CN106540754B - A kind of catalyst for catalytic combustion and its preparation method and application - Google Patents
A kind of catalyst for catalytic combustion and its preparation method and application Download PDFInfo
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- CN106540754B CN106540754B CN201510598906.2A CN201510598906A CN106540754B CN 106540754 B CN106540754 B CN 106540754B CN 201510598906 A CN201510598906 A CN 201510598906A CN 106540754 B CN106540754 B CN 106540754B
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Abstract
The present invention relates to a kind of catalyst for catalytic combustion and its preparation method and application.The catalyst is made of ceramic fibre carrier with coating and active component.In the catalyst, ceramic fibre carrier with coating before being coated through peracid treatment and hydro-thermal process.The coating of catalyst is the combination or carbon nanotube of one or more kinds of metal oxides, and coating and active component are loaded using infusion process.Catalyst of the invention has the characteristics that secured coating, noble metal active component utilization rate height, good hydrothermal stability, high temperature resistant, preparation method are simple.The catalyst for catalytic combustion can be used for methane catalytic combustion process or other hydrocarbons and VOC, H2, CO gas catalysis burn subtractive process.
Description
Technical field
The invention belongs to catalyst for catalytic combustion fields, and in particular to a kind of catalyst for catalytic combustion and preparation method thereof and
Using the catalyst is in using energy source and environmental protection technology.
Background technique
Catalysis burning is to carry out non-flaming combustion under low light-off temperature by catalyst, and the oxidations such as organic exhaust gas are divided
Solution is the technology of carbon dioxide and water.The essence of catalysis burning is the violent oxidation reaction that active oxygen participates in, catalyst activity
When activating oxygen molecule is contacted with reactant molecule energy transmission is occurred for air oxygen activation by component, and reactant molecule is activated,
To the progress of accelerated oxidation reaction.Catalysis burning is with initiation temperature is low, purification efficiency is high, it is big etc. excellent to adapt to oxygen ranges
Gesture, the common concern in terms of VOCs treatment, energy regenerating utilization and power generation by people.
The core of catalytic combustion technology is the suitable catalyst of selection.Since catalysis ignition temperature is higher, combustion reaction
The a large amount of water vapours of Cheng Shengcheng, and there are a small amount of impurity chlorine and sulphur, therefore catalytic combustion technology is very high to catalyst requirement, need to urge
Agent has that low temperature active is good, high-temperature stability is high, large specific surface area, active component high degree of dispersion, anti-sintering and anti-chlorine and sulphur
Poisoning capability.In practical applications, the active component of combustion catalyst is the noble metal and transition metal based on Pd, Pt etc.
Oxide and rare earth oxide etc..It the use of more carrier material is γ-Al2O3、α-Al2O3, molecular sieve, silica gel, cordierite
Deng they are mostly spherical shape, cylindrical body, bar shaped, irregular particle and annular etc..Novel catalyst carrier is selected, catalysis is improved
The hydrothermal stability of agent is still the hot spot of research.
Ceramic fibre is a kind of fibrous light refractory material, has that light-weight, high temperature resistant, thermal stability be good, thermal conductivity
The advantages that low, specific heat is small and mechanical resistant shakes, thus the industries such as machinery, metallurgy, chemical industry, petroleum, ceramics, glass, electronics all
The thermal shock resistance and mechanical flexibility for being widely used catalytic ceramic fibre are better than ceramic honeycomb carrier material
Material, and can be formed according to the shape of reactor to meet different needs.The diffusional resistance very little of ceramic fibre catalyst, for expanding
The reaction of control is dissipated, fiber catalyst has high efficiency than granular catalyst.Both at home and abroad for substituting violet with ceramic fibre
Green stone expands research as catalyst carrier for purifying vehicle tail gas, and shows splendid catalytic performance and hydrothermally stable
Property.But it is in the application in combustion catalyst field, there is not yet report.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst for catalytic combustion and preparation method thereof.
Another object of the present invention is to be used for catalyst combustion reaction for ceramic fibre as carrier.
The catalyst includes treated ceramic fibre carrier, coating and noble metal active component, and the coating is gold
Belong to oxide or carbon nanotube.
The ceramic fibre can be commercially available ceramic fiber cloth, felt, paper, can be needed to be processed into required shape according to reaction
Shape, it is 1cm that ceramic fibre carrier, which is rolled into diameter, in embodiments of the present invention, is highly the cylindric of 0.5cm, it is anti-to be put into fixed bed
It answers in device and is evaluated.
