CN111744498A - Manganese-copper composite oxide catalyst and preparation method and application thereof - Google Patents
Manganese-copper composite oxide catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910000896 Manganin Inorganic materials 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 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 20
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 20
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005751 Copper oxide Substances 0.000 claims abstract description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 229940071125 manganese acetate Drugs 0.000 claims description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- PNEBHVWHKXQXDR-UHFFFAOYSA-N [O].[Mn].[Cu] Chemical compound [O].[Mn].[Cu] PNEBHVWHKXQXDR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 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
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- B01J23/002—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
- B01J23/76—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
-
- B01J35/40—
-
- B01J35/615—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/04—Purification or separation of nitrogen
- C01B21/0405—Purification or separation processes
- C01B21/0411—Chemical processing only
- C01B21/0416—Chemical processing only by oxidation
-
- 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
Abstract
The invention provides a manganese-copper composite oxide catalyst and a preparation method and application thereof. The manganese-copper composite oxide catalyst comprises the following components: amorphous manganin oxide, activated alumina, pseudo-boehmite; the molar ratio of manganese to copper in the amorphous manganin oxide is (2-3): 1; the particle size of manganese oxide in the amorphous manganin oxide is 1-10 mu m, and the particle size of copper oxide in the amorphous manganin oxide is 1-10 mu m. According to the invention, the amorphous manganin oxide with the particle size is matched with the activated alumina and the pseudo-boehmite, so that the obtained manganin composite oxide catalyst can effectively remove low-concentration CO in nitrogen and can be used for production and preparation of high-purity nitrogen.
Description
Technical Field
The invention relates to the technical field of high-purity nitrogen preparation, and particularly relates to a manganese-copper composite oxide catalyst and a preparation method and application thereof.
Background
With the rapid development of Chinese economy, industrial gas is one of the basic industrial factors of national economy, and the important position and the function in national economy are increasingly highlighted. Particularly, with the coming of the internet era, industries such as electronics, polysilicon and the like are widely aroused, and the demand of high-purity gas is more and more. As a large amount of high-purity gas, high-purity nitrogen is more and more widely applied in the industries of electronics, polycrystalline silicon and the like, at present, the high-purity nitrogen is mainly obtained from a nitrogen production device by adopting a cryogenic rectification method, and the obtained gas often contains impurity water and carbon dioxide (CO)2) And carbon monoxide (CO), the purity requirement of the high-purity gas is higher and higher, the requirement on the content of impurities in the gas is stricter and stricter, nitrogen is often required to be purified, and at present, the impurity water and CO in the nitrogen are2Easier to remove, and CO is more difficult to remove.
The catalysts used for removing CO at present mainly comprise supported Au, Pt and Pd noble metal catalysts and non-noble metal catalysts, such as manganese-copper-based catalysts. Because noble metals are expensive, the development of transition metal oxide catalysts containing little or no noble metals is the mainstream of research at present, for example, catalysts with manganin-based oxides as the main component, and Chinese patent (CN201710812414.8) discloses a supported copper-manganese catalyst which is mainly used for CO catalytic removal in a closed space and can catalyze CO with the concentration of 4000ppm or more. However, when the high-purity nitrogen is subjected to impurity removal, the concentration of CO in the gas is low (generally, the concentration is less than 2500ppmv), so that the CO cannot be effectively and completely eliminated, and the removal rate of the whole CO is low.
Disclosure of Invention
The invention provides a manganese-copper composite oxide catalyst for overcoming the defect that low-concentration CO in high-purity nitrogen cannot be effectively removed by manganese-copper-based catalysis in the prior art, wherein the manganese-copper composite oxide catalyst can effectively remove the low-concentration CO in the nitrogen, and the removal rate can reach more than 90%.
Another object of the present invention is to provide a method for preparing the manganese-copper composite oxide catalyst.
It is still another object of the present invention to provide use of the manganese-copper composite oxide catalyst.
In order to solve the technical problems, the invention adopts the technical scheme that:
the manganese-copper composite oxide catalyst comprises the following components in parts by mass: 70-100 parts of amorphous manganin oxide, 10-30 parts of activated alumina and 10-30 parts of pseudo-boehmite; the molar ratio of manganese to copper in the amorphous manganin oxide is (2-3): 1;
the particle size of manganese oxide in the amorphous manganin oxide is 1-10 mu m, and the particle size of copper oxide in the amorphous manganin oxide is 1-10 mu m.
