CN114534740A - Copper-manganese composite catalyst with three-dimensional porous structure and preparation method and application thereof - Google Patents
Copper-manganese composite catalyst with three-dimensional porous structure and preparation method and application thereof Download PDFInfo
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- CN114534740A CN114534740A CN202210051577.XA CN202210051577A CN114534740A CN 114534740 A CN114534740 A CN 114534740A CN 202210051577 A CN202210051577 A CN 202210051577A CN 114534740 A CN114534740 A CN 114534740A
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- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 238000000016 photochemical curing Methods 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 15
- 238000010146 3D printing Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011148 porous material Substances 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 11
- 229940099596 manganese sulfate Drugs 0.000 claims description 11
- 235000007079 manganese sulphate Nutrition 0.000 claims description 11
- 239000011702 manganese sulphate Substances 0.000 claims description 11
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- SYBFKRWZBUQDGU-UHFFFAOYSA-N copper manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Cu++] SYBFKRWZBUQDGU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a copper-manganese composite catalyst with a three-dimensional porous structure, and a preparation method and application thereof. The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the following steps: firstly, uniformly mixing photocuring resin, copper-manganese mixed salt, active alumina and a photoinitiator to form a catalyst precursor; then 3D printing is carried out on the copper-manganese composite catalyst to obtain a three-dimensional porous blank, and then heat treatment and calcination treatment are carried out to obtain the copper-manganese composite catalyst with the three-dimensional porous structure; wherein the weight ratio of the photo-curing resin, the copper-manganese mixed salt and the active alumina is (13-25): 6-13): 1-3; the aperture of the three-dimensional porous blank is 20-80 μm; the temperature of the heat treatment is 300-500 ℃, the time is 1-3 h, the temperature of the calcination treatment is 500-800 ℃, and the time is 1-3 h. The copper-manganese composite catalyst with the three-dimensional porous structure has the advantages of high specific surface area, excellent catalytic efficiency and excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of high-purity gas preparation, and particularly relates to a copper-manganese composite catalyst with a three-dimensional porous structure, and a preparation method and application thereof.
Background
CO is colorless, tasteless, flammable and explosive gas, has strong toxicity, is one of common toxicants at present, and is called as a drug unknown in the 21 st century. At present, the catalysts for catalytically decomposing CO mainly comprise two main types of supported noble metal catalysts such as Au, Pt, Pd and the like and non-noble metal catalysts such as copper-manganese composite catalysts. Due to the high price of noble metals, the development of high-activity copper-manganese composite catalysts has become a research hotspot at present.
The prior art (CN111744498A) discloses a manganese-copper composite oxide catalyst and a preparation method and application thereof, the particle size of manganese oxide and copper oxide in amorphous copper-manganese oxide is further controlled by controlling the concentration and stirring speed of raw materials in the preparation process of copper-manganese oxide, and the copper-manganese composite oxide catalyst is obtained, can effectively remove low-solubility CO in high-purity nitrogen, but has smaller specific surface area and poor recycling stability.
Disclosure of Invention
The invention aims to overcome the defects and defects of small specific surface area and poor cycle stability of the existing granular copper-manganese composite oxide catalyst, and provides a preparation method of a copper-manganese composite catalyst with a three-dimensional porous structure.
The invention also aims to provide a copper-manganese composite catalyst with a three-dimensional porous structure.
The invention further aims to provide application of the copper-manganese composite catalyst with the three-dimensional porous structure in catalytic decomposition of CO.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a copper-manganese composite catalyst with a three-dimensional porous structure comprises the following steps:
s1, uniformly mixing light-cured resin, copper-manganese mixed salt and active alumina to form a catalyst precursor;
s2, performing 3D printing treatment on the catalyst precursor in the S1 to obtain a three-dimensional porous blank;
s3, carrying out heat treatment and calcination treatment on the three-dimensional porous blank in the S2 to obtain the copper-manganese composite catalyst with the three-dimensional porous structure;
wherein the weight ratio of the photocuring resin, the copper-manganese mixed salt and the activated alumina in S1 is (13-25): (6-13): 1-3);
the three-dimensional porous blank in the S2 has a microporous structure, and the pore diameter of the three-dimensional porous blank is 20-80 mu m;
the temperature of the heat treatment in the S3 is 300-500 ℃, and the time is 1-3 h; the calcining temperature is 500-800 ℃, and the time is 1-3 h.
