CN112619656A - Carbon monoxide conversion catalyst using copper wire mesh corrugated packing as carrier - Google Patents
Carbon monoxide conversion catalyst using copper wire mesh corrugated packing as carrier Download PDFInfo
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- CN112619656A CN112619656A CN202011494841.4A CN202011494841A CN112619656A CN 112619656 A CN112619656 A CN 112619656A CN 202011494841 A CN202011494841 A CN 202011494841A CN 112619656 A CN112619656 A CN 112619656A
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- filler
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- wire mesh
- copper wire
- copper
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 28
- 238000012856 packing Methods 0.000 title claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 52
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000005751 Copper oxide Substances 0.000 claims abstract description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000004480 active ingredient Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000906 Bronze Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010974 bronze Substances 0.000 claims description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 229910001369 Brass Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000010951 brass Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 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
- 229910052592 oxide mineral Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 229910020200 CeO2−x Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- 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
-
- 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
- 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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention relates to a carbon monoxide conversion catalyst taking copper wire mesh corrugated packing as a carrier, which comprises a carrier and an active ingredient loaded on the carrier, wherein the carrier is the copper wire mesh corrugated packing, and the active ingredient is copper oxide, zinc oxide and cerium oxide; the preparation method comprises the following steps: 1) a plurality of copper wire mesh sheets are sequentially arranged in a staggered manner and are combined and fixed together according to a certain size proportion to form a disc filler; 2) carrying out ozone oxidation treatment on the obtained filler to obtain a filler carrier covering the copper oxide film; 3) preparing nitrate of Zn and Ce metal into solution with certain concentration, and mixing the solution uniformly under full stirring; 4) soaking the filler into the prepared solution, drying, roasting, and cooling to normal temperature to obtain the composite material; compared with the prior art, the catalyst has higher low-temperature catalytic activity and stability for carbon monoxide, and is simple in preparation process, lower in cost and easy for industrial production.
Description
[ technical field ]
The invention relates to the technical field of preparation of carbon monoxide catalysts, in particular to a carbon monoxide conversion catalyst taking copper wire mesh corrugated packing as a carrier.
[ background art ]
Carbon monoxide (CO) is a colorless, odorless, flammable, toxic gas. The carbon monoxide has stable chemical property at normal temperature, is not easy to react and has long existence time in the air. Currently, the more common methods of carbon monoxide removal are torch ignition and catalyst conversion. Carbon monoxide catalyst conversion can convert carbon monoxide to carbon dioxide at relatively low temperatures. The carbon monoxide catalyst has wide application in different fields such as tail gas treatment, hydrogen fuel cells, mine escape capsules, refuge chambers and other underground coal mine emergency refuge spaces.
The catalyst applied to carbon monoxide removal earlier is a noble metal catalyst, typically Au, Pd, Pt and the like, particularly the Au catalyst has good low-temperature activity and can generate carbon monoxide oxidation reaction at low temperature or even room temperature. Such catalysts are expensive and cannot be used on a large scale. Another kind of non-noble metal catalyst is represented by Hopalite (hopcalite), which mainly comprises CuO and Mn2O3And the like are main components, so that the cost is relatively low, but the efficiency is not high, the water resistance is poor, and the water-based paint can be quickly inactivated due to the existence of water in an environment with slightly high humidity.
Patent application No. CN201810861689.5 discloses a catalyst which takes titanium dioxide and active alumina as carriers and takes manganese oxide and copper oxide as active ingredients; the proposal is that after mixing the precursor of the active substance and the carrier, the precursor of the catalyst is extruded on a die to be made into a honeycomb shape with the specification of 50mm multiplied by 200mm, and then the honeycomb shape is roasted and formed.
Patent application No. CN201911322551.9 discloses a catalyst with cordierite as a carrier and precious metal Au as an active substance; the scheme is that cordierite is roasted to prepare a honeycomb ceramic carrier, and a catalyst is coated on the carrier.
