drying and roasting to obtain the super-hydrophobic silicon-based molecular sieve; (2) Mixing the template agent with the precursor, co-precipitating to obtain a precipitate, filtering, drying and roasting; (3) Washing the material roasted in the step (2) with water, and drying to obtain copper-indium mixed oxide; (4) And (3) respectively grinding the super-hydrophobic silicon-based molecular sieve obtained in the step (1) and the copper-indium mixed oxide obtained in the step (3), mixing, and grinding again to obtain the composite material. However, it discloses a conventional preparation method, and its carbon dioxide conversion rate is low.
Therefore, there is a need to find a method for preparing copper-indium catalyst which is low in cost, easy to operate and capable of improving the carbon dioxide conversion rate.
Disclosure of Invention
The invention aims to provide a copper-indium catalyst with a broken shell hollow sphere morphology and a preparation method thereof, wherein a spray pyrolysis method is adopted to prepare the copper-indium catalyst CuO-In by combining a reducing gas reduction means 2 O 3 The prepared copper-indium catalyst has special morphology, is spherical, and the spherical shell is broken in a pore-forming manner, and is hollow and spherical as a whole, and the spherical shell has the pore-forming breakage, so that the specific surface area is large, the density is low, the cost is low, and the pollution is small.
The invention also aims to provide the application of the copper indium catalyst with the shell-broken hollow sphere morphology, which is used for gas-solid phase catalytic reaction, is used for catalyzing carbon dioxide hydrogenation to prepare methanol, can improve the carbon dioxide conversion rate and shows excellent catalytic performance.
The specific technical scheme of the invention is as follows:
the preparation method of the copper-indium catalyst with the shell-broken hollow sphere morphology comprises the following steps:
1) Mixing a copper source, an indium source, a reducing agent, a protective agent, a surfactant and a solvent, and stirring to obtain a suspension;
2) And (3) carrying out ultrasonic oscillation, atomization, pyrolysis and vacuum drying on the suspension, and then roasting and reducing to obtain the copper-indium catalyst with the shell-broken hollow sphere morphology.
In the step 1), the ratio of the amounts of the substances of the copper source and the indium source is 0.25-4.0: 1, a step of;
in the step 1), the ratio of the total substances of the copper source and the indium source to the solvent is 0.075-0.2mol/L;
in the step 1), the dosage ratio of the reducing agent to the solvent is 0.05-0.25 mol/L;
in the step 1), the dosage ratio of the protective agent to the solvent is 10-30g/L;
in the step 1), the dosage ratio of the surfactant to the solvent is 10-30g/L;
in the step 1), stirring is carried out for 1-2 h under intense stirring; stirring frequency is 400-600 rpm, suspension temperature is 20-25 ℃;
in step 1), the copper source is selected from soluble copper salts, preferably copper nitrate trihydrate;
in step 1), the indium source is selected from soluble indium salts, preferably indium nitrate;
in step 1), the reducing agent is selected from sodium borohydride or ascorbic acid;
in step 1), the protective agent is selected from polyvinylpyrrolidone PVP, and the average molecular weight is 30000;
in step 1), the surfactant is selected from surfactants F127, selected from pluronic F127;
in the step 1), the solvent is water;
in the step 2), the ultrasonic oscillation refers to ultrasonic power of 600W and ultrasonic time of 10-15s;
in the step 2), ultrasonic atomization is adopted, the atomization frequency is 1.7MHz, and the power is 35-50W;
in the step 2), pyrolysis is carried out, micro mist drops generated by atomization are introduced into a tube furnace for high-temperature pyrolysis treatment, the length of a heating area is 30cm, the temperature is 400-800 ℃, and precursor powder is collected;
in the step 2), the vacuum drying is carried out at the temperature of 40-80 ℃ for 12-24 hours;
in the step 2), the roasting reduction is carried out, and in the muffle furnace, the temperature is firstly increased to 350-500 ℃ at the heating rate of 2-10 ℃/min under the air atmosphere, and the roasting time is 2-4 h; under the reducing atmosphere, the temperature is increased to 400-750 ℃ at the heating rate of 2-10 ℃/min, the reducing time is 2-5 h, and the reducing atmosphere is 20-120 mL/min air flow;
the reducing atmosphere is hydrogen and nitrogen, wherein the volume fraction of the hydrogen is 20%;
the copper-indium catalyst with the broken hollow sphere morphology provided by the invention is prepared by adopting the method, and the copper-indium catalyst with the broken hollow sphere morphology is CuO-In 2 O 3 The spherical shape has a diameter of 1-2 μm, and the shell of the sphere is broken in a pore-forming manner, and the diameter of the pore is 100-500nm.