Metal oxide is one or more of aluminium, cerium, zirconium, manganese, cobalt, the metal oxide of titanium, preferred gold
Category oxide is MnO2、Co3O4、ZrO2.Coating of metal oxides load capacity be 2~50wt%, preferably 10~30%.Your gold
Category active component is one or more of palladium, platinum, rhodium, iridium, ruthenium, and load capacity is 0.1~5wt%, preferred load capacity
0.2~2wt%.
The preparation method of the catalyst for catalytic combustion handles ceramic fibre carrier the following steps are included: (1) is sour, will be ceramic
Fiber carrier, which is put into acid solution, to be impregnated, dry after being washed repeatedly with deionized water to neutrality；(2) hydro-thermal process ceramic fibre carries
Body, it is dry after ceramic fibre carrier is handled in hydro-thermal atmosphere；(3) load of coating use infusion process, will treated pottery
Porcelain fiber carrier is put into one or more of aluminium, cerium, zirconium, manganese, cobalt, vanadium, titanium, tungsten metal oxide or carbon nanotube
Slurry in impregnate after, then in 80~150 DEG C of dry 6~48h, finally in 400~1200 DEG C of 1~6h of roasting, preferably dry
Temperature is 100~120 DEG C, and preferred maturing temperature is 500~800 DEG C.Painting can be controlled by the solid content of modulation slurry
The load capacity of layer, the slurry after metal oxide or carbon nanotube and deionized water mixing and ball milling by forming；(4) supported active
Component supports noble metal active component equally by the way of excessively impregnating, will load the ceramic fibre of coating palladium, platinum,
It is impregnated in one or more of rhodium, iridium, ruthenium precursor solution, and drying and roasting, drying temperature is 30~150 DEG C, is done
The dry time is 6~48h, and finally in 200~600 DEG C of 1~6h of roasting, preferred drying temperature is 50~100 DEG C, preferred to roast
Temperature be 250~400 DEG C to get arrive catalyst for catalytic combustion.
(4) presoma described in is preferably one or more of the villaumite of palladium, platinum, rhodium, iridium, ruthenium.
Sour treatment process is first to handle ceramic fibre carrier in 1%~65% nitric/sulfuric acid/phosphoric acid/hydrochloric acid
0.5~48h obtains deimpurity ceramic fibre carrier using processes such as washing dryings.
Hydrothermal treatment process is temperature of the ceramic fibre carrier at 150~700 DEG C, the gas of 0.5%~30% water vapour
After handling 0.5~48h in atmosphere, it is dried to obtain the ceramic fibre carrier with good hydrothermal stability, when processing, preferable temperature model
Enclosing is 200~500 DEG C, and the preferred mass fraction of water vapour is 4%~20%.
It is provided by the invention using ceramic fibre as the combustion catalyst of carrier be used equally for methane catalytic combustion process or its
His hydrocarbon and VOC, H2, the gases such as CO catalysis burn subtractive process.
It is provided by the invention need to be in H before use by the combustion catalyst of carrier of ceramic fibre2-N2It is passed through in mixed airflow
200~500 DEG C of 1~4h of pretreatment, or with 2% hydrazine hydrate solution reductase 12 4h.
Catalyst for catalytic combustion provided by the invention compared with prior art, advantage and technical effect are as follows:
Catalyst of the invention secured, noble metal active component utilization rate height, good hydrothermal stability, resistance to height with coating
Temperature, the features such as preparation method is simple, coating not only with carrier firm connection, increase carrier specific surface area, improve active component point
Divergence also acts as the effect for helping active component.
Catalyst is first handled before the use with acid and hydro-thermal method to improve catalyst using ceramic fibre as carrier
Hydrothermal stability allow catalyst to form various shapes due to the individual elastic property and heat-resistant impact property of ceramic fibre
Shape and have good hydrothermal stability.
Detailed description of the invention
Fig. 1 is the microscope photograph of ceramic fibre carrier.
Fig. 2 is the microscope photograph after the carrier loaded 30wt% coating of ceramic fibre.
