CN105268452A - Mesoporous supported copper-manganese compound oxide catalyst and preparation and catalysis methods - Google Patents
Mesoporous supported copper-manganese compound oxide catalyst and preparation and catalysis methods Download PDFInfo
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- CN105268452A CN105268452A CN201510769581.XA CN201510769581A CN105268452A CN 105268452 A CN105268452 A CN 105268452A CN 201510769581 A CN201510769581 A CN 201510769581A CN 105268452 A CN105268452 A CN 105268452A
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Abstract
A mesoporous supported copper-manganese compound oxide catalyst is prepared from an active component 10%-25% copper-manganese compound oxide, an additive 5%-20% CeO2, ZrO2 or La2O3 and the balance mesoporous oxide Al2O3, TiO2 or SiO2 serving as a carrier. A preparation method includes the following steps that 1, the mesoporous oxide carrier is prepared, namely the mesoporous oxide carrier Al2O3, TiO2 or SiO2 is prepared; 2, the active component and the additive are supported, and the mesoporous supported copper-manganese compound oxide catalyst is prepared. The catalyst can perform formaldehyde catalysis and oxidation reaction at low temperature and completely oxidizes formaldehyde into water and carbon dioxide at the low temperature (75-125 DEG C) so as to remove the formaldehyde. The mesoporous supported copper-manganese compound oxide catalyst can effectively catalyze and oxidize formaldehyde, convert the formaldehyde into non-toxic CO2 and H2O, no other by-product is produced, the production process of the catalyst is simple, the cost is low, and the catalyst has good economy.
Description
Technical field
The invention belongs to catalysis material, environmental catalysis and environmental protection technical field, be specifically related to the mesoporous carried copper Mn complex oxide catalyst and preparation method thereof for catalytic oxidation indoor formaldehyde.
Background technology
Indoor formaldehyde is mainly derived from building decoration and finishing material, as taken Lauxite as the various wood-based plates (as glued board, fiberboard and particieboard etc.) of adhesive, the water soluble paint etc. of arteries and veins urea formaldehyde heat-barrier material, aldehyde-containing type disinfection preservative, it is one of pollutant the most serious in China's present stage room air, China's toxic chemical priority acccess control list is in second, and is defined as carcinogenic by the World Health Organization and causes deformed material.According to statistics, fit up in 1 ~ 6 month, formaldehyde rate is up to 80%; To fit up after 3 years formaldehyde rate still up to more than 50%; The Form aldehyde release phase in indoor furniture and finishing material is generally 8 ~ 15 years." Indoor Air Quality standards " that China promulgates specifies that resident's formaldehyde in indoor air sanitary standard (maximum permissible concentration) is 0.08mg/m
3, be at room temperature about 0.06ppm.People in life about 90% time spend in indoor, therefore, IAQ situation and health closely bound up, the formaldehyde removed in indoor or closed system is imperative.Study new and effective, low-cost net formed material and technology, formaldehyde in indoor air of effectively degrading, improves working environment, protection health, builds well-off society, harmonious society has great importance to China.
At present, the minimizing technology of indoor formaldehyde mainly contains bioanalysis, absorption method, plasma technique, chemical reaction method, photochemical catalytic oxidation and heat catalytic oxidation method.Wherein, heat catalytic oxidation because treatment effeciency is high, relative cost is low, treating capacity is large, process is thorough, and does not have secondary pollution problems, is to eliminate the most effective method of formaldehyde, and the key of the method is catalyst.Research for the catalyst system of formaldehyde through catalytic oxidation mainly concentrates on the aspect such as loaded noble metal catalyst and non-precious metal catalyst.Wherein, the research of loaded noble metal catalyst is comparatively extensive and treatment effect is better, and disclosed in the patent of [201110087511.8], a kind of silver-carrying nano manganese dioxide-catalyst can at 0 ~ 120 DEG C of complete catalysts oxidation formaldehyde; The activity that disclosed in [200910098633.X] patent, a kind of loaded noble metal catalyst can keep PARA FORMALDEHYDE PRILLS(91,95) higher at low temperatures and stability.But loaded noble metal catalyst price is higher and reserves are limited, be not easy to promote.Non-noble metal oxide catalyst becomes more readily available, and price is relatively low, has wide development space and market prospects.With regard to the document of current all reports, use the report of Cu-Mn complex oxide catalyze oxidation of formaldehyde few, use the mesopore oxide (Al of high-specific surface area
2o
3, TiO
2or SiO
2) have no report especially as carrier.This research uses mesoporous carried copper Mn complex oxide catalyst to obtain good catalytic performance in catalyze oxidation of formaldehyde reaction.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art, the object of the present invention is to provide mesoporous carried copper Mn complex oxide catalyst and preparation method thereof, the catalyst provided can under comparatively low reaction temperatures (75 ~ 125 DEG C) catalytic purification formaldehyde completely, good catalyst activity, cost is low, and preparation technology is simple.