The addition amount of the photocuring resin not only influences the 3D printing forming of the catalyst precursor, but also influences the pore structure and the structural stability of the finally prepared copper-manganese composite catalyst with the three-dimensional porous structure; when the addition amount of the light-cured resin is too small, the three-dimensional porous blank is not beneficial to being printed and formed in the 3D printing process, and the structure collapse of the copper-manganese composite catalyst with the three-dimensional porous structure is easily caused in the heat treatment and calcination treatment processes, so that the structure stability and the specific surface area of the catalyst are influenced, and the catalytic efficiency and the cycle stability are reduced; when the addition amount of the photo-curing resin is too large, although the preparation of the three-dimensional porous blank is facilitated, the three-dimensional porous blank contains a large amount of polymers formed by the photo-curing resin, and excessive pores are left due to decomposition of the polymers in the heat treatment and calcination treatment processes, so that the structural stability of the copper-manganese composite catalyst is reduced, and the catalytic efficiency and the cycle stability of the catalyst are also reduced. The addition of the active alumina can play a role in coordinating catalysis, so that the catalytic activity of the catalyst is improved, and the improvement of the catalytic performance of the copper-manganese composite catalyst with the three-dimensional porous structure is not facilitated by too much or too little addition amount of the active alumina.
The three-dimensional porous blank printed and molded by the mixture of the photocuring resin, the copper-manganese mixed salt and the activated alumina has a uniformly distributed microporous structure with the pore diameter of 20-80 microns, the microporous structure with a proper pore diameter is beneficial to forming a multi-level composite microporous structure after heat treatment and calcination treatment of the three-dimensional porous blank, and the porous structure is beneficial to reducing the gas flow resistance in the catalysis process and cannot cause the gas diffusion rate to be too high to influence the catalysis effect; in addition, the multilevel composite pore structure can provide abundant contact crosslinking points, improve the structural stability of the copper-manganese composite catalyst with the three-dimensional porous structure and further improve the cycle stability.
When the pore diameter of the microporous structure of the three-dimensional porous blank is too large, an oversized macroporous structure can be formed after heat treatment and calcination treatment, and the structural stability of the copper-manganese composite catalyst with the three-dimensional porous structure is reduced; when the pore diameter is too small, the formation of a multi-stage composite microporous structure is not facilitated, and the catalytic performance of the catalyst is also affected.
The heat treatment mainly affects the synthesis of the copper-manganese composite catalyst, and the calcination treatment mainly aims to ensure that the copper-manganese composite catalyst further reacts completely and simultaneously removes polymers formed by the light-cured resin; if the time of heat treatment is too short and the temperature is too low, the formation of the copper-manganese composite catalyst is not facilitated, and otherwise, the structural stability and the catalytic activity of the copper-manganese composite catalyst are influenced; if the time of the calcination treatment is too short and the temperature is too low, the further reaction of the copper-manganese composite catalyst and the removal of the polymer formed by the photocurable resin are not facilitated.
Preferably, the weight ratio of the light-cured resin, the copper-manganese mixed salt and the activated alumina in S1 is (15-19): (7-11): (1-3).
Preferably, the aperture of the three-dimensional porous blank in S2 is 30-50 μm.
Preferably, the temperature of the heat treatment in S2 is 400-450 ℃, and the time is 2-3 h; the temperature of the calcination treatment is 600-700 ℃, and the time is 1.5-2 h.
Preferably, the light-cured resin consists of acrylic acid and multifunctional acrylate, and the weight ratio of the acrylic acid to the multifunctional acrylate is (8-15): (5-10).
When the weight ratio of acrylic acid to the multifunctional acrylate is (8-15): (5-10), a polymer formed in the 3D printing process has a proper crosslinking degree, so that a three-dimensional porous blank has excellent stability, and the three-dimensional porous structure copper-manganese composite catalyst after heat treatment and calcination has good structural stability.
Preferably, the copper-manganese mixed salt consists of potassium permanganate, manganese sulfate and copper sulfate, and the catalyst precursor comprises the following components in parts by weight: 8-15 parts of acrylic acid, 5-10 parts of multifunctional acrylate, 2-5 parts of potassium permanganate, 2-4 parts of manganese sulfate, 2-4 parts of copper sulfate, 0.3-2 parts of photoinitiator and 1-3 parts of activated alumina.
The invention also discloses a three-dimensional porous structure copper-manganese composite catalyst prepared by the preparation method of the three-dimensional porous structure copper-manganese composite catalyst.
In a specific embodiment, the specific surface area of the copper-manganese composite catalyst with the three-dimensional porous structure is 88-96 m2The average pore diameter of the nano pores is 24-80 nm.
In particular embodiments, the multifunctional acrylate of the present invention may be one or more of tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, octapentanediol diacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and propoxylated pentaerythritol triacrylate;
the photoinitiator may be one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.