Specific embodiment
Unless otherwise noted, all numbers occurred in description of the invention and claims, such as active component,
The numerical value such as maturing temperature and time, gas conversions are not construed as absolute exact value, which is in the art
Those of ordinary skill understood, in the permitted error range of well-known technique.Although being exerted in the example that the present invention provides
Power accomplishes to guarantee the accuracy of numerical value, but due to the standard deviation of various measuring techniques, any obtained numerical value that measures all can not
Avoid there are certain errors.Above content is further described with several embodiments again below.It should be noted that these
Embodiment does not make the restriction in all senses to above content.
The ceramic fibre that the present invention uses is commercially available ceramic fiber cloth, can be needed to be processed into required shape according to reaction
Shape, it is 1cm that ceramic fibre carrier, which is rolled into diameter, in embodiments of the present invention, is highly the cylindric of 0.5cm, it is anti-to be put into fixed bed
It answers in device and is evaluated.
Embodiment 1: ceramic fibre carrier 12 h is handled in 25% nitric acid, is washed out drying.Again in 5% steam
Under air atmosphere, for 24 hours, removal impurity is obtained after dry, and there is 500 DEG C of hydro-thermal process the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in TiO2And ZrO2Molar ratio is to use compressed air in the mixed slurry of 2:1
Purging is to remove extra slurry, after 150 DEG C of dry 7h, 800 DEG C of roasting 2h, and the load of coating in ceramic fibre catalyst carrier
Amount is 10wt%.Configuration concentration is the H of 6mgPt/ml2PtCl6With the PdCl of 6mgPd/ml2Mixed solution is as active group sub-dip
The ceramic fibre carrier for being coated with titanium oxide and zirconium oxide is put into after impregnating in activity component impregnation liquid and takes out, with pressure by stain liquid
Contracting air blows away residual solution in hole, then 80 DEG C of dry 10h in an oven, and 400 DEG C of roasting 5h in air obtain noble metal
Content is the catalyst for catalytic combustion of 0.4wt%.
Embodiment 2: ceramic fibre carrier is handled for 24 hours in 5% sulfuric acid, is washed out drying.Again in 10% steam
Under air atmosphere, 700 DEG C of hydro-thermal process 8h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in CeO2And MnO2Molar ratio is to use compressed air in the mixed slurry of 8:1
Purging is to remove extra slurry, and after 100 DEG C of dry 18h, 600 DEG C of roasting 2h, coating is born in ceramic fibre catalyst carrier
Carrying capacity is 20wt%.Configuration concentration is the H of 3mgPt/ml2PtCl6Solution will be coated with cerium oxide as activity component impregnation liquid
With the ceramic fibre carrier of manganese oxide be put into activity component impregnation liquid impregnate after take out, blown away with compressed air remained in hole it is molten
Liquid, then 50 DEG C of dry 20h in an oven, 500 DEG C of roasting 2h in air, obtaining active component content is urging for 0.1wt%
Change combustion catalyst.
Embodiment 3: ceramic fibre carrier 20h is handled in 3% hydrochloric acid, is washed out drying.Again in 30% steam
Under air atmosphere, 400 DEG C of hydro-thermal process 2h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in Al2O3And Co3O4Molar ratio is in the mixed slurry of 5:1, with compression sky
Air-blowing is swept to remove extra slurry, after 120 DEG C of dry 20h, 700 DEG C of roasting 2h, and coating in ceramic fibre catalyst carrier
Load capacity are as follows: 8wt%.Configuration concentration is the RuCl of 60mgRu/ml2Mixed solution will be coated with as activity component impregnation liquid
The ceramic fibre carrier of aluminium oxide and cobalt oxide is put into activity component impregnation liquid and takes out after dipping, is blown away in hole with compressed air
Residual solution, then for 24 hours, 600 DEG C of roasting 3h in air, obtaining bullion content is 2wt%'s for 120 DEG C of dryings in an oven
Catalyst for catalytic combustion.
Embodiment 4: ceramic fibre carrier 0.5h is handled in 10% phosphoric acid, is washed out drying.Again in 9% steam
Under air atmosphere, 200 DEG C of hydro-thermal process 5h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in TiO2And CeO2Molar ratio is to use compressed air in the mixed slurry of 4:1
Purging is to remove extra slurry, after 90 DEG C of dry 15h, 600 DEG C of roasting 4h, and the load of coating in ceramic fibre catalyst carrier
Amount is 30wt%.Configuration concentration is the H of 12mgPt/ml2PtCl6With the RhCl of 12mgRh/ml2Mixed solution is as active component
The ceramic fibre carrier for being coated with titanium oxide and cerium oxide is put into after impregnating in activity component impregnation liquid and takes out, uses by maceration extract
Compressed air blows away residual solution in hole, then 150 DEG C of dry 10h in an oven, and 250 DEG C of roasting 1h in air are obtained expensive
Tenor is the catalyst for catalytic combustion of 0.8wt%.