The invention can obtain the product with the appearance and the size by adding proper PVP, F127 and proper indium oxide into copper and adopting the raw materials and the preparation method.
The invention provides an application of a copper indium catalyst with a broken shell hollow sphere morphology, which is used for preparing methanol and CO by catalyzing carbon dioxide hydrogenation 2 The conversion rate can reach more than 20 percent, and the selectivity of methanol can reach more than 70 percent.
The specific application method comprises the following steps:
tabletting, grinding and screening the copper-indium catalyst with the shell-broken hollow sphere morphology, mixing the obtained sample and quartz sand, loading the mixture into a reactor, and introducing CO with the molar ratio of 1:3 2 And H 2 Two gases with Gas Hourly Space Velocity (GHSV) of 6000-12000 mL.g cat -1 ·h -1 The reaction is carried out under the pressure of 0.5-3MPa, and then the catalytic hydrogenation reaction is started when the temperature is raised to 250-350 ℃; the product produced was detected on-line using gas chromatography.
The tabletting is carried out under the pressure of 3-10 MPa;
the granularity of grinding is 10-80 meshes;
the mass ratio of the copper indium catalyst with the broken hollow sphere morphology to the quartz sand is 1:5.
Compared with the prior art, the preparation method realizes the preparation target of the cheap and easily available copper-indium catalyst, the process utilizes a spray pyrolysis method to obtain a preliminary sample, and the preliminary sample is reduced at high temperature to form the copper-indium catalyst, so that the catalytic performance is obviously improved. The shell-broken hollow sphere structure with special morphology is obtained by controlling the parameters of the preparation method, which is beneficial to the transportation and diffusion of reactants in the shell. The invention adopts a spray pyrolysis method to prepare hollow spheres which are all in micron order. For the catalyst containing noble metal, the shell-breaking hollow sphere structure optimizes the use of metal, and saves the cost for practical application. The catalyst is used for gas-solid phase catalytic reaction, is used for catalyzing carbon dioxide hydrogenation to prepare methanol, can improve the carbon dioxide conversion rate, and shows excellent catalytic performance. The catalyst can be applied to the fields of new energy solar cells and gas-solid catalysis, and has excellent performance. The copper nitrate and the indium nitrate required by the synthesis method are cheap, easy to obtain and nontoxic, and the preparation process is simple.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the copper indium catalyst of example 1;
FIG. 2 is an X-ray powder diffraction pattern of the copper indium catalyst of example 2;
FIG. 3 is an X-ray powder diffraction pattern of the copper indium catalyst of example 3;
FIG. 4 is a scanning electron microscope image of the copper indium catalyst in example 1;
FIG. 5 is a scanning electron microscope image of the copper indium catalyst in example 2;
FIG. 6 is a scanning electron microscope image of the copper indium catalyst in example 3;
FIG. 7 is a scanning electron microscope image of the copper indium catalyst in example 4;
FIG. 8 is a scanning electron microscope image of the copper indium catalyst in example 5.
Detailed Description
The present invention will be described in further detail with reference to the following examples, which are only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
The reducing atmosphere is hydrogen and nitrogen, wherein the volume fraction of the hydrogen is 20%;
example 1
The preparation method of the copper-indium catalyst with the shell-broken hollow sphere morphology comprises the following steps:
1) 0.4832g of copper nitrate trihydrate, 1.2032g of indium nitrate, 1g of PVP,1.408g of ascorbic acid and 1g of F127 are dissolved in 60mL of water until the solution is completely and uniformly mixed to obtain a mixed solution. The mixture was reacted for 1 hour with magnetic stirring at a stirring frequency of 400 rpm.
2) The reaction solution was subjected to ultrasonic treatment with an ultrasonic cleaner at 600W for 10s. And (3) placing the obtained solution into an ultrasonic atomizer, atomizing at the frequency of 1.7MHz and under the power of 50W, introducing micro mist drops generated by atomization into a 600 ℃ tubular furnace for reaction, heating the powder with the length of a region of 30cm, placing the powder collected by filter paper into a vacuum drying box, vacuum drying at 60 ℃ for 12 hours, placing the powder into a muffle furnace, heating the powder from room temperature to 400 ℃ at the speed of 5 ℃/min for roasting for 2 hours, naturally cooling the powder to room temperature, and then heating the sample from room temperature to 600 ℃ for reduction for 3 hours at the speed of 5 ℃/min in a 60mL/min reducing atmosphere to obtain the product.