The inventor finds that the manganese-copper composite oxide catalyst formed by matching the manganese-copper oxide with the particle size with active alumina and pseudo-boehmite has strong CO catalyzing capability and can effectively remove low-concentration CO.
Preferably, the composition comprises the following components in parts by mass: 80-100 parts of amorphous manganin oxide, 10-20 parts of activated alumina and 10-15 parts of pseudo-boehmite.
Preferably, the molar ratio of manganese to copper in the amorphous manganin oxide is (2.3-2.6): 1, more preferably 2.5: 1
The specific surface area of the activated alumina is 150-280 m2/g。
The specific surface area of the pseudo-boehmite is 300-380 m2/g。
The preparation method of the manganese-copper composite oxide catalyst comprises the following steps: mixing manganese copper oxide, activated alumina and pseudo-boehmite according to a proportion; drying at 100-110 ℃, and then activating at 230-260 ℃ for 2-3 hours to obtain the manganese-copper composite oxide catalyst. Preferably, drying is carried out at 100 ℃ and then activation is carried out at 250 ℃ for 2 hours.
In the preparation of amorphous manganin oxide, the stirring speed can have an important influence on the particle size of manganese oxide and copper oxide in the manganin oxide generated in the reaction process. The inventors have summarized a large number of experiments and found that the particle size of manganese oxide and copper oxide in the manganin oxide can be controlled to 1 to 10 μm by controlling the concentration of the raw material and the stirring speed to be in specific ranges.
The preparation method of the amorphous manganin oxide comprises the following steps: preparing manganese acetate and copper nitrate into a mixed solution according to a ratio, then adding a potassium permanganate solution while stirring, controlling the stirring speed at 8000-10000 rpm, filtering, washing and drying to obtain a solid which is amorphous manganin oxide; in the mixed solution, the concentration of manganese acetate is 1.6-1.8 mol/L, and the concentration of copper nitrate is 0.6-0.8 mol/L; the concentration of the potassium permanganate solution is 1.1-1.3 mol/L.
Further, in the mixed solution, the concentration of the manganese acetate is 1.8mol/L, and the concentration of the copper nitrate is 0.72 mol/L; the concentration of the potassium permanganate solution is 1.2 mol/L.
The manganese-copper composite oxide catalyst can effectively catalyze and oxidize carbon monoxide, so that the application of the manganese-copper composite oxide catalyst in the catalytic oxidation of carbon monoxide is also in the protection range of the invention.
Likewise, the manganese-copper composite oxide catalyst of the present invention can be used for removing carbon monoxide contained in nitrogen gas, and therefore, the use of the manganese-copper composite oxide catalyst in removing carbon monoxide contained in nitrogen gas is also within the scope of the present invention. In the above application, the manganin composite oxide can remove low-concentration CO in nitrogen, and generally, the concentration of CO is 3-2000 ppmv.
Further, the removing step is: and (3) passing nitrogen through the manganese-copper composite oxide catalyst, wherein the gas flow is 80-120L/min, the reaction temperature is 10-45 ℃, and the general reaction temperature is 25 ℃ (room temperature).
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the amorphous manganin oxide with the particle size of 1-10 mu m is matched with the activated alumina and the pseudo-boehmite, so that the obtained manganin composite oxide catalyst can effectively remove low-concentration CO in nitrogen and can be used for production and preparation of high-purity nitrogen.
Drawings
FIG. 1 is a scanning electron micrograph of a manganese-copper composite oxide catalyst obtained in example 1 on a coordinatometer of 1 μm.
FIG. 2 is a scanning electron micrograph of a manganin composite oxide catalyst obtained in example 1 with a coordinatometer at 300 nm.
Detailed Description
The present invention will be further described with reference to the following embodiments. The raw materials in the examples and the comparative examples can be obtained by commercial method, wherein the specific surface area of the activated alumina is 150-280 m2(ii)/g; the specific surface area of the pseudo-boehmite is 300-380 m2/g。
The invention carries out detection statistics on the particle size of the manganin oxide according to the following method: and (3) performing scanning electron microscope characterization on the obtained manganin oxide, randomly selecting not less than 5 areas in a scanning electron microscope image, observing the morphology of the manganin oxide and counting the particle size of the manganin oxide.