Embodiment 5: ceramic fibre carrier 1h is handled in 30% sulfuric acid, is washed out drying.Again in 0.5% steam
Under air atmosphere, 150 DEG C of hydro-thermal process 48h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in Al2O3、MnO2And ZrO2Molar ratio is to use in the mixed slurry of 1:1:5
Compressed air purging is to remove extra slurry, after 100 DEG C of dry 12h, 500 DEG C of roasting 3h, in ceramic fibre catalyst carrier
The load capacity of coating is 5wt%.Configuration concentration is the H of 100mgPt/ml2PtCl6With the RuCl of 50mgRu/ml2Mixed solution is made
For activity component impregnation liquid, the ceramic fibre carrier for being coated with aluminium oxide, manganese oxide and zirconium oxide is put into activity component impregnation
It is taken out after being impregnated in liquid, blows away residual solution in hole with compressed air, then 90 DEG C of dry 15h in an oven, 250 DEG C in air
3h is roasted, the catalyst for catalytic combustion that bullion content is 5wt% is obtained.
Embodiment 6: ceramic fibre carrier 0.5h is handled in 60% nitric acid, is washed out drying.Again in 15% steam
Air atmosphere under, 600 DEG C of hydro-thermal process 1h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in ZrO2And Co3O4Molar ratio is in the mixed slurry of 10:1, with compression sky
Air-blowing is swept to remove extra slurry, after 120 DEG C of dry 15h, 700 DEG C of roasting 1h, and coating in ceramic fibre catalyst carrier
Load capacity is 50wt%.Configuration concentration is the H of 6mgPt/ml2PtCl6With the PdCl of 9mgPd/ml2Mixed solution is as active group
Divide maceration extract, the ceramic fibre carrier for being coated with zirconium oxide and cobalt oxide be put into after being impregnated in activity component impregnation liquid and taken out,
Residual solution in hole is blown away with compressed air, then 80 DEG C of dry 10h in an oven, 400 DEG C of roasting 5h in air are obtained expensive
Tenor is the catalyst for catalytic combustion of 0.5wt%.
Embodiment 7: ceramic fibre carrier 48h is handled in 8% sulfuric acid, is washed out drying.Again in 20% steam
Under air atmosphere, 150 DEG C of hydro-thermal process 36h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in Al2O3And Co3O4Molar ratio is in the mixed slurry of 4:1, with compression sky
Air-blowing is swept to remove extra slurry, after 100 DEG C of dry 20h, 400 DEG C of roasting 5h, and coating in ceramic fibre catalyst carrier
Load capacity is 5wt%.Configuration concentration is the PdCl of 40mgPd/ml2Solution will be coated with aluminium oxide as activity component impregnation liquid
With the ceramic fibre carrier of cobalt oxide be put into activity component impregnation liquid impregnate after take out, blown away with compressed air remained in hole it is molten
Liquid, then 80 DEG C of dry 12h in an oven, 600 DEG C of roasting 1h in air, obtaining active component content is urging for 1.3wt%
Change combustion catalyst.
Embodiment 8: ceramic fibre carrier 30 as one kind h is handled in 20% phosphoric acid, is washed out drying.Again in 8% steam
Under air atmosphere, 400 DEG C of hydro-thermal process 16h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in carbon nano tube paste, extra slurry is removed with compressed air purging
Material, after 110 DEG C of drying for 24 hours, 300 DEG C of roasting 2h, the load capacity of coating is 7wt% in ceramic fibre catalyst carrier.It configures dense
Degree is the PdCl of 19mgPd/ml2With the RhCl of 2mgRh/ml2Mixed solution will be coated with carbon nanometer as activity component impregnation liquid
The ceramic fibre carrier of pipe is put into activity component impregnation liquid and takes out after dipping, blows away residual solution in hole with compressed air, so
80 DEG C of dry 20h in an oven afterwards, 200 DEG C of roasting 4h in air, obtain the catalysis that active component content is 0.7wt% and burn
Catalyst.
