CN115055186B - High-embedding CuO/CeO for removing CO in flue gas 2 Multi-layer catalyst and preparation method thereof - Google Patents
High-embedding CuO/CeO for removing CO in flue gas 2 Multi-layer catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003546 flue gas Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 42
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 239000003245 coal Substances 0.000 claims abstract description 23
- 239000012876 carrier material Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 15
- 150000000703 Cerium Chemical class 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001994 activation Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 15
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 32
- 239000000306 component Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003077 lignite Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J23/70—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
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- 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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- 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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- Health & Medical Sciences (AREA)
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Abstract
The invention discloses a high chimeric CuO/CeO for removing CO in flue gas 2 The preparation method of the multi-layer catalyst comprises the following steps: grinding low-metamorphic coal, copper acetate, ammonium cerium nitrate and a binder as raw materials, mixing, adding water for molding after fully and uniformly mixing, drying, carrying out grading degradation and carrier carbonization on the dried raw materials at low temperature, and activating a carbonized carrier material by high-temperature steam to obtain the carbonized Cu and Ce multi-compound catalyst base material. And washing and drying the obtained carbonaceous base material, and then impregnating and loading Cu under a high-temperature hydrothermal condition to directly realize baking-free decomposition of the carbonaceous base material, thereby obtaining the multi-level catalyst. The active components of the prepared catalyst are firmly embedded and are not easy to fall off; cu species are distributed in a multi-valence level, active components are highly dispersed, and effective active sites are more, so that the catalyst can be used for producing high-performance CuO/CeO for removing CO from high-performance industrial flue gas 2 A catalyst.
Description
Technical Field
The invention belongs to the technical field of catalysts, and in particular relates to a high-embedding CuO/CeO for removing CO in flue gas 2 A multi-layer catalyst and a preparation method thereof.
Background
CO is one of the main pollutants in the atmosphere and has a wide source. Industrial kiln, metallurgical industry flue gas and motor vehicle exhaust all contain a large amount of CO. CO can be combined with hemoglobin in human body to weaken oxygen transmission capacity, damage central nervous system, and increase CO content in air by more than 30mg/m 3 Can have toxic and harmful effects on human body. Introducing catalyst inHigh-efficiency conversion of CO into non-toxic CO at low temperature 2 Is currently recognized as the most promising CO elimination technology. CuO/CeO supported by carbonaceous material 2 The catalyst is considered as the most promising industrial flue gas CO removal catalyst due to higher catalytic activation and low cost, but Cu and Ce active components loaded on the surface of the carrier are easy to be washed out by gas in the application process, so that the catalytic activity is reduced. Therefore, a CuO/CeO is designed in which the active component is not easy to fall off 2 The preparation method of the catalyst has practical significance for eliminating CO in industrial flue gas.
The preparation method of the sintered flue gas carbonaceous adsorbing material (patent application number: CN 201710807924.6) applied by the university of Western-style building technology takes iron-containing materials, low-metamorphic coal, cerium-containing components, binders and pore formers as raw materials, and the sintered flue gas carbonaceous adsorbing material is obtained through high-temperature pyrolysis and steam activation. The preparation method has certain requirements on the catalytic active components, and has low application degree in the field of copper-cerium catalyst preparation. Copper cerium is easy to reduce in the process of preparing the copper cerium catalyst, and the copper cerium catalyst cannot be prepared based on the method. A catalyst for removing nitrogen oxide and carbon monoxide at low temperature and its preparation method (patent application number: CN201310338656. X) applied by Hunan university are to dip activated carbon in copper salt solution after washing with acid, washing with water and drying, then drying and roasting to obtain the catalyst finished product, and the preparation method has great environmental pollution.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a high chimeric CuO/CeO for removing CO in flue gas 2 The invention relates to a multi-layer catalyst and a preparation method thereof, which comprises the active component CuO/CeO 2 Uniformly embedded on the surface of the carbonaceous base material, and is not easy to fall off; and the active metal copper is distributed in a multi-valence level, the dispersibility of the active component is high, the effective activity is more, and the catalytic performance is excellent.
The aim of the invention is realized by the following technical scheme:
high-embedding CuO/CeO for removing CO in flue gas 2 A method for preparing a multi-layered catalyst comprising the steps of:
uniformly mixing low-metamorphic coal, copper salt, cerium salt and a binder, and forming and drying to obtain a formed body;
classifying the molded body for decomposition and carbonizing the carrier to obtain a carbonized carrier material;
activating the carbonaceous carrier material by utilizing steam to obtain a carbonaceous base material;
washing and drying the carbonaceous base material, impregnating and loading Cu under a hydrothermal condition, and drying the carbonaceous base material loaded with Cu to obtain the high chimeric CuO/CeO for removing CO in the flue gas 2 A multi-stage catalyst.