The application of the copper-manganese composite catalyst with the three-dimensional porous structure prepared by the invention in catalytic decomposition of CO is also in the protection scope of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a copper-manganese composite catalyst with a three-dimensional porous structure, which comprises the steps of uniformly mixing a photocuring resin, a copper-manganese mixed salt and active alumina, forming a three-dimensional porous blank with a specific microporous structure through 3D printing, and then forming a multi-stage composite microporous structure through heat treatment and calcination treatment, wherein the specific surface area of the copper-manganese composite catalyst is remarkably increased, the contact surface area and the contact time of the copper-manganese composite catalyst and gas are further effectively increased, and the highest catalytic efficiency of catalytic decomposition of CO can reach 97%; the catalyst has good structural stability, the number of recycling times can reach more than 7, and the catalyst has excellent catalytic efficiency and cycling stability.
Drawings
FIG. 1 is a surface structure view of a three-dimensional porous body in example 1;
fig. 2 is a structure diagram of a multi-stage composite micropore of a copper-manganese composite catalyst with a three-dimensional porous structure in example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of a copper-manganese composite catalyst with a three-dimensional porous structure comprises the following steps of:
s1, shearing and uniformly mixing 10 parts of acrylic acid, 7 parts of multifunctional acrylate, 3 parts of potassium permanganate, 3 parts of manganese sulfate, 3 parts of copper sulfate, 1 part of photoinitiator and 1 part of activated alumina at a high speed to form a catalyst precursor;
s2, placing the catalyst precursor in the S1 in a photocuring ceramic 3D printer for 3D printing to prepare a three-dimensional porous blank with the aperture of 30 microns;
s3, carrying out heat treatment on the three-dimensional porous blank in the S2 at 400 ℃ for 2h, and then calcining at 600 ℃ for 2h to obtain the copper-manganese composite catalyst with the three-dimensional porous structure;
wherein the weight ratio of the photocuring resin, the copper-manganese mixed salt and the activated alumina is 17:9: 1.
Example 2
The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the steps which are basically the same as those in example 1 in parts by weight, and is characterized in that the pore diameter of a three-dimensional porous body in step S2 is 20 microns.
Example 3
The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the steps which are basically the same as those in example 1 in parts by weight, and is characterized in that the pore diameter of a three-dimensional porous body in step S2 is 50 microns.
Example 4
The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the steps which are basically the same as those in example 1 in parts by weight, and is characterized in that the pore diameter of a three-dimensional porous body in step S2 is 80 microns.
Example 5
A preparation method of a copper-manganese composite catalyst with a three-dimensional porous structure comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that the temperature of heat treatment in step S3 is 450 ℃, the time is 3 hours, the temperature of calcination treatment is 700 ℃, and the time is 1.5 hours.
Example 6
The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the steps which are basically the same as those in example 1 in parts by weight, and is characterized in that the temperature of heat treatment in step S3 is 300 ℃ and the time is 3 hours, the temperature of calcination treatment is 500 ℃ and the time is 3 hours.
Example 7
A preparation method of a copper-manganese composite catalyst with a three-dimensional porous structure comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that the temperature of heat treatment in step S3 is 500 ℃, the time is 1h, the temperature of calcination treatment is 800 ℃, and the time is 1 h.
Example 8
A preparation method of a three-dimensional porous structure copper-manganese composite catalyst comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that in step S1, the components in a catalyst precursor are as follows: 10 parts of acrylic acid, 7 parts of multifunctional acrylate, 3 parts of potassium permanganate, 3 parts of manganese sulfate, 3 parts of copper sulfate, 1 part of photoinitiator and 3 parts of activated alumina;
wherein the weight ratio of the photocuring resin, the copper-manganese mixed salt and the activated alumina is 17:9: 3.
Example 9
A preparation method of a three-dimensional porous structure copper-manganese composite catalyst comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that in step S1, the components in a catalyst precursor are as follows: 8 parts of acrylic acid, 5 parts of multifunctional acrylate, 5 parts of potassium permanganate, 4 parts of manganese sulfate, 4 parts of copper sulfate, 1 part of photoinitiator and 1 part of activated alumina;
wherein the weight ratio of the photocuring resin to the copper-manganese mixed salt to the activated alumina is 13:13: 1.
Example 10
A preparation method of a three-dimensional porous structure copper-manganese composite catalyst comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that in step S1, the components in a catalyst precursor are as follows: 15 parts of acrylic acid, 10 parts of multifunctional acrylate, 2 parts of potassium permanganate, 2 parts of manganese sulfate, 2 parts of copper sulfate, 1 part of photoinitiator and 1 part of activated alumina;
wherein the weight ratio of the photocuring resin, the copper-manganese mixed salt and the activated alumina is 25:6: 1.