Embodiment 9: ceramic fibre carrier 32h is handled in 10% nitric acid, is washed out drying.Again in 9% steam
Under air atmosphere, 300 DEG C of hydro-thermal process 10h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in Al2O3And ZrO2Molar ratio is to use compressed air in the mixed slurry of 2:3
Purging is to remove extra slurry, and after 120 DEG C of dry 12h, 400 DEG C of roasting 3h, coating is born in ceramic fibre catalyst carrier
Carrying capacity is 15wt%.Configuration concentration is the PdCl of 18mgPd/ml2The RuCl of solution and 15mgRu/ml2As activity component impregnation
The ceramic fibre carrier for being coated with aluminium oxide and zirconium oxide is put into after impregnating in activity component impregnation liquid and takes out, with compression by liquid
Air blows away residual solution in hole, then 80 DEG C of dry 18h in an oven, and 550 DEG C of roasting 5h in air obtain active component
Content is the catalyst for catalytic combustion of 1.1wt%.
Embodiment 10: ceramic fibre carrier 6h is handled in 15% hydrochloric acid, is washed out drying.Again in 30% steam
Under air atmosphere, 200 DEG C of hydro-thermal process 5h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in TiO2And CeO2Molar ratio is to use compressed air in the mixed slurry of 5:1
Purging is to remove extra slurry, after 150 DEG C of dry 8h, 450 DEG C of roasting 3h, and the load of coating in ceramic fibre catalyst carrier
Amount is 18wt%.Configuration concentration is the PdCl of 3mgPd/ml2With the PtCl of 21mgPt/ml2Solution as activity component impregnation liquid,
The ceramic fibre carrier for being coated with titanium oxide and cerium oxide is put into after being impregnated in activity component impregnation liquid and is taken out, uses compressed air
Residual solution in hole is blown away, then 80 DEG C of dry 12h in an oven, 600 DEG C of roasting 1h in air obtain active component content
For the catalyst for catalytic combustion of 0.8wt%.
Embodiment 11: ceramic fibre carrier 3h is handled in 12% hydrochloric acid, is washed out drying.Again in 10% steam
Under air atmosphere, 350 DEG C of hydro-thermal process 6h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in MnO2And Co3O4Molar ratio is to use compressed air in the mixed slurry of 1:1
Purging is to remove extra slurry, and after 110 DEG C of dry 12h, 350 DEG C of roasting 4h, coating is born in ceramic fibre catalyst carrier
Carrying capacity is 20wt%.Configuration concentration is the PtCl of 20mgPd/ml2With the RuCl of 40mgRu/ml2Solution is as activity component impregnation
The ceramic fibre carrier for being coated with manganese oxide and cobalt oxide is put into after impregnating in activity component impregnation liquid and takes out, with compression by liquid
Air blows away residual solution in hole, then 100 DEG C of dry 18h in an oven, and 600 DEG C of roasting 2h in air obtain active group
Dividing content is the catalyst for catalytic combustion of 2wt%.
Embodiment 12: ceramic fibre carrier 40h is handled in 5% phosphoric acid, is washed out drying.Again in 30% steam
Under air atmosphere, 500 DEG C of hydro-thermal process 3h, removal impurity is obtained after dry, and there is the ceramic fibre of good hydrothermal stability to carry
Body.By 1g treated ceramic fibre carrier impregnation in Al2O3And TiO2Molar ratio is to use compressed air in the mixed slurry of 1:3
Purging is to remove extra slurry, after 80 DEG C of dryings for 24 hours, 500 DEG C of roasting 2h, and the load of coating in ceramic fibre catalyst carrier
Amount is 18wt%.Configuration concentration is the PdCl of 9mgPd/ml2Solution will be coated with aluminium oxide and oxygen as activity component impregnation liquid
The ceramic fibre carrier for changing titanium is put into activity component impregnation liquid to be taken out after dipping, blows away residual solution in hole with compressed air,
Then 80 DEG C of dry 12h in an oven, 600 DEG C of roasting 2h in air, obtain the catalysis that active component content is 0.3wt% and fire
Burn catalyst.
Comparative example 1: 1g cordierite honeycomb ceramic carrier is immersed in CeO2And MnO2Molar ratio be 8:1 mixed slurry in,
Remove extra slurry with compressed air purging, after 150 DEG C of dry 7h, 800 DEG C of roasting 2h, iolite honeycomb ceramic catalyst
The load capacity of coating is 20wt% on carrier.Configuration concentration is the H of 15mgPt/ml2PtCl6Solution as activity component impregnation liquid,
The cordierite honeycomb ceramic carrier for being coated with cerium oxide and manganese oxide is put into after being impregnated in activity component impregnation liquid and is taken out, with pressure
Contracting air blows away residual solution in hole, then 50 DEG C of dry 20h in an oven, and 500 DEG C of roasting 2h in air obtain active group
The cordierite honeycomb ceramic that point content is 0.5wt% is the catalyst for catalytic combustion of carrier.