The product prepared in the example 1 is used as a catalyst for preparing methanol by hydrogenation of carbon dioxide:
tabletting, crushing, grinding and screening the product obtained in the step 2) to obtain particles with the particle size of 40-60 meshes, mixing 0.2g of sample (40-60 meshes) with 1g of quartz sand (40-60 meshes), loading the mixture into a reactor, and introducing CO with the molar ratio of 1:3 2 And H 2 Two gases, the Gas Hourly Space Velocity (GHSV) is 12000 mL.g cat -1 ·h -1 The reaction is carried out under the pressure of 3MPa, and then the catalytic hydrogenation reaction is started when the temperature is raised to 300 ℃; on-line detection of the product produced by gas chromatography to measure CO 2 The conversion was 22.6% and the methanol selectivity was 83.5%.
Example 2
The preparation method of the copper-indium catalyst with the shell-broken hollow sphere morphology comprises the following steps:
1) 0.4832g of copper nitrate trihydrate, 2.4064g of indium nitrate, 1.5g of PVP,0.1513g of sodium borohydride and 1.5g of F127 are dissolved in 60ml of water until the solution is completely and uniformly mixed to obtain a mixed solution. The mixture was reacted for 2 hours under magnetic stirring at a stirring frequency of 400 rpm.
2) The reaction solution was subjected to ultrasonic treatment with an ultrasonic cleaner for 15 seconds at 600W. Placing the obtained solution into an ultrasonic atomizer, introducing micro mist drops generated by atomization into a 700 ℃ tubular furnace for reaction under the conditions of the frequency of 1.7MHz and the power of 50W, heating the powder with the length of a heating area of 30cm, placing the powder collected by filter paper into a vacuum drying box, vacuum drying at 70 ℃ for 14 hours, then placing the powder into a muffle furnace, heating the powder from room temperature to 450 ℃ for 3 hours at the speed of 5 ℃/min, naturally cooling the powder to room temperature, and reducing the sample from room temperature to 500 ℃ for 3 hours at the speed of 5 ℃/min in 80mL/min reducing atmosphere to obtain the product. Roasting, tabletting, grinding and reducing to obtain the copper-indium catalyst. And tabletting, grinding and reducing to obtain the copper indium catalyst.
The product prepared in the example 2 is used as a catalyst for preparing methanol by hydrogenation of carbon dioxide:
tabletting, grinding, crushing and screening the product obtained in the step 2) to obtain particles with the particle size of 40-60 meshes, mixing 0.2g of sample (40-60 meshes) with 1g of quartz sand (40-60 meshes), loading the mixture into a reactor, and introducing CO with the molar ratio of 1:3 2 And H 2 Two gases, the Gas Hourly Space Velocity (GHSV) is 6000 mL.g cat -1 ·h -1 The reaction is carried out under the pressure of 2MPa, and then the catalytic hydrogenation reaction is started when the temperature is raised to 260 ℃; on-line detection of the product produced by gas chromatography to measure CO 2 The conversion was 20.5% and the methanol selectivity was 96.5%.
Example 3
The preparation method of the copper-indium catalyst with the shell-broken hollow sphere morphology comprises the following steps:
1) 0.9884g copper nitrate trihydrate, 1.2032g indium nitrate, 1g PVP,1.408g ascorbic acid, 1g F127 were dissolved in 60ml water until the solution was thoroughly mixed to obtain a mixed solution. The mixture was reacted for 2 hours under magnetic stirring at a stirring frequency of 400 rpm.
2) The reaction solution was subjected to ultrasonic treatment with an ultrasonic cleaner at 600W for 10s. Placing the obtained solution into an ultrasonic atomizer with the frequency of 1.7MHz and the power of 50W, introducing micro mist drops generated by atomization into a 600 ℃ tubular furnace for reaction, wherein the length of a heating area is 30cm, placing powder collected by filter paper into a vacuum drying oven, drying at 50 ℃ for 18 hours in vacuum, then placing the powder into the muffle furnace, heating from room temperature to 400 ℃ at the speed of 5 ℃/min for roasting for 2 hours, naturally cooling to room temperature, and reducing the sample in a 100mL/min reducing atmosphere at the speed of 5 ℃/min from room temperature to 500 ℃ for 3 hours to obtain the product.