Preferably, the low-deterioration coal, copper salt, cerium salt and binder are respectively ground into powder, uniformly mixed, then mixed with water for molding, and then dried to obtain the molded body.
Preferably, the low-metamorphic coal content in the mixture of the low-metamorphic coal, the copper salt, the cerium salt and the binder is 70.5-80.5% in percentage by mass; the content of the binder is 2.0-10.0%;
the content of copper salt and cerium salt is 10.5% -20.5%, wherein the molar ratio of copper to cerium is 1: (3.5-5).
Preferably, the copper salt is copper acetate, and the cerium salt is ceric ammonium nitrate.
Preferably, the process of classifying the molded body into a decomposition and a carbonization of the carrier comprises: heating the molded body to 250-300 ℃, then preserving heat until the copper acetate decomposition rate is more than 90%, and then heating to 500-600 ℃ to decompose ceric ammonium nitrate and carbonize, wherein the temperature is preserved until the volatile component of the carbonize carrier material is 5-15%.
Preferably, the process for activating a carbonaceous carrier material with steam to obtain a carbonaceous base material comprises: heating the carbonaceous carrier material to 1000-1100 ℃ at a heating rate of 10-12 ℃/min in an inert atmosphere, preserving heat for 5-10 min, then cooling to 700-750 ℃ and then introducing steam for activation until the specific surface area of the carbonaceous material is 500-600 m 2 /g。
Preferably, when the dried carbonaceous base material is impregnated with Cu under hydrothermal conditions, the solution used is a copper acetate solution, and the hydrothermal temperature of impregnation is 220-260 ℃.
Preferably, the dry carbonaceous base material is impregnated with a load of Cu in an amount of 1.2 to 3.0 times the Cu content of the carbonaceous base material under hydrothermal conditions.
Preferably, the binder is sodium carboxymethyl cellulose or soluble starch.
The invention also provides a high chimeric CuO/CeO for removing CO in the flue gas 2 Multi-layer catalyst, the high chimeric CuO/CeO for removing CO in flue gas 2 The multi-layered catalyst is prepared by the preparation method of the invention as described above.
The invention has the following beneficial effects:
the invention removes high chimeric CuO/CeO of CO in the flue gas 2 The preparation method of the multi-layer catalyst can be used for preparing the active component CuO/CeO 2 Uniformly embedded on the surface of the carbonaceous base material, and is not easy to fall off; and the active metal copper is distributed in a multi-valence level, the dispersibility of the active component is high, the effective activity is more, and the catalytic performance is excellent.
Further, in the process of classifying decomposition of the molded body and carbonization of the carrier, the molded body is heated to 250-300 ℃ firstly, then the molded body is insulated until the copper acetate decomposition rate is more than 90%, and then the molded body is heated to 500-600 ℃ again to decompose and carbonize ceric ammonium nitrate, so that the mechanical strength of the carbonized carrier is ensured to be less influenced by copper acetate and ceric ammonium nitrate, and meanwhile, cu and Ce active components are firmly embedded on the surface of the carbonized carrier and are not easy to fall off.
Further, in the process of activating the carbonaceous carrier material by using water vapor, the carbonaceous carrier is firstly and rapidly heated to 1000-1100 ℃ in an inert atmosphere (at a heating rate of 10-12 ℃/min), and is kept for 5-10 min, so that the closed holes on the surface of the carbonaceous carrier are opened, and then the temperature is reduced to 700-750 ℃ for activating the carbonaceous carrier material, and then the carbonaceous carrier material is activated by introducing water vapor, so that the mass base material with large specific surface area, which is favorable for exposing more active sites, is obtained.
Further, when the dried carbonaceous base material is impregnated with Cu under hydrothermal conditions, the Cu is loaded with water at 220-260 ℃ by using a copper acetate solutionAnd (3) impregnating and loading Cu under a thermal condition, wherein Cu is highly dispersed and uniformly adhered on the surface of the carbonaceous base material. The active components of the obtained catalyst are tightly embedded on the surface of the carbonized base material, copper species are distributed in a multivalent level, and CuO/CeO is improved while the falling of the active components is prevented 2 Catalytic activity.
Detailed Description
The invention will be further illustrated with reference to the following examples.