The supported catalyst in the above patent is prepared by conventional coprecipitation method, impregnation method, sol-gel method, oxide or silicate mineral as carrier, metal or metal oxide as active component. Due to the limitation of the material and processing scheme of the carrier, the contact area of the catalyst and the gas is small, the carrier is difficult to form and is difficult to enlarge. Therefore, it would be of great importance to provide a supported catalyst and a preparation method thereof, which have low synthesis cost and are easy for industrial application.
[ summary of the invention ]
The invention aims to solve the defects and provide a carbon monoxide conversion catalyst taking copper wire mesh corrugated packing as a carrier, which has higher low-temperature catalytic activity and stability for carbon monoxide, and has the advantages of simple preparation process, lower cost and easy industrial production.
The carbon monoxide conversion catalyst with the copper wire mesh corrugated packing as the carrier comprises the carrier and an active ingredient loaded on the carrier, wherein the carrier is the copper wire mesh corrugated packing, and the active ingredient is copper oxide, zinc oxide and cerium oxide.
Further, the copper of the copper wire mesh corrugated packing is a copper-containing alloy including, but not limited to, phosphor bronze, brass.
Further, the molar mass ratio of the copper oxide to the zinc oxide to the cerium oxide is (50-70): (70-90): (90-100).
The invention also provides a preparation method of the carbon monoxide conversion catalyst taking the copper wire mesh corrugated packing as the carrier, which comprises the following steps: 1) a plurality of copper wire mesh sheets are sequentially staggered and fixedly combined together according to a certain size ratio to form a disc-shaped filler; 2) carrying out ozone oxidation treatment on the filler obtained in the step 1) to obtain a filler carrier covering the copper oxide film; 3) preparing nitrate of Zn and Ce metal into solution with certain concentration, and mixing the solution uniformly under full stirring; 4) and (3) soaking the filler carrier obtained in the step 2) into the solution prepared in the step 3), drying, roasting, and cooling to normal temperature to obtain the carbon monoxide conversion catalyst taking the copper wire mesh corrugated filler as a carrier.
Further, in the step 1), the filler is formed by taking a plurality of single-layer or double-layer copper wire nets as base materials, the base materials are punched into isosceles trapezoid corrugated wire net pieces through a die and are sequentially arranged in a staggered mode, and the net pieces are arranged together according to the size and a certain sheet number ratio to form the disc filler.
Further, in the step 2), the specific process of oxidizing the filler by ozone comprises the following steps: filling a stainless steel reactor with a plurality of discs of filler, connecting an ozone generator, introducing ozone, and carrying out ozone oxidation treatment; the gas generated by the ozone generator is a mixed gas of ozone and air or oxygen, and the concentration of the ozone in the mixed gas is not more than 50g/m3The volume space velocity of the introduced mixed gas is 1000-3000 h-1The reaction time is 30-120 min.
Further, in the step 3), the nitrates are cerium nitrate and zinc nitrate, the concentrations of the solutions are respectively not more than 0.5mol/L calculated by the cerium nitrate and the zinc nitrate, the solvent is pure water, and the preparation temperature is normal temperature.
Further, in the step 4), the filler is soaked completely to fully absorb the solution, the filler is taken out after soaking, drained and placed into drying equipment for drying, the drying temperature is 100-110 ℃, and the drying time is 8-16 hours; the roasting temperature is 250-500 ℃, and the roasting time is 3-6 hours.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst has high low-temperature catalytic activity and stability on carbon monoxide, the active components consist of copper, copper oxide, zinc oxide and cerium oxide, the four components supplement each other, and the removal efficiency of the catalyst on CO can be enhanced in a synergistic manner under the condition of low temperature;
(2) the copper wire mesh corrugated packing is used as a carrier, the air resistance of the packing is small, the gas diffusion is good, the packing is fully contacted with active components, the specific surface area is large, the void ratio is large, more and more uniform active substances can be loaded, and the reaction performance of the catalyst is improved;
(3) compared with the method using oxide or silicate mineral as a carrier, the method has the advantages that the extrusion molding is difficult and difficult to be large, the preparation process of the wire mesh filler is simple, the cost is low, the industrial production is easy, the molding is easy, and the size can be customized according to the requirement;
to sum up: the reverse-loaded catalyst prepared by the method has the advantages of large specific surface area, strong catalytic activity, high low-temperature catalytic activity and stability for carbon monoxide, simple preparation process, low cost and easy industrial production, and can be widely applied to the fields of environmental protection, hydrogen fuel cells, CO sensors, special closed space environment control and the like.