For achieving the above object, the technical solution used in the present invention is: mesoporous carried copper Mn complex oxide catalyst, comprises following component: active component 10% ~ 25%; Auxiliary agent 5% ~ 20% surplus is mesopore oxide is carrier loaded.
Described mesopore oxide adopts Al
2o
3, TiO
2or SiO
2.
Described active component is Cu-Mn complex oxide.
Described auxiliary agent adopts CeO
2, ZrO
2or La
2o
3
The preparation method of mesoporous carried copper Mn complex oxide catalyst, comprises the following steps:
1) preparation of mesopore oxide carrier: 1.0 ~ 3.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 10 ~ 30mL absolute ethyl alcohol or distilled water, magnetic agitation 1 ~ 3h, instillation 2.0 ~ 4.0mL hydrochloric acid or nitric acid, continue stirring 10 ~ 30min, then the one in 2.0 ~ 6.0g aluminium isopropoxide, butyl titanate or ethyl orthosilicate is added, stir 4 ~ 6h, dry 6 ~ 12h in 40 ~ 80 DEG C of baking ovens, in Muffle furnace, 400 ~ 600 DEG C of roasting 4 ~ 6h, obtain mesopore oxide carrier A l
2o
3, TiO
2or SiO
2;
2) load of active component and auxiliary agent: be that copper nitrate and 50% manganese nitrate aqueous solution of 1:1 ~ 1:5 joins in the distilled water of 50 ~ 150mL by molar ratio, then the one in the cerous nitrate of 0.1262 ~ 0.5046g, 0.1742 ~ 0.6968g zirconium nitrate or 0.0664 ~ 0.2658g lanthanum nitrate is added, be made into mixed solution, drop into mesopore oxide carrier A l subsequently
2o
3, TiO
2or SiO
2, stir 4 ~ 8h in 30 ~ 60 DEG C of waters bath with thermostatic control, dry 6 ~ 12h at 90 ~ 120 DEG C, 400 ~ 600 DEG C of roasting 3 ~ 6h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst.
By the method for mesoporous carried copper Mn complex oxide catalyst catalyze oxidation of formaldehyde, catalytic oxidation performance evaluation is carried out in miniature fixed bed continuous-flow reaction system, comprises the following steps:
1) take 200mg, 40 ~ 60 object catalyst with etc. the quartz sand of particle diameter mix, load the hard glass pipe reactor that internal diameter is 10cm;
2) gaseous formaldehyde produces by N
2gas flow purging is placed in the paraformaldehyde of thermostat, then with primary air 20%O
2/ N
2mixing;
3) concentration of formaldehyde is controlled by the weight of paraformaldehyde and the flow velocity of thermostat and carrier gas, obtains consisting of of unstripped gas: 100 ~ 900ppm formaldehyde, the O of 20%
2/ N
2;
4) reactor outlet gas GC1690 type gas chromatographic analysis, chromatogram configuration TCD and fid detector, assemble a nickel converter in front of the detector;
5) this catalyst at ambient pressure gas volume air speed be 3 × 10
3~ 3 × 10
5h
-1time, reaction temperature is under the condition of 25 ~ 125 DEG C, can be CO by formaldehyde complete catalysts oxidation
2and H
2o.
Beneficial effect of the present invention is:
Compared with prior art, formaldehyde complete catalysts oxidation (75 ~ 125 DEG C) can be become CO by catalyst of the present invention at low temperatures
2and H
2o, catalytic activity is good, without other accessory substance; The preparation process of this catalyst is simple, and raw material is easy to get, and cost is low, and Feasible degree is high, has excellent economy.Can be applicable to indoor, in car, decoration material processing factory, wood-working factory etc. environment and other spacecraft, spaceship, submarine etc. microenvironment formaldehyde through catalytic oxidation.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
embodiment 1:
Mesoporous carried copper Mn complex oxide catalyst CuMnO
x-CeO
2/ Al
2o
3(brief note CMCA), includes following component: the Al of 70%
2o
3, the Cu-Mn complex oxide of 25%, the CeO of 5%
2.