The invention removes high chimeric CuO/CeO of CO in the flue gas 2 A method for preparing a multi-layered catalyst comprising the steps of:
grinding low-metamorphic coal, copper acetate, ammonium cerium nitrate and binder into powder respectively, mixing, adding water into the raw materials after fully and uniformly mixing, stirring uniformly, pressing, drying, heating the dried raw materials to 250-300 ℃, preserving heat until the copper acetate decomposition rate is more than 90%, heating to 500-600 ℃ and preserving heat to perform ammonium cerium nitrate decomposition and carbonization processes, and preserving heat until the volatile components of the carbonized carrier material are 5-15%, thus obtaining the carbonized carrier. Rapidly heating the carbonaceous carrier to 1000-1100 ℃ at a heating rate of 10-12 ℃/min in an inert atmosphere, preserving heat for 5-10 min, cooling to 700-750 ℃ and then introducing steam for activation until the specific surface area of the carbonaceous carrier is 500-600 m 2 Between/g, a carbonaceous Cu, ce multi-element compound catalyst base material is obtained. Wherein, the raw materials for preparing the carbonaceous base material comprise the following components in percentage by mass: 70.5 to 80.5 percent of low metamorphic coal; copper acetate and ammonium cerium nitrate are 10.5% -20.5% in total, the binder is 2.0% -10.0%, and the Cu/Ce molar ratio is 1:3.5 to 5.
Washing and drying the obtained carbonized base material, and impregnating and loading Cu with a copper acetate solution under the high-temperature hydrothermal condition of 220-260 ℃ until Cu content in the prepared carbonized base material is 1.2-3.0 times, thereby obtaining the high chimeric CuO/CeO for removing the CO in the flue gas 2 A multi-stage catalyst.
The active components of the catalyst prepared by the method are firmly embedded and are not easy to fall off; cu species are distributed in a multi-valence level, active components are highly dispersed, and effective active sites are more, so that the Cu-based composite material can be used for producing high-performance workersHigh-performance CuO/CeO for removing CO from industrial flue gas 2 A catalyst.
The invention will be further illustrated with reference to the following examples.
In the following examples of the invention, the simulated reaction gas composition containing CO used in the experiments was: 1% CO, 20% O 2 、79％N 2 The gas flow rate was 100ml/min.
The calculation formula of the CO removal efficiency is as follows: CO removal rate= (content of CO in feed gas-content of CO in tail gas)/content of CO in feed gas x 100%.
Example 1:
in the embodiment, the raw materials are calculated according to mass fraction: the low metamorphic coal content is 70.5%, the binder content is 9.0%, the sum of copper salt and cerium salt is 20.5%, wherein the molar ratio of copper to cerium is 1:5, the content of copper acetate and ammonium cerium nitrate is 1.3% and 19.2% respectively. (wherein, the low metamorphic coal is brown coal, the industrial analysis is that ash content is 6.7%, volatile matter is 37.4%, fixed carbon is 55.9%, and the binder is sodium carboxymethyl cellulose.) the low metamorphic coal, copper acetate, ceric ammonium nitrate and the binder are respectively ground into powder and then mixed, the fully and uniformly mixed raw materials are added with water and uniformly stirred, are dried after being pressed and molded, the dried raw materials are heated to 250 ℃ and kept for 50min, the decomposition rate of copper acetate is detected to be 93.5%, then heated to 500 ℃ and kept for 80min, the decomposition rate of ceric ammonium nitrate is detected to be 93.7%, and the temperature is kept until the volatile component of the carbonized carrier material is 5%, thus obtaining the carbonized carrier material. Carbonaceous support material in N 2 Heating to 1000 ℃ at a heating rate of 10-12 ℃/min in the atmosphere, preserving heat for 5min, then cooling to 700 ℃, introducing steam, activating for 50min, and detecting that the specific surface area of the base material of the C-Cu and Ce multi-compound catalyst is 536m 2 And/g. Washing and drying the obtained carbonized base material, impregnating and loading Cu with a copper acetate solution under 220 ℃ hydrothermal condition, wherein the Cu content of the hydrothermal impregnation and loading is 1.2 times of Cu in the carbonized base material, and obtaining the high chimeric CuO/CeO for removing the CO in the flue gas 2 A multi-stage catalyst.
High embedding CuO/CeO for removing CO in the obtained flue gas 2 Performance testing of the multi-layered catalyst: 300mg of catalyst is filled in 8mm quartz for reactionIn the tube, controlling the reaction temperature to be 180 ℃, introducing simulated reaction gas containing CO, and detecting the concentration of CO in the inlet and outlet gas; the high chimeric CuO/CeO for removing the CO in the flue gas prepared by the method 2 The multi-level catalyst has the CO removal rate of 95.6% in the simulation reaction, the CO conversion rate is only reduced by 1.3% after the catalytic reaction is carried out for 128h, and the catalytic performance is superior to that of CuO/CeO prepared by the conventional method 2 A catalyst.