Example 1
The manganese-copper composite oxide catalyst comprises the following components in parts by mass: 80 parts of amorphous manganin oxide, 10 parts of activated alumina and 10 parts of pseudo-boehmite; the molar ratio of manganese to copper in the amorphous manganin oxide is 2.5: 1; the specific surface area of the activated alumina was 280m2(ii) in terms of/g. The specific surface area of the pseudo-boehmite is 380m2/g。
The manganese-copper composite oxide catalyst is prepared by the following preparation method:
firstly, preparing manganese copper oxide: manganese acetate and copper nitrate are prepared into a mixed solution according to the proportion, the concentration of the manganese acetate is 1.8mol/L, the concentration of the copper nitrate is 0.72mol/L, then potassium permanganate solution with the concentration of 1.2mol/L is added for oxidation, the stirring speed is controlled at 8000rpm, the stirring is carried out for 2 hours, and after a product is filtered, washed by ethanol and washed by distilled water, the product is dried for 2 hours at the temperature of 100 ℃, and then the manganin oxide is obtained. Through detection and statistics, the particle size distribution of manganese oxide and copper oxide in the prepared manganin oxide is within the range of 1-10 mu m.
Then mixing the manganese copper oxide, the activated alumina and the pseudo-boehmite according to the proportion, and extruding into 1/16-inch thin strips by a strip extruding machine; drying at 100 ℃, and then activating for 2 hours at 250 ℃ to obtain the manganese-copper composite oxide catalyst.
Examples 2 to 7 and comparative examples 1 to 4
The compositions of the manganese-copper composite oxide catalysts of examples 2 to 7 and comparative examples 1 to 4 are shown in table 1 below, and the preparation steps thereof are substantially the same as those of example 1.
TABLE 1
Example 8
The manganese-copper composite oxide catalyst comprises the following components in parts by mass: 90 parts of amorphous manganin oxide, 20 parts of activated alumina and 15 parts of pseudo-boehmite; the molar ratio of manganese to copper in the amorphous manganin oxide is 2: 1.
the procedure for preparing the manganin composite oxide catalyst of this example was substantially the same as in example 1, except that the method for preparing the manganin oxide in the manganin composite oxide catalyst was: manganese acetate and copper nitrate are prepared into a mixed solution according to the proportion, the concentration of the manganese acetate in the mixed solution is 1.6mol/L, the concentration of the copper nitrate is 0.8mol/L, then potassium permanganate solution with the concentration of 1.1mol/L is added for oxidation, the stirring speed is controlled at 1000rpm, the stirring is carried out for 2 hours, and after a product is filtered, washed by ethanol and washed by distilled water, the product is dried for 2 hours at the temperature of 100 ℃, and then the manganin oxide is obtained. Through detection and statistics, the particle size distribution of manganese oxide and copper oxide in the prepared manganin oxide is within the range of 1-10 mu m.
Example 9
The manganese-copper composite oxide catalyst comprises the following components in parts by mass: 80 parts of amorphous manganin oxide, 10 parts of activated alumina and 10 parts of pseudo-boehmite; the molar ratio of manganese to copper in the amorphous manganin oxide is 3: 1; the specific surface area of the activated alumina was 150m2(ii) in terms of/g. The specific surface area of the pseudo-boehmite is 300m2/g。
The procedure for preparing the manganin composite oxide catalyst of this example was substantially the same as in example 1, except that the method for preparing the manganin oxide in the manganin composite oxide catalyst was: manganese acetate and copper nitrate are prepared into a mixed solution according to the proportion, the concentration of the manganese acetate in the mixed solution is 1.8mol/L, the concentration of the copper nitrate is 0.6mol/L, then potassium permanganate solution with the concentration of 1.3mol/L is added for oxidation, the stirring speed is controlled at 1000rpm, the stirring is carried out for 2 hours, and after a product is filtered, washed by ethanol and washed by distilled water, the product is dried for 2 hours at the temperature of 100 ℃, and then the manganin oxide is obtained. Through detection and statistics, the particle size distribution of manganese oxide and copper oxide in the prepared manganin oxide is within the range of 1-10 mu m.
Comparative example 5
The composition of the manganin composite oxide catalyst of this comparative example was the same as that of example 1 except that the preparation method of the manganin oxide in the manganin composite oxide catalyst was: manganese acetate and copper nitrate are prepared into a mixed solution according to the proportion, the concentration of the manganese acetate in the mixed solution is 3mol/L, the concentration of the copper nitrate is 1.2mol/L, then a potassium permanganate solution with the concentration of 2mol/L is added for oxidation, the stirring speed is controlled at 8000rpm, the stirring is carried out for 2 hours, and after a product is filtered, washed by ethanol and washed by distilled water, the product is dried for 2 hours at the temperature of 100 ℃, so that the manganin oxide is obtained. Through detection statistics, only a small part of the particle size distribution of manganese oxide and copper oxide in the prepared manganin oxide is within the range of 1-10 mu m.