Comparative example 2: by 1g, treated that cordierite honeycomb ceramic carrier is immersed in Al2O3And Co3O4Molar ratio is 4:1's
In mixed slurry, extra slurry is removed with compressed air purging, after 100 DEG C of dry 20h, 400 DEG C of roasting 5h, cordierite bee
The load capacity of coating is 5wt% on nest ceramic monolith.Configuration concentration is the PdCl of 40mgPd/ml2Solution is as active group sub-dip
The ceramic fibre carrier for being coated with aluminium oxide and cobalt oxide is put into after impregnating in activity component impregnation liquid and takes out, with pressure by stain liquid
Contracting air blows away residual solution in hole, then 80 DEG C of dry 12h in an oven, and 600 DEG C of roasting 1h in air obtain active group
Point content is 3wt% using cordierite honeycomb ceramic as the catalyst for catalytic combustion of carrier.
By Catalyst packing prepared by the above embodiment of the present invention 1-6 and comparative example 1 in fixed-bed catalytic combustion reaction
In device, the loadings of catalyst are 0.5g, and catalyst need to be in 10%H before use2-N2It is pre- through 200~500 DEG C in mixed airflow
1~4h is handled, or with 2% hydrazine hydrate solution reductase 12 4h.CO content is 0.02%, CO in inlet gas2Content is 6%, Air
Content is 10%, H2O steam content 9%, SO2Content is 20ppm, N2As Balance Air, gas space velocity 110,000h- 1.?
Reaction temperature is the initial activity of catalyst to be investigated within the scope of 0-200 DEG C and in 200 DEG C of hydrothermal stability (t=50h).Knot
Fruit is shown in Table 1, from the experimental data in table it can be found that embodiment 1-6 is mobile to low temperature direction compared with the activity curve of comparative example 1,
And compared to 1 embodiment of comparative example have good hydrothermal stability, react 50h after CO conversion ratio still 90% or more, and
The conversion ratio of CO after 10h of comparative example 1 begins to continue to decline, and 60% or so is just dropped to after 50h.
1 catalyst removal CO performance table of table
| Embodiment | T10/℃ | T50/℃ | T90/℃ | T=50h/% |
| 1 | 92.6 | 110.3 | 133.7 | 100 |
| 2 | 91.5 | 117.2 | 138.5 | 93 |
| 3 | 81.8 | 103.8 | 110.7 | 91 |
| 4 | 78.3 | 93.4 | 120.3 | 97 |
| 5 | 88.2 | 105.3 | 111.5 | 100 |
| 6 | 95.4 | 118.1 | 127.8 | 90 |
| Comparative example 1 | 97.8 | 125.3 | 148.5 | 62 |
By Catalyst packing prepared by the above embodiment of the present invention 7-12 and comparative example 2 in fixed-bed catalytic combustion reaction
In device, it is passed through simulation coalmine ventilation device in Gas, the loadings of catalyst are 0.5g, and catalyst need to be in 10%H before use2-N2It is mixed
It closes in air-flow through 200~500 DEG C of 1~4h of pretreatment, or with 2% hydrazine hydrate solution reductase 12 4h.Methane content is in inlet gas
0.2%, HCl 10ppm, remaining is air, gas space velocity 20000h- 1.It is to be investigated within the scope of 0-500 DEG C in reaction temperature
The initial activity of catalyst reacts the stability of 50h at 500 DEG C, the results are shown in Table 2.Activity data embodiment and comparison in table
Example difference is little, but from the point of view of stability data, and embodiment has good hydrothermal stability and chlorine-resistant property.
By above-mentioned experiment as it can be seen that catalyst for catalytic combustion of the present invention, using ceramic fibre as carrier, in low concentration
CO and CH4It is catalyzed under the experiment condition of burning and the performance of catalyst is evaluated, the results showed that the disclosed catalysis of this patent
Agent not only has excellent catalytic activity and hydrothermal stability, but also has the mithridatisms performances such as good resistant to sulfur/chlorine.