Example 2
In the embodiment, the raw materials are calculated according to mass fraction: the low metamorphic coal content is 79.5%, the binder content is 10.0%, the sum of copper salt and cerium salt is 10.5%, wherein the molar ratio of copper to cerium is 1:4, the content of copper acetate and ammonium cerium nitrate is 0.8% and 9.7% respectively. (wherein, the low-metamorphic coal is brown coal, the industrial analysis is that ash content is 6.7 percent, volatile matter is 37.4 percent, fixed carbon is 55.9 percent, and the binder is soluble starch.) respectively grinding the low-metamorphic coal, copper acetate, ceric ammonium nitrate and the binder into powder, mixing, adding water into the fully and uniformly mixed raw materials, uniformly stirring, pressing, drying, heating the dried raw materials to 275 ℃, preserving heat for 60 minutes, and detecting that the decomposition rate of copper acetate is 95.5 percent; and then heating to 550 ℃ and preserving heat for 100min, wherein the decomposition rate of ceric ammonium nitrate is detected to be 96.1%, and preserving heat until the volatile components of the carbonized carrier material are 11%, thus obtaining the carbonized carrier material. Carbonaceous support material in N 2 Heating to 1050 ℃ at a heating rate of 10-12 ℃/min in the atmosphere, preserving heat for 7min, then cooling to 725 ℃, introducing steam, activating for 60min, and detecting that the specific surface area of the carbonaceous Cu, ce multi-compound catalyst base material is 578m 2 And/g. Washing and drying the obtained carbonized base material, impregnating and loading Cu with a copper acetate solution under a hydrothermal condition at 240 ℃, wherein the Cu content of the hydrothermal impregnation and loading is 2.2 times of that of Cu in the carbonized base material, and obtaining the high chimeric CuO/CeO for removing the CO in the flue gas 2 A multi-stage catalyst.
High embedding CuO/CeO for removing CO in the obtained flue gas 2 Performance testing of the multi-layered catalyst: filling 300mg of catalyst into an 8mm quartz reaction tube, controlling the reaction temperature to be 180 ℃, introducing simulated reaction gas containing CO, and detecting the concentration of CO in inlet and outlet gases; the method for removing CO in the flue gasHigh mosaic CuO/CeO 2 The multi-level catalyst has the CO removal rate of 97.2% in the simulation reaction, the CO conversion rate is reduced by 0.7% after the catalytic reaction is carried out for 128h, and the catalytic performance is superior to that of CuO/CeO prepared by the conventional method 2 A catalyst.
Example 3
In the embodiment, the raw materials are calculated according to mass fraction: the low metamorphic coal content is 80.5%, the binder content is 2.0%, the sum of copper salt and cerium salt is 17.5%, wherein the molar ratio of copper to cerium is 1:3.5, the content of copper acetate and ammonium cerium nitrate is 1.6% and 15.9% respectively. (wherein, the low metamorphic coal is brown coal, the industrial analysis is that ash content is 6.7%, volatile matter is 37.4%, fixed carbon is 55.9%, and the binder is sodium carboxymethyl cellulose.) the low metamorphic coal, copper acetate, ceric ammonium nitrate and the binder are respectively ground into powder and then mixed, the fully and uniformly mixed raw materials are added with water and uniformly stirred, are dried after being pressed and molded, the dried raw materials are heated to 300 ℃ and kept for 70min, the decomposition rate of copper acetate is detected to be 96.2%, then heated to 600 ℃ and kept for 120min, the decomposition rate of ceric ammonium nitrate is detected to be 98.6%, and the temperature is kept until the volatile component of the carbonized carrier material is 15%, thus obtaining the carbonized carrier material. Carbonaceous support material in N 2 Heating to 1100 ℃ at a heating rate of 10-12 ℃/min in the atmosphere, preserving heat for 10min, cooling to 750 ℃, introducing steam, activating for 70min, and detecting that the specific surface area of the carbonaceous Cu, ce multi-compound catalyst base material is 592m 2 And/g. Washing and drying the obtained carbonized base material, impregnating and loading Cu with a copper acetate solution under a hydrothermal condition at 260 ℃, wherein the Cu content of the hydrothermal impregnation and loading is 3 times of that of Cu in the carbonized base material, and obtaining the high chimeric CuO/CeO for removing CO in flue gas 2 A multi-stage catalyst.