[ detailed description of the invention ]
The invention provides a carbon monoxide conversion catalyst taking copper wire mesh corrugated packing as a carrier, which comprises a carrier and an active component loaded on the carrier. The catalyst uses copper wire mesh corrugated packing as a carrier, and the copper can be phosphor bronze, brass or other copper-containing alloy. The active ingredients are copper oxide (CuO), zinc oxide (ZnO), and cerium oxide (CeO)2) Copper oxide (CuO), zinc oxide (ZnO), cerium oxide (CeO)2) The molar mass ratio of (50-70): (70-90): (90-100).
The preparation method of the catalyst comprises the following steps: 1) a plurality of copper wire mesh sheets are sequentially arranged in a staggered manner and are combined and fixed together according to a certain size proportion to form a disc filler; 2) carrying out ozone oxidation treatment on the obtained filler to obtain a filler carrier covering the copper oxide film; 3) preparing nitrate of Zn and Ce metal into solution with certain concentration, and mixing the solution uniformly under full stirring; 4) and (3) soaking the filler into the prepared solution, drying, roasting and cooling to normal temperature to obtain the carbon monoxide conversion catalyst taking the copper wire mesh corrugated filler as a carrier.
Wherein, the filling material in the step 1) is formed by stamping a plurality of single-layer or double-layer copper wire nets serving as base materials into an isosceles ladder through a dieThe corrugated wire mesh sheets are arranged in a staggered mode in sequence, and the mesh sheets are arranged together according to the size and a certain sheet number ratio to form the disc packing. Step 2) the specific process of the filler oxidation treatment by ozone is as follows: filling a stainless steel reactor with a plurality of discs of disc fillers, connecting an ozone generator, introducing ozone, and performing ozone oxidation treatment; the gas generated by the ozone generator is a mixed gas of ozone and air or oxygen, and the concentration of the ozone in the mixed gas is not more than 50g/m3The volume space velocity of the introduced mixed gas is 1000-3000 h-1The reaction time is 30-120 min. And 3) nitrate is cerium nitrate and zinc nitrate, the concentration of the solution is not more than 0.5mol/L calculated by the cerium nitrate and the zinc nitrate respectively, the solvent is pure water, and the preparation temperature is normal temperature. Step 4), soaking the material to completely soak the filler, and fully absorbing the solution; after dipping, taking out the filler, draining, and drying in drying equipment at the drying temperature of 100-110 ℃ for 8-16 hours; the roasting temperature is 250-500 ℃, and the roasting time is 3-6 hours.
In the invention, the carrier is copper wire mesh corrugated packing, which is widely applied in various countries in the world at present and is disc-shaped packing formed by arranging a plurality of parallel and straight-lined metal corrugated net sheets. The wire mesh packing has large specific surface area, large porosity and light weight; the gas phase passage has small inclination angle, regularity and reduced pressure; good radial diffusion, full gas contact and the like.