Comparative example 1
A preparation method of a copper-manganese composite catalyst comprises the following steps of:
after 3 parts of potassium permanganate, 3 parts of manganese sulfate, 3 parts of copper sulfate and 1 part of activated alumina are mixed uniformly, the mixture is directly subjected to heat treatment at 400 ℃ for 2 hours, and then calcined at 600 ℃ for 2 hours, so that the copper-manganese composite catalyst is obtained.
Comparative example 2
The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the steps which are basically the same as those in example 1 in parts by weight, and is characterized in that the pore diameter of a three-dimensional porous body in the step S2 is 10 microns.
Comparative example 3
The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure comprises the steps which are basically the same as those in example 1 in parts by weight, and is characterized in that the pore diameter of a three-dimensional porous body in step S2 is 100 microns.
Comparative example 4
A preparation method of a three-dimensional porous structure copper-manganese composite catalyst comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that in step S1, the components in a catalyst precursor are as follows: 8 parts of acrylic acid, 5 parts of multifunctional acrylate, 5 parts of potassium permanganate, 5 parts of manganese sulfate, 5 parts of copper sulfate, 1 part of photoinitiator and 1 part of activated alumina;
wherein the weight ratio of the photocuring resin to the copper-manganese mixed salt to the activated alumina is 13:15: 1.
Comparative example 5
A preparation method of a three-dimensional porous structure copper-manganese composite catalyst comprises the steps which are basically the same as those in example 1 according to the parts by weight, and is characterized in that in step S1, the components in a catalyst precursor are as follows: 15 parts of acrylic acid, 10 parts of multifunctional acrylate, 1 part of potassium permanganate, 1 part of manganese sulfate, 2 parts of copper sulfate, 1 part of photoinitiator and 1 part of activated alumina;
wherein the weight ratio of the photocuring resin, the copper-manganese mixed salt and the activated alumina is 25:4: 1.
Result detection
(1) Scanning electron microscope test
FIG. 1 is a surface structure diagram of a three-dimensional porous body in example 1, and it can be seen from the diagram that the surface has uniformly distributed microporous structures, which is beneficial to forming a multi-level composite microporous structure after heat treatment and calcination treatment; fig. 2 is a structure diagram of a hierarchical composite micropore of the three-dimensional porous copper-manganese composite catalyst in example 1, which shows a hierarchical pore structure with nested micropores in macropores, and is not only beneficial to increasing the catalytic contact area of the copper-manganese composite catalyst and improving the catalytic efficiency, but also capable of providing rich contact cross-linking points and enhancing the structural stability.
(2) Porosity test
The test method comprises the following steps: the specific surface area and pore size distribution of the copper-manganese composite catalyst with the three-dimensional porous structure of the invention were measured using a multi-station full-automatic specific surface area and porosity analyzer (NOVAtouch) of antopa ltd, and the test results are shown in table 1.
The average pore diameter of the nano-pores in the three-dimensional porous structure copper-manganese composite catalyst has important influence on the catalytic efficiency and the cycle stability, and the suitable average pore diameter range of the nano-pores is 24-80 nm.
(3) Dynamic testing of catalytic decomposition of CO
The test method comprises the following steps: introducing nitrogen containing 2000ppmv CO into a fixed bed reactor filled with 100mL of a catalyst to be tested, wherein the test temperature is 30 ℃, the gas flow is 100L/min, the outlet gas uses a Thermo 48i CO analyzer to test the outlet CO content, after the stable operation is performed for 30min, the removal rate calculated by the inlet and outlet CO concentration is the catalytic efficiency when the test is performed for 30min, and the test result is shown in Table 1.
(4) Test for cycling stability
The test method comprises the following steps: the same catalyst was used repeatedly until its catalytic activity decreased to 10% of the first catalytic efficiency, and the number of cycles was recorded, and the test results are shown in table 1.
