CN109939689A - A kind of Rare Earth Mine monolithic catalyst, preparation method and applications - Google Patents
A kind of Rare Earth Mine monolithic catalyst, preparation method and applications Download PDFInfo
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- CN109939689A CN109939689A CN201910325369.2A CN201910325369A CN109939689A CN 109939689 A CN109939689 A CN 109939689A CN 201910325369 A CN201910325369 A CN 201910325369A CN 109939689 A CN109939689 A CN 109939689A
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Abstract
The invention discloses a kind of Rare Earth Mine monolithic catalysts, have multilayered structure, which includes carrier, load coating, auxiliary agent, active component；Wherein: the carrier is rare-earth tailing foamed ceramics, and the load coating is Al2O3Coating, the auxiliary agent are CeO2、ZrO2、La2O3、Y2O3、TiO2、SiO2One or more of combination, the active component be First Transition system Ni metal, Mn, Fe, Co, Ni, Zn or one or more of precious metals pd, Au, Pt, Rh, Ru, Ir combination.Preparation method and its application is also disclosed.This catalyst can be applied to low-concentration methane catalysis burning in ventilation air gas, it can also be used for the efficient removal of NOx in other VOC gas and vehicle exhaust, a feasible approach is provided for Bayan Obo rare-earth tailing secondary resource green recycling, while also achieving the purpose that energy conservation and environmental protection.
Description
Technical field
The present invention relates to environmental protections and solid waste secondary recovery to utilize technical field, and in particular to a kind of Rare Earth Mine
Monolithic catalyst, preparation method and and its application.
Background technique
Low-concentration methane is that main flammable organic component, direct emission can not only be further exacerbated by atmosphere in coal bed gas
The greenhouse effects of environment, and it is serious when will cause the generation of great mine disaster.The methane number for being discharged into atmosphere every year is huge, passes through
Not only required temperature height can also can generate NOx and CO because of incomplete combustion for flame combustion processing；Methane is released in the form of visible light
Exoergic amount, to reduce capacity usage ratio.Currently, low-concentration methane using major way be to