Characterization and testing
The manganese-copper composite oxide catalysts prepared in the above examples and comparative examples were characterized and tested.
1) The morphology and the size of the manganese-copper composite oxide catalyst prepared in the example were observed by a scanning electron microscope, as shown in fig. 1 and 2. As can be seen from fig. 1, in the manganese-copper composite oxide catalyst of example 1, the manganese-copper oxide is in an amorphous state and is attached to the activated alumina or the pseudo-boehmite, and the manganese-copper composite oxide catalyst has a large number of pores of 1um or more, and has a small macroscopic diffusion resistance when a fluid passes through the material. Further, as can be seen from fig. 2, the manganese-copper composite oxide catalyst of example 1 had nanoscale crystal tips as active centers.
2) The catalytic activity of the manganese-copper composite oxide catalysts prepared in the above examples and comparative examples was subjected to a CO dynamic test,
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 gas flow is 100L/min, the room temperature is about 25 ℃, outlet gas uses a Thermo 48i CO analyzer to test the content of outlet CO, and after the stable operation is carried out for 30 minutes, the inlet and outlet CO concentrations are tested for 30 minutes to calculate the removal rate, and the test results are as follows:
TABLE 2
As can be seen from the data in Table 2, the CO removal rates of the manganese-copper composite oxide catalysts prepared in examples 1 to 9 are all above 90%, wherein in the preferred embodiment of the invention, the CO removal rates of examples 1 and 3 to 5 can be above 98%.
The CO content in nitrogen was further reduced to 3ppmv, and the effect of the manganese-copper composite oxide catalyst prepared in example 1 was tested, the test method was the same as the above method, and the CO removal rate% was 100% by the test.
It should be understood that the above-described embodiments 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 manganese-copper composite oxide catalyst is characterized by comprising the following components in parts by mass: 70-100 parts of amorphous manganin oxide, 10-30 parts of activated alumina and 10-30 parts of pseudo-boehmite; the molar ratio of manganese to copper in the amorphous manganin oxide is (2-3): 1;
the particle size of manganese oxide in the amorphous manganin oxide is 1-10 mu m, and the particle size of copper oxide in the amorphous manganin oxide is 1-10 mu m.
2. The manganese-copper composite oxide catalyst according to claim 1, comprising the following components in parts by mass: 80-100 parts of amorphous manganin oxide, 10-20 parts of activated alumina and 10-15 parts of pseudo-boehmite.
3. The manganin composite oxide catalyst according to claim 1 or 2, wherein the molar ratio of manganese to copper in the amorphous manganin oxide is (2.3-2.6): 1.
4. the manganin composite oxide catalyst according to claim 1, wherein the specific surface area of the activated alumina is 150 to 280m2/g。
5. The manganin composite oxide catalyst according to claim 1 or 4, wherein the pseudo-boehmite has a specific surface area of 300-380 m2/g。
6. The method for producing a manganese-copper composite oxide catalyst according to any one of claims 1 to 5, characterized by comprising the steps of: mixing manganese copper oxide, activated alumina and pseudo-boehmite according to a proportion; drying at 100-110 ℃, and then activating at 230-260 ℃ for 2-3 hours to obtain the manganese-copper composite oxide catalyst.
7. The method according to claim 6, wherein the method for preparing the manganin oxide comprises the following steps: preparing manganese acetate and copper nitrate into a mixed solution according to a ratio, then adding a potassium permanganate solution while stirring, controlling the stirring speed at 8000-10000 rpm, filtering, washing and drying to obtain a solid which is amorphous manganin oxide; in the mixed solution, the concentration of manganese acetate is 1.6-1.8 mol/L, and the concentration of copper nitrate is 0.6-0.8 mol/L.
8. Use of the manganese-copper composite oxide catalyst according to any one of claims 1 to 5 for the catalytic oxidation of carbon monoxide.
9. Use of the manganese-copper composite oxide catalyst according to any one of claims 1 to 5 for removing carbon monoxide in nitrogen.
10. Use according to claim 9, wherein the removing step is: and passing nitrogen through the manganese-copper composite oxide catalyst, wherein the reaction temperature is 10-45 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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