2 catalyst removal CH of table4Performance table
| Embodiment | T10/℃ | T50/℃ | T90/℃ | T=50h/% |
| 7 | 221 | 352 | 465 | >90 |
| 8 | 238 | 362 | 481 | >90 |
| 9 | 247 | 371 | 478 | >90 |
| 10 | 253 | 368 | 475 | >90 |
| 11 | 223 | 241 | 458 | >90 |
| 12 | 245 | 381 | 462 | >90 |
| Comparative example 2 | 252 | 377 | 483 | >50 |
Claims (6)
1. a kind of catalyst for catalytic combustion, which is characterized in that the catalyst includes that the ceramics through peracid treatment and hydro-thermal process are fine
Tie up carrier, coating and noble metal active component, the coating is metal oxide or carbon nanotube, coating and noble metal active group
Divide and is loaded on ceramic fibre using infusion process；
For the ceramic fibre carrier when being handled with acid, acid used is nitric acid, sulfuric acid, phosphoric acid, one of hydrochloric acid or two
Kind or more, acid concentration 1%-65%, the processing time is 0.5-48 hours；
The ceramic fibre carrier is in hydro-thermal process, water vapor concentration 0.5%-30%, treatment temperature 150-700
DEG C, the processing time is 0.5-48 hours；
The coating accounts for the 2-50wt% of total catalyst weight, and noble metal active component accounts for the 0.1-5wt% of total catalyst weight；
The metal oxide is one or more of aluminium, cerium, zirconium, manganese, cobalt, the metal oxide of titanium, and noble metal is living
Property group is divided into one or more of palladium, platinum, rhodium, iridium, ruthenium.
2. the preparation method of catalyst for catalytic combustion described in a kind of claim 1, method includes the following steps: the processing of (1) acid
Ceramic fibre carrier is put into acid solution and impregnates by ceramic fibre carrier, dry after being washed repeatedly with deionized water to neutrality；
(2) hydro-thermal process ceramic fibre carrier, it is dry after ceramic fibre carrier is handled in hydro-thermal atmosphere；(3) coating is loaded, will be located
Ceramic fibre carrier after reason is put into one or more of aluminium, cerium, zirconium, manganese, cobalt, titanium metal oxide or carbon nanometer
Re-dry roasts after impregnating in the slurry of pipe, after the slurry is by metal oxide or carbon nanotube and deionized water mixing and ball milling
Composition；(4) load active component will load the ceramic fibre of coating in one or more of palladium, platinum, rhodium, iridium, ruthenium
It is impregnated in precursor solution, and drying and roasting obtains catalyst for catalytic combustion.
3. preparation method as claimed in claim 2, which is characterized in that (3) drying temperature in is 80-150 DEG C, drying time
For 6-48h, maturing temperature is 400-1200 DEG C, calcining time 1-6h；(4) drying temperature is 30-150 DEG C in, drying time
For 6-48h, maturing temperature is 200~600 DEG C, calcining time 1-6h.
4. catalyst for catalytic combustion as described in claim 1 is in methane catalytic combustion process or other hydrocarbons and H2、CO
Application in gas catalytic combustion subtractive process.
5. application as claimed in claim 4, which is characterized in that for the reaction condition during methane catalytic combustion are as follows: enter
Methane content is 0.2~1%, 0~30ppm of chloride content in gas, remaining is air, gas space velocity is 5000~
40000h- 1, reaction temperature is within the scope of 0~600 DEG C；For the reaction condition in catalyzing carbon monoxide combustion process are as follows: entrance
CO content is 0.005~0.5%, CO in gas2Content is that 0~10%, Air content is 5~20%, H2O steam content be 0~
15%, sulfide content is 0~30ppm, N2As Balance Air, gas space velocity is 20000~200,000h- 1, reaction temperature 0
Within the scope of~300 DEG C.
6. application as claimed in claim 5, which is characterized in that need to be in 10%H before use2-N2In mixed airflow through 200~
500 DEG C of 1~4h of pretreatment, or with 2% hydrazine hydrate solution reductase 12 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598906.2A CN106540754B (en) | 2015-09-18 | 2015-09-18 | A kind of catalyst for catalytic combustion and its preparation method and application |
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| CN116713006A (en) * | 2023-06-05 | 2023-09-08 | 郑州大学 | Pt/MnCo 2 O 4 Preparation method and application of foam nickel composite material |
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