The preparation method of mesoporous carried copper Mn complex oxide catalyst CMCA, comprises the following steps: 1) mesoporous Al
2o
31.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 10mL absolute ethyl alcohol by the preparation of carrier, magnetic agitation 1h, instillation 2.0mL nitric acid, continue to stir 10min, then add 3.0g aluminium isopropoxide, stir 4h, dry 10h in 60 DEG C of baking ovens, in Muffle furnace, 600 DEG C of roasting 4h, obtain mesoporous Al
2o
3carrier; 2) load of active component and auxiliary agent, is that copper nitrate and 50% manganese nitrate aqueous solution of 1:3 joins in the distilled water of 100mL by molar ratio, then adds the cerous nitrate of 0.1262g, be made into mixed solution, drops into mesopore oxide carrier A l subsequently
2o
3, stir 6h in 50 DEG C of waters bath with thermostatic control, dry 10h at 100 DEG C, 500 DEG C of roasting 4h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst CMCA.Wherein, Cu-Mn content accounts for 25% of catalyst gross mass, auxiliary agent CeO
2content accounts for 5% of catalyst gross mass.
The CMCA catalyst adopting said method obtained is used for catalyze oxidation of formaldehyde, its course of reaction is, this reaction is carried out in miniature fixed bed continuous-flow reaction system, take 200mg(40 ~ 60 order) catalyst mix with waiting the quartz sand of particle diameter, load the hard glass pipe reactor that internal diameter is 10cm; Gaseous formaldehyde produces by N
2gas flow purging is placed in the paraformaldehyde of thermostat, then with primary air 20%O
2/ N
2mixing; The concentration of formaldehyde is controlled by the weight of paraformaldehyde and the flow velocity of thermostat and carrier gas, obtains consisting of of unstripped gas: 600ppm formaldehyde, 20%O
2/ N
2, gas volume air speed is 3 × 10
4h
-1time; A temperature spot is established for every 25 DEG C from 25 DEG C, to 150 DEG C, each temperature spot reaction 1h; After reaction reaches stable state, reactor outlet gas GC1690 type gas chromatographic analysis, chromatogram configuration fid detector, assembles a nickel converter in front of the detector.By the CO that detection reaction exports
2concentration calculates the conversion ratio of HCHO.
The result of CMCA catalyst oxidation of formaldehyde is as follows under these conditions: when 25 DEG C, formaldehyde conversion 80.4%; When 50 DEG C, formaldehyde conversion 87.6%; When 75 DEG C, formaldehyde conversion 100%; When 100 DEG C, formaldehyde conversion 100%; When 125 DEG C, formaldehyde conversion 100%.
embodiment 2:
Mesoporous carried copper Mn complex oxide catalyst CuMnO
x-ZrO
2/ Al
2o
3(brief note CMZA), comprises following component: the Al of 70%
2o
3, the Cu-Mn complex oxide of 20%, the ZrO of 10%
2.
The preparation method of mesoporous carried copper Mn complex oxide catalyst brief note CMZA, comprises the following steps: 1) mesoporous Al
2o
3the preparation of carrier is with in example 1 1) step; 2) molar ratio is that the copper nitrate of 1:5 and 50% manganese nitrate aqueous solution join in the distilled water of 150mL by the load of active component and auxiliary agent, then adds the zirconium nitrate of 0.3484g, is made into mixed solution, drop into mesopore oxide carrier A l subsequently
2o
3, stir 4h in 60 DEG C of waters bath with thermostatic control, dry 6h at 120 DEG C, 500 DEG C of roasting 3h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst CMZA.Wherein, Cu-Mn content accounts for 20% of catalyst gross mass, auxiliary agent ZrO
2content accounts for 10% of catalyst gross mass.
The performance test of catalyst CMZA is with embodiment 1, and the result of CMZA catalyst oxidation of formaldehyde is as follows under these conditions: when 25 DEG C, formaldehyde conversion 70.4%; When 50 DEG C, formaldehyde conversion 80.2%; When 75 DEG C, formaldehyde conversion 89.5%; When 100 DEG C, formaldehyde conversion 95.7%; When 125 DEG C, formaldehyde conversion 100%.
embodiment 3:
Mesoporous carried copper Mn complex oxide catalyst CuMnO
x-La
2o
3/ Al
2o
3(brief note CMLA), includes following component: the Al of 70%
2o
3, the Cu-Mn complex oxide of 10%, the La of 20%
2o
3.