The product prepared in example 3 is used as a catalyst for preparing methanol by hydrogenation of carbon dioxide:
tabletting, grinding, crushing and screening the product obtained in the step 2) to obtain particles with the particle size of 40-60 meshes, mixing 0.2g of sample (40-60 meshes) with 1g of quartz sand (40-60 meshes), loading the mixture into a reactor, and introducing CO with the molar ratio of 1:3 2 And H 2 Two gases, the Gas Hourly Space Velocity (GHSV) is 9000 mL.g cat -1 ·h -1 The reaction is carried out under the pressure of 0.5MPa, and then the catalytic hydrogenation reaction is started when the temperature is raised to 330 ℃; on-line detection of the product produced by gas chromatography to measure CO 2 The conversion was 31.8% and the methanol selectivity was 72.6%.
Characterization of the products of examples 1-3, as In XRD patterns of FIGS. 1-3, diffraction peaks were attributed to Cu and In 2 O 3 . SEM images were characterized as in fig. 4-6, and a clear appearance of the shelled hollow spheres was seen.
Example 4 (as a comparison)
The synthesis method of the copper indium catalyst comprises the following steps:
1) 0.9884g of copper nitrate trihydrate,0g of indium nitrate1g PVP,1.408g ascorbic acid, 1g F127 were dissolved in 60ml water until the solution was thoroughly mixed to give a mixture. The mixture was reacted for 2 hours under magnetic stirring at a stirring frequency of 400 rpm.
2) The reaction solution was subjected to ultrasonic treatment with an ultrasonic cleaner at 600W for 10s. Placing the obtained solution into an ultrasonic atomizer with the frequency of 1.7MHz and the power of 50W, introducing micro mist drops generated by atomization into a 700 ℃ tubular furnace for reaction, heating the micro mist drops to the length of 30cm, placing powder collected by filter paper into a vacuum drying box, drying the powder at the temperature of 50 ℃ for 16 hours in vacuum, placing the powder into a muffle furnace, heating the powder at the speed of 5 ℃/min from room temperature to 450 ℃ for roasting for 2 hours, naturally cooling the powder to room temperature, and reducing the sample in 80mL/min reducing atmosphere at the speed of 5 ℃/min from room temperature to 500 ℃ for 3 hours to obtain the product.
The product prepared in example 4 is used as a catalyst for preparing methanol by hydrogenation of carbon dioxide:
tabletting, grinding, crushing and screening the product obtained in the step 2) to obtain particles with the particle size of 40-60 meshes, mixing 0.2g of sample (40-60 meshes) with 1g of quartz sand (40-60 meshes), loading the mixture into a reactor, and introducing CO with the molar ratio of 1:3 2 And H 2 Two gases, the Gas Hourly Space Velocity (GHSV) is 9000 mL.g cat -1 ·h -1 The reaction is carried out under the pressure of 0.5MPa, and then the catalytic hydrogenation reaction is started when the temperature is raised to 330 ℃; the gas chromatography is adopted to detect the generated product on line, 2 CO conversion was measured to be 4.2% and methanol selectivity was measured to be 21.4％。
Example 5 (as a comparison)
The synthesis method of the copper indium catalyst comprises the following steps:
1) 0.9664g of copper nitrate trihydrate, 1.2032g of indium nitrate,0.5g PVP1.408g of ascorbic acid, which is preferably sodium ascorbate,0.5g f127 is dissolvedThe mixture was obtained by thoroughly mixing 60ml of water until the solution was completely mixed. The mixture was reacted under magnetic stirring at a stirring frequency of 400rpm4h。
2) The reaction solution which is kept stillAnd (3) centrifuging by using a centrifugal machine, wherein the rotating speed is 10000r/min, and centrifuging for 10min. Will collect Placing the precipitate into a vacuum drying ovenVacuum drying at 50 ℃ for 24 hours, then placing the mixture into a muffle furnace, heating the mixture from room temperature to 450 ℃ at a speed of 5 ℃/min for roasting for 3 hours, naturally cooling the mixture to room temperature, and reducing the sample in a 60mL/min reducing atmosphere at a speed of 5 ℃/min from room temperature to 500 ℃ for 3 hours to obtain the product.