The Cu-based catalyst has been widely studied because it shows good catalytic activity in the CO catalytic oxidation reaction, and is abundant in resources and low in cost. Ce is a rare earth material with low price, so that the reactivity of the noble metal type catalyst can be enhanced, and the reactivity of the non-noble metal type catalyst can be improved. Pure CeO2The temperature required for the material to achieve complete oxidation of CO is relatively high and generally cannot be used alone as a catalyst, often being used as one of the carriers or active components. Copper species present Cu0，Cu+,Cu2+Three forms, cerium species due to Ce3+And Ce4+Two oxidation states, in which oxidation-reduction cycles readily occur. Under oxygen-deficient or reducing conditions, surface part Ce4+Is reduced to the valence of +3,generation of oxygen vacancies to form CeO having an oxygen-deficient structure2-x(ii) a Under oxygen-rich or oxidizing conditions, Ce3+And is easily oxidized into +4 valence to make CeO2-xConversion to CeO2. Therefore, the combination of the two components can easily mutually transform due to the interaction under the reaction atmosphere
The reaction cycle is accelerated, thereby improving the catalytic activity. The zinc oxide is used as transition metal oxide, and can greatly improve the CO adsorption performance of the catalyst and promote CuO-CeO2Catalyst formation of active metastable copper species (Cu)+) And oxygen defects, thereby widening the temperature window of the catalytic reaction and improving the low-temperature activity. The zinc oxide can also enhance the water resistance of the catalyst, ensure that the catalyst can still keep good activity in an environment with high humidity and is not easy to be poisoned.
The filler is formed by weaving and combining copper meshes, has a large specific surface, and is beneficial to the reaction of copper and ozone to generate copper oxide to form a CuO-Cu active interface. The ozone concentration must be controlled in a certain concentration range, too high results in the surface of a copper mesh being overoxidized and covering the whole active interface, and too low results in the CuO content being less and the interface activity being reduced. Sampling, detecting the content of CuO, and calculating the configuration concentrations of cerium nitrate and zinc nitrate according to the content of CuO and the water absorption of the filler. Impregnating, drying and roasting the filler to convert cerium nitrate and zinc nitrate into cerium oxide and zinc oxide to form CuO-ZnO-CeO with Cu as a carrier2Is a catalyst of active material. Wherein if the baking temperature is too low, the conversion of the cerium nitrate and the zinc nitrate is not thorough; if the baking temperature is too high, a sintering phenomenon occurs, and the catalyst activity is lowered.
The invention is further illustrated below with reference to specific examples:
in the following examples, unless otherwise specified, the starting materials or processing techniques are all those conventionally available in the art.
Example 1:
an 80-mesh phosphorus bronze wire mesh with the wire diameter of 0.15mm is used as a base material, and is punched into a corrugated filler with the crest included angle alpha of 80 degrees, the corrugated inclination angle beta of 45 degrees (namely, the corrugated channel forms an inclination angle of 45 degrees with the vertical direction), the straight side length m of the wave crest and the wave trough of 0.6mm, the corrugated filler is cut and spliced into the corrugated filler with the diameter of 100mm and the disc height of 50 mm.
The multi-disc packing is sequentially filled into a fixed bed reactor, the ripple directions of two adjacent discs of packing are overlapped at an angle of 90 degrees, the packing is well contacted with the inside of the reactor, and no gap exists. And (3) introducing air mixed with ozone into the reactor, and keeping for 90min to obtain the carrier filler covering the copper oxide film. Wherein the ozone concentration is 10g/m3The flow rate of the mixed gas is 65L/min, and the space velocity of the air mixed with ozone is about 2000h-1。
The filler was removed and a portion of the wire mesh sheet was removed from the filler and the copper oxide content was determined to be 0.9%. Through actual measurement, the liquid holdup of the filler is 10 percent, and the bulk density of the filler is 216kg/m3. The mol ratio of the active components of copper oxide, zinc oxide and cerium oxide is set as 6: 9: 10. according to the calculation configuration, the concentrations of zinc nitrate and cerium nitrate in the mixed solution are respectively as follows: 0.36mol/L and 0.40 mol/L.
Completely soaking the filler into the prepared solution, taking out the filler after absorbing the solution, draining, and drying in an oven at 105 ℃ for 16 hours; and (3) roasting the dried filler in a muffle furnace at 400 ℃ for 4 hours to obtain the carbon monoxide conversion catalyst taking the copper wire mesh corrugated filler as a carrier.