The preparation method of mesoporous carried copper Mn complex oxide catalyst CMLA, comprises the following steps: 1) mesoporous Al
2o
3the preparation of carrier is with in example 1 1) step; 2) molar ratio is that the copper nitrate of 1:1 and 50% manganese nitrate aqueous solution join in the distilled water of 50mL by the load of active component and auxiliary agent, then adds the lanthanum nitrate of 0.2658g, is made into mixed solution, drop into mesopore oxide carrier A l subsequently
2o
3, stir 8h in 30 DEG C of waters bath with thermostatic control, dry 12h at 90 DEG C, 400 DEG C of roasting 6h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst CMLA.Wherein, Cu-Mn content accounts for 10% of catalyst gross mass, auxiliary agent La
2o
3content accounts for 20% of catalyst gross mass.
The performance test of catalyst is with embodiment 1, and the result of mesoporous carried copper Mn complex oxide catalyst CMLA catalyze oxidation of formaldehyde is as follows under these conditions: when 25 DEG C, formaldehyde conversion 75.2%; When 50 DEG C, formaldehyde conversion 86.3%; When 75 DEG C, formaldehyde conversion 90.6%; When 100 DEG C, formaldehyde conversion 95.7%; When 125 DEG C, formaldehyde conversion 100%.
embodiment 4:
Mesoporous carried copper Mn complex oxide catalyst CuMnO
x-CeO
2/ TiO
2(brief note CMCT) includes following component: the TiO of 70%
2, the Cu-Mn complex oxide of 25%, the CeO of 5%
2.
The preparation of mesoporous carried copper Mn complex oxide catalyst CMCT: 1) mesoporous TiO
23.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 30mL distilled water by the preparation of carrier, magnetic agitation 3h, instillation 4.0mL hydrochloric acid, continue to stir 30min, then add 6.0g butyl titanate, stir 6h, dry 12h in 40 DEG C of baking ovens, in Muffle furnace, 400 DEG C of roasting 6h, obtain mesoporous TiO
2carrier; 2) load of active component and auxiliary agent is with in embodiment 1 2) step.
The performance test of catalyst is with embodiment 1, and the result of CMCT catalyst oxidation of formaldehyde is as follows under these conditions: when 25 DEG C, formaldehyde conversion 76.5%; When 50 DEG C, formaldehyde conversion 84.3%; When 75 DEG C, formaldehyde conversion 89.4%; When 100 DEG C, formaldehyde conversion 94.5%; When 125 DEG C, formaldehyde conversion 100%.
Embodiment 5:
Mesoporous carried copper Mn complex oxide catalyst CuMnO
x-CeO
2/ SiO
2(brief note CMCS), comprises following component: the SiO of 70%
2, the Cu-Mn complex oxide of 22%, the CeO of 8%
2.
The preparation method of mesoporous carried copper Mn complex oxide catalyst CMCS, comprises the following steps: 1) mesoporous SiO
22.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 20mL absolute ethyl alcohol by the preparation of carrier, magnetic agitation 2h, instillation 3.0mL hydrochloric acid, continue to stir 30min, then add 2.0g ethyl orthosilicate, stir 5h, dry 6h in 80 DEG C of baking ovens, in Muffle furnace, 500 DEG C of roasting 5h, obtain mesoporous SiO
2carrier; 2) load of active component and auxiliary agent is with in embodiment 1 2) step.
The performance test of catalyst is with embodiment 1, and the result of CMCS catalyst oxidation of formaldehyde is as follows under these conditions: when 25 DEG C, formaldehyde conversion 75.4%; When 50 DEG C, formaldehyde conversion 79.6%; When 75 DEG C, formaldehyde conversion 84.5%; When 100 DEG C, formaldehyde conversion 95.7%; When 125 DEG C, formaldehyde conversion 100%.
embodiment 6:
By the catalyst preparation step of embodiment 1, obtained mesoporous carried copper Mn complex oxide catalyst CMCA, the catalytic oxidation of formaldehyde is carried out with this catalyst, Catalyst Testing Conditions is with embodiment 1,100ppm is adjusted to unlike by the concentration of formaldehyde, its result is: when 25 DEG C, formaldehyde conversion 84.6%; When 50 DEG C, formaldehyde conversion 98.1%; When 75 DEG C, formaldehyde conversion 100%; When 100 DEG C, formaldehyde conversion 100%; When 125 DEG C, formaldehyde conversion 100%.