TABLE 1 Performance of catalysts in examples 1 to 10 and comparative examples 1 to 5
From examples 1 to 10, it is known that the specific surface area of the copper-manganese composite catalyst with the three-dimensional porous structure reaches 88 to 96m2The average pore diameter of the nanometer pore diameter reaches 24-80 nm, so that the catalytic contact area can be obviously increased, and the catalytic efficiency is improved to 90-97%; the multi-stage composite microporous structure can also provide abundant contact crosslinking points, so that the structural stability of the copper-manganese composite catalyst with the three-dimensional porous structure is improved, the cycle stability of the copper-manganese composite catalyst is improved, and the cycle use frequency reaches more than 7 times;
as can be seen from example 1 and comparative example 1, the specific surface area of the copper-manganese composite catalyst formed by direct heat treatment and calcination is smaller (54m2(g), the average pore diameter of the nano pore is larger (100nm), so that the catalytic efficiency is lower (71%), and the cycling stability is poorer (the number of recycling times is only 2);
as can be seen from examples 1 to 4 and comparative examples 2 to 3, the pore diameter of the three-dimensional porous blank has an important influence on the average pore diameter of the nanopores of the copper-manganese composite catalyst with the three-dimensional porous structure, and when the average pore diameter of the nanopores is 20nm (<24nm), the catalytic efficiency is reduced to 85%, and the number of recycling times is reduced to 5; when the average pore diameter of the nano-pores is 100nm (>80nm), the catalytic efficiency is reduced to 80%, and the recycling frequency is reduced to 5 times.
From examples 1, 8 to 10 and 4 to 5, when the weight ratio of the photocurable resin, the copper-manganese mixed salt and the activated alumina is 13:15:1 (i.e., the addition amount of the photocurable resin is too small), the catalytic efficiency is reduced to 82%, and the number of recycling times is reduced to 3; when the weight ratio of the light-cured resin to the copper-manganese mixed salt to the activated alumina is 25:4:1 (namely, the addition amount of the light-cured resin is too much), the catalytic efficiency is reduced to 75%, and the recycling frequency is reduced to 3 times.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure is characterized by comprising the following steps of:
s1, uniformly mixing light-cured resin, copper-manganese mixed salt, activated alumina and a photoinitiator to form a catalyst precursor;
s2, 3D printing is carried out on the catalyst precursor in the S1 to obtain a three-dimensional porous blank body;
s3, carrying out heat treatment and calcination treatment on the three-dimensional porous blank in the S2 to obtain the copper-manganese composite catalyst with the three-dimensional porous structure;
wherein the weight ratio of the photocuring resin, the copper-manganese mixed salt and the activated alumina in S1 is (13-25): (6-13): 1-3);
the aperture of the three-dimensional porous blank in the S2 is 20-80 μm;
the temperature of the heat treatment in the S3 is 300-500 ℃, and the time is 1-3 h; the calcining temperature is 500-800 ℃, and the time is 1-3 h.
2. The method for preparing the copper-manganese composite catalyst with the three-dimensional porous structure as claimed in claim 1, wherein the weight ratio of the photocurable resin, the copper-manganese mixed salt and the activated alumina in S1 is (15-19): (7-11): (1-3).
3. The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure according to claim 1, wherein the pore diameter of the three-dimensional porous blank in S2 is 30-50 μm.
4. The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure according to claim 1, wherein the temperature of the heat treatment in S2 is 400-450 ℃ and the time is 2-3 h; the temperature of the calcination treatment is 600-700 ℃, and the time is 1.5-2 h.
5. The preparation method of the copper-manganese composite catalyst with the three-dimensional porous structure as claimed in claim 1, wherein the photocurable resin is composed of acrylic acid and multifunctional acrylate, and the weight ratio of the acrylic acid to the multifunctional acrylate is (8-15): (5-10).
6. The preparation method of the three-dimensional porous structure copper-manganese composite catalyst as claimed in claim 5, wherein the copper-manganese mixed salt is composed of potassium permanganate, manganese sulfate and copper sulfate, and the catalyst precursor comprises the following components in parts by weight: 8-15 parts of acrylic acid, 5-10 parts of multifunctional acrylate, 2-5 parts of potassium permanganate, 2-4 parts of manganese sulfate, 2-4 parts of copper sulfate, 0.3-2 parts of photoinitiator and 1-3 parts of activated alumina.
7. The method for preparing the copper-manganese composite catalyst with the three-dimensional porous structure according to claim 5, wherein the multifunctional acrylate is one or more of tripropylene glycol diacrylate, pentaerythritol tetraacrylate and trimethylolpropane triacrylate.
8. The three-dimensional porous structure copper-manganese composite catalyst prepared by the preparation method of the three-dimensional porous structure copper-manganese composite catalyst according to any one of claims 1 to 7.
9. The three-dimensional porous structure copper-manganese composite catalyst according to claim 8, wherein the specific surface area of the three-dimensional porous structure copper-manganese composite catalyst is 88-96 m2The average pore diameter of the nano pores is 24-80 nm.
10. Use of the three-dimensional porous structure copper-manganese composite catalyst according to claim 8 in catalytic decomposition of CO.
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