Example 2:
an experiment for removing carbon monoxide from a gas phase was carried out using the catalyst prepared in example 1. 5 pieces of catalyst are selected and sequentially filled into a fixed bed reactor, the ripple directions of two adjacent upper and lower discs of filler are overlapped at an angle of 90 degrees, the catalyst is well contacted with the inside of the reactor, and no gap exists. Air with the inlet CO concentration of 1000ppm is introduced, and the volume space velocity is 3000h-1And the reaction product is analyzed on line by gas chromatography. Test results show that the conversion rate of the catalyst to CO can reach 90% when the reaction temperature is 60 ℃; when the reaction temperature is increased to 90 ℃, the conversion rate of the catalyst to CO can reach more than 99%.
Example 3:
a filler was prepared according to the protocol of example 1, except that only 0.40mol/L of cerium nitrate was added to the solution, and the conditions were completely identical, and the catalyst obtained was evaluated according to the method of example 2, and the catalyst hardly converted carbon monoxide at a temperature of 60 ℃ and the conversion was 60% when the temperature was increased to 110 ℃.
As is clear from example 3, zinc oxide functions to lower the reaction temperature and improve the efficiency of the active material.
The present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.
Claims (10)
1. A carbon monoxide conversion catalyst taking copper wire mesh corrugated packing as a carrier is characterized in that: the carrier is copper wire mesh corrugated packing, and the active ingredients are copper oxide, zinc oxide and cerium oxide.
2. The catalyst of claim 1, wherein: the copper of the copper wire mesh corrugated packing is a copper-containing alloy including, but not limited to, phosphor bronze, brass.
3. The catalyst of claim 1, wherein: the molar mass ratio of the copper oxide to the zinc oxide to the cerium oxide is (50-70): (70-90): (90-100).
4. A preparation method of a carbon monoxide conversion catalyst taking copper wire mesh corrugated packing as a carrier is characterized by comprising the following steps:
1) a plurality of copper wire mesh sheets are sequentially staggered and fixedly combined together according to a certain size ratio to form a disc-shaped filler;
2) carrying out ozone oxidation treatment on the filler obtained in the step 1) to obtain a filler carrier covering the copper oxide film;
3) preparing nitrate of Zn and Ce metal into solution with certain concentration, and mixing the solution uniformly under full stirring;
4) and (3) soaking the filler carrier obtained in the step 2) into the solution prepared in the step 3), drying, roasting, and cooling to normal temperature to obtain the carbon monoxide conversion catalyst taking the copper wire mesh corrugated filler as a carrier.
5. The method of claim 4, wherein: in the step 1), the filler is formed by taking a plurality of single-layer or double-layer copper wire nets as base materials, the corrugated wire nets punched into isosceles trapezoids through a die are sequentially arranged in a staggered mode, and the nets are arranged together according to the size and a certain number of the nets to form the disc filler.
6. The preparation method according to claim 4, wherein in the step 2), the specific process of oxidizing the filler with ozone comprises the following steps: filling a stainless steel reactor with a plurality of discs of packing materials, connecting an ozone generator, introducing ozone, and carrying out ozone oxidation treatment.
7. The method of claim 6, wherein: the gas generated by the ozone generator is a mixed gas of ozone and air or oxygen, and the concentration of the ozone in the mixed gas is not more than 50g/m3The volume space velocity of the introduced mixed gas is 1000-3000 h-1The reaction time is 30-120 min.
8. The method of claim 4, wherein: in the step 3), the nitrates are cerium nitrate and zinc nitrate, the concentrations of the solutions are respectively not more than 0.5mol/L calculated by the cerium nitrate and the zinc nitrate, the solvent is pure water, and the preparation temperature is normal temperature.
9. The method of claim 4, wherein: and 4) soaking the material to completely soak the filler, fully absorbing the solution, taking out the filler after soaking, draining, and drying in drying equipment at the drying temperature of 100-110 ℃ for 8-16 hours.
10. The method of claim 9, wherein: in the step 4), the roasting temperature is 250-500 ℃, and the roasting time is 3-6 hours.
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