embodiment 7:
By the catalyst preparation step of embodiment 1, obtained mesoporous carried copper Mn complex oxide catalyst CMCA, the catalytic oxidation of formaldehyde is carried out with this catalyst, Catalyst Testing Conditions is with embodiment 1,900ppm is adjusted to unlike by the concentration of formaldehyde, its result is: when 25 DEG C, formaldehyde conversion 56.9%; When 50 DEG C, formaldehyde conversion 61.2%; When 75 DEG C, formaldehyde conversion 74.3%; When 100 DEG C, formaldehyde conversion 82.3%; When 125 DEG C, formaldehyde conversion 95.3%.
embodiment 8:
By the catalyst preparation step of embodiment 1, obtained mesoporous carried copper Mn complex oxide catalyst CMCA, carry out the catalytic oxidation of formaldehyde with this catalyst, Catalyst Testing Conditions, with embodiment 1, is adjusted to 3.0 × 10 unlike by gas volume air speed
3h
-1, its result is: when 25 DEG C, formaldehyde conversion 85.6%; When 50 DEG C, formaldehyde conversion 96.3.3%; When 75 DEG C, formaldehyde conversion 100%; When 100 DEG C, formaldehyde conversion 98.6%; When 125 DEG C, formaldehyde conversion 100%.
embodiment 9:
By the catalyst preparation step of embodiment 1, obtained mesoporous carried copper Mn complex oxide catalyst CMCA, carry out the catalytic oxidation of formaldehyde with this catalyst, Catalyst Testing Conditions, with embodiment 1, is adjusted to 3.0 × 10 unlike by gas volume air speed
5h
-1, its result is: when 25 DEG C, formaldehyde conversion 70.6%; When 50 DEG C, formaldehyde conversion 76.3%; When 75 DEG C, formaldehyde conversion 81.3%; When 100 DEG C, formaldehyde conversion 88.2%; When 125 DEG C, formaldehyde conversion 92.6%.
Claims (9)
1. mesoporous carried copper Mn complex oxide catalyst, is characterized in that, comprises following component: active component 10% ~ 25%; Auxiliary agent 5% ~ 20%; Surplus is mesopore oxide is carrier loaded.
2. mesoporous carried copper Mn complex oxide catalyst according to claim 1, is characterized in that, it is characterized in that, described mesopore oxide adopts Al
2o
3, TiO
2or SiO
2.
3. mesoporous carried copper Mn complex oxide catalyst according to claim 1, is characterized in that, described active component is Cu-Mn complex oxide.
4. mesoporous carried copper Mn complex oxide catalyst according to claim 1, is characterized in that, described auxiliary agent adopts CeO
2, ZrO
2or La
2o
3.
5. the preparation method of mesoporous carried copper Mn complex oxide catalyst, is characterized in that, comprise the following steps:
1) preparation of mesopore oxide carrier: 1.0 ~ 3.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 10 ~ 30mL absolute ethyl alcohol or distilled water, magnetic agitation 1 ~ 3h, instillation 2.0 ~ 4.0mL hydrochloric acid or nitric acid, continue stirring 10 ~ 30min, then the one in 2.0 ~ 6.0g aluminium isopropoxide, butyl titanate or ethyl orthosilicate is added, stir 4 ~ 6h, dry 6 ~ 12h in 40 ~ 80 DEG C of baking ovens, in Muffle furnace, 400 ~ 600 DEG C of roasting 4 ~ 6h, obtain mesopore oxide carrier A l
2o
3, TiO
2or SiO
2;
2) load of active component and auxiliary agent: be that copper nitrate and 50% manganese nitrate aqueous solution of 1:1 ~ 1:5 joins in the distilled water of 50 ~ 150mL by molar ratio, then the one in the cerous nitrate of 0.1262 ~ 0.5046g, 0.1742 ~ 0.6968g zirconium nitrate or 0.0664 ~ 0.2658g lanthanum nitrate is added, be made into mixed solution, drop into mesopore oxide carrier A l subsequently
2o
3, TiO
2or SiO
2, stir 4 ~ 8h in 30 ~ 60 DEG C of waters bath with thermostatic control, dry 6 ~ 12h at 90 ~ 120 DEG C, 400 ~ 600 DEG C of roasting 3 ~ 6h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst.