High embedding CuO/CeO for removing CO in the obtained flue gas 2 Performance testing of the multi-layered catalyst: filling 300mg of catalyst into an 8mm quartz reaction tube, controlling the reaction temperature to be 180 ℃, introducing simulated reaction gas containing CO, and detecting the concentration of CO in inlet and outlet gases; the high chimeric CuO/CeO for removing the CO in the flue gas prepared by the method 2 The multi-level catalyst has a CO removal rate of 94.5% in the simulated reaction, and the CO conversion rate is only reduced after 128h of the catalytic reaction is carried out1.6 percent, the catalytic performance is better than that of CuO/CeO prepared by the conventional method 2 A catalyst.
In conclusion, the invention prepares the high chimeric CuO/CeO for removing the CO in the flue gas from the perspective of CO catalytic oxidation 2 A multi-stage catalyst. Mixing, molding, drying, grading degradation, carbonization and activation of low-metamorphic coal, copper acetate, ammonium cerium nitrate and a binder to obtain a carbonized base material; the obtained carbonaceous base material is subjected to high-temperature hydrothermal impregnation to obtain high-embedding CuO/CeO 2 The multi-level catalyst has low cost, simple production process and easy implementation. The prepared catalyst has large specific surface area, high mechanical strength, firm embedding of active components, difficult falling off, high dispersibility, copper oxide in multi-valence level distribution, high catalytic activity and good stability, and is favorable for producing high-performance CuO/CeO for removing CO in industrial flue gas 2 A catalyst.
Claims (2)
1. High-embedding CuO/CeO for removing CO in flue gas 2 The preparation method of the multi-level catalyst is characterized by comprising the following steps:
uniformly mixing low-metamorphic coal, copper salt, cerium salt and a binder, and forming and drying to obtain a formed body;
classifying the molded body for decomposition and carbonizing the carrier to obtain a carbonized carrier material;
activating the carbonaceous carrier material by utilizing steam to obtain a carbonaceous base material;
washing and drying the carbonaceous base material, impregnating and loading Cu under a hydrothermal condition, and drying the carbonaceous base material loaded with Cu to obtain the high chimeric CuO/CeO for removing CO in the flue gas 2 A multi-level catalyst;
wherein, the specific process for obtaining the molded body comprises the following steps of uniformly mixing low-metamorphic coal, copper salt, cerium salt and a binder, molding and drying: grinding low-deterioration coal, copper salt, cerium salt and binder into powder respectively, uniformly mixing, mixing with water for molding, and drying to obtain the molded body;
when the dried carbonaceous base material is impregnated with Cu under hydrothermal condition, the used solution is copper acetate solution, and the impregnating hydrothermal temperature is 220-260 ℃;
the low-metamorphic coal content in the mixture of the low-metamorphic coal, the copper salt, the cerium salt and the binder is 70.5-80.5% in percentage by mass; the content of the binder is 2.0-10.0%; the content of copper salt and cerium salt is 10.5% -20.5%, wherein the molar ratio of copper to cerium is 1: (3.5-5);
the copper salt adopts copper acetate, and the cerium salt adopts ceric ammonium nitrate;
the process of classifying and decomposing the molded body and carbonizing the carrier comprises the following steps: heating the molded body to 250-300 ℃, then preserving heat until the copper acetate decomposition rate is more than 90%, and then heating to 500-600 ℃ to decompose ceric ammonium nitrate and carbonize the molded body until the volatile components of the carbonize carrier material are 5-15%;
the process for activating a carbonaceous carrier material with steam to obtain a carbonaceous base material comprises: heating the carbonaceous carrier material to 1000-1100 ℃ at a heating rate of 10-12 ℃/min in an inert atmosphere, preserving heat for 5-10 min, cooling to 700-750 ℃ and then introducing steam for activation until the specific surface area of the carbonaceous carrier material is 500-600 m 2 /g；
The Cu content of the impregnation load of the dried carbonized base material under the hydrothermal condition is 1.2-3.0 times of the Cu content in the carbonized base material;
the binder adopts sodium carboxymethyl cellulose or soluble starch.
2. High-embedding CuO/CeO for removing CO in flue gas 2 The multi-level catalyst is characterized in that the high chimeric CuO/CeO for removing CO in the flue gas 2 The multi-layer catalyst is prepared by removing high chimeric CuO/CeO of CO in flue gas according to claim 1 2 The preparation method of the multi-layer catalyst is provided.
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