The product prepared in example 5 is used as a catalyst for preparing methanol by hydrogenation of carbon dioxide:
tabletting, grinding, crushing and screening the product obtained in the step 2) to obtain particles with the particle size of 40-60 meshes, mixing 0.2g of sample (40-60 meshes) with 1g of quartz sand (40-60 meshes), loading the mixture into a reactor, and introducing CO with the molar ratio of 1:3 2 And H 2 Two gases, the Gas Hourly Space Velocity (GHSV) is 9000 mL.g cat -1 ·h -1 The reaction is carried out under the pressure of 0.5MPa, and then the catalytic hydrogenation reaction is started when the temperature is raised to 330 ℃; the gas chromatography is adopted to detect the generated product on line, 2 CO conversion was measured to be 6.4% and methanol selectivity was measured to be 33.5％。
Example 4 is a failure case, only copper nitrate trihydrate is added, indium nitrate is not added, even if the preparation is carried out by adopting the spray pyrolysis method of the invention and combining a reducing gas reduction means, the appearance of the shell-broken hollow sphere cannot be obtained, and the performance of example 4 is poor, which shows that the interaction between metallic copper and indium is helpful for the generation of the shell-broken hollow sphere. The SEM image is shown in fig. 7, and the addition of indium is a factor affecting the morphology of the catalyst.
Example 5 is a failure case, and the catalyst prepared by the liquid phase reduction method is compared with the catalyst prepared by the spray pyrolysis method, although the amount ratio of the raw materials adopted by the method does not meet the requirement of the invention. The result shows that the appearance of the shell-broken hollow sphere is not generated, the performance is poor, and an SEM (scanning electron microscope) graph is shown in figure 8, so that the preparation method has obvious influence on the appearance of the catalyst.
CO in the above embodiments 1 to 3 2 The conversion rate and the selectivity of the methanol are experimental data of the performance test of the catalyst. The data show that the catalyst with the appearance of the broken hollow sphere has better catalytic performance.
Claims (10)
1. The preparation method of the copper-indium catalyst with the shell-broken hollow sphere morphology is characterized by comprising the following steps of:
1) Mixing a copper source, an indium source, a reducing agent, a protective agent, a surfactant and a solvent, and stirring to obtain a suspension;
2) And (3) carrying out ultrasonic oscillation, atomization, pyrolysis and vacuum drying on the suspension, and then roasting and reducing to obtain the copper-indium catalyst with the shell-broken hollow sphere morphology.
2. The method according to claim 1, wherein in step 1), the ratio of the amounts of the substances of the copper source and the indium source is 0.25 to 4.0:1, a step of; the dosage ratio of the protective agent to the solvent is 10-30g/L; the dosage ratio of the surfactant to the solvent is 10-30g/L.
3. The process according to claim 1 or 2, wherein in step 1), the stirring is carried out for 1 to 2 hours under vigorous stirring; the frequency of stirring is 400-600 rpm.
4. The method of preparation according to claim 1 or 2, wherein in step 1) the protecting agent is selected from polyvinylpyrrolidone PVP.
5. The method of preparation according to claim 1 or 2, wherein in step 1) the surfactant is selected from the group consisting of surfactant F127.
6. The method according to claim 1, wherein in the step 2), the atomization is performed by ultrasonic atomization, the atomization frequency is 1.7MHz, and the power is 35-50W.
7. The preparation method according to claim 1, wherein in the step 2), the pyrolysis is performed, and the micro mist droplets generated by atomization are introduced into a tube furnace for high-temperature pyrolysis treatment, wherein the heating area is 30cm long and the temperature is 400-800 ℃.
8. The preparation method according to claim 1, wherein in the step 2), the roasting reduction is performed in an air atmosphere, the temperature is firstly increased to 350-500 ℃ at a heating rate of 2-10 ℃/min, and the roasting duration is 2-4 h; under the reducing atmosphere, the temperature is raised to 400-750 ℃ at the heating rate of 2-10 ℃/min, the reducing time is 2-5 h, and the reducing atmosphere is 20-120 mL/min air flow.
9. A copper-indium catalyst in the shape of a broken hollow sphere prepared by the preparation method according to any one of claims 1 to 8, wherein the copper-indium catalyst in the shape of a broken hollow sphere is spherical, the diameter of the sphere is 1 to 2 μm, the shell of the sphere is broken in a pore-forming manner, and the diameter of the pore is 100 to 500nm.
10. The use of a copper indium catalyst of the broken hollow sphere morphology of claim 9 for catalyzing the hydrogenation of carbon dioxide to methanol.
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