6. the preparation method of mesoporous carried copper Mn complex oxide catalyst according to claim 5, is characterized in that, comprise the following steps:
1) mesoporous Al
2o
31.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 10mL absolute ethyl alcohol by the preparation of carrier, magnetic agitation 1h, instillation 2.0mL nitric acid, continue to stir 10min, then add 3.0g aluminium isopropoxide, stir 4h, dry 10h in 60 DEG C of baking ovens, in Muffle furnace, 600 DEG C of roasting 4h, obtain mesoporous Al
2o
3carrier;
2) molar ratio is that the copper nitrate of 1:3 and 50% manganese nitrate aqueous solution join in the distilled water of 100mL by the load of active component and auxiliary agent, then adds the cerous nitrate of 0.1262g, is made into mixed solution, drop into mesopore oxide carrier A l subsequently
2o
3, stir 6h in 50 DEG C of waters bath with thermostatic control, dry 10h at 100 DEG C, 500 DEG C of roasting 4h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst CuMnO
x-CeO
2/ Al
2o
3.
7. the preparation method of mesoporous carried copper Mn complex oxide catalyst according to claim 1, is characterized in that, comprise the following steps:
1) mesoporous TiO
23.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 30mL distilled water by the preparation of carrier, magnetic agitation 3h, instillation 4.0mL hydrochloric acid, continue to stir 30min, then add 6.0g butyl titanate, stir 6h, dry 12h in 40 DEG C of baking ovens, in Muffle furnace, 400 DEG C of roasting 6h, obtain mesoporous TiO
2carrier;
2) molar ratio is that the copper nitrate of 1:3 and 50% manganese nitrate aqueous solution join in the distilled water of 100mL by the load of active component and auxiliary agent, then adds the cerous nitrate of 0.1262g, is made into mixed solution, drop into mesopore oxide carrier A l subsequently
2o
3, stir 6h in 50 DEG C of waters bath with thermostatic control, dry 10h at 100 DEG C, 500 DEG C of roasting 4h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst CuMnO
x-CeO
2/ TiO
2.
8. the preparation method of mesoporous carried copper Mn complex oxide catalyst according to claim 1, is characterized in that, comprise the following steps:
1) mesoporous SiO
22.0g non-ionic surfactant polyoxyethylene-polyoxypropylene polyoxyethylene (P123) is dissolved in 20mL absolute ethyl alcohol by the preparation of carrier, magnetic agitation 2h, instillation 3.0mL hydrochloric acid, continue to stir 30min, then add 2.0g ethyl orthosilicate, stir 5h, dry 6h in 80 DEG C of baking ovens, in Muffle furnace, 500 DEG C of roasting 5h, obtain mesoporous SiO
2carrier;
2) load of active component and auxiliary agent, is that copper nitrate and 50% manganese nitrate aqueous solution of 1:3 joins in the distilled water of 100mL by molar ratio, then adds the cerous nitrate of 0.1262g, be made into mixed solution, drops into mesopore oxide carrier A l subsequently
2o
3, stir 6h in 50 DEG C of waters bath with thermostatic control, dry 10h at 100 DEG C, 500 DEG C of roasting 4h in Muffle furnace, obtain mesoporous carried copper Mn complex oxide catalyst CuMnO
x-CeO
2/ SiO
2.
9. by the method for mesoporous carried copper Mn complex oxide catalyst catalyze oxidation of formaldehyde, it is characterized in that, catalytic oxidation performance evaluation is carried out in miniature fixed bed continuous-flow reaction system, comprises the following steps:
1) take 200mg, 40 ~ 60 object catalyst with etc. the quartz sand of particle diameter mix, load the hard glass pipe reactor that internal diameter is 10cm;
2) gaseous formaldehyde produces by N
2gas flow purging is placed in the paraformaldehyde of thermostat, then with primary air 20%O
2/ N
2mixing;
3) concentration of formaldehyde is controlled by the weight of paraformaldehyde and the flow velocity of thermostat and carrier gas, obtains consisting of of unstripped gas: 100 ~ 900ppm formaldehyde, the O of 20%
2/ N
2;
4) reactor outlet gas GC1690 type gas chromatographic analysis, chromatogram configuration TCD and fid detector, assemble a nickel converter in front of the detector;
5) this catalyst at ambient pressure gas volume air speed be 3 × 10
3~ 3 × 10
5h
-1time, reaction temperature is under the condition of 25 ~ 125 DEG C, can be CO by formaldehyde complete catalysts oxidation
2and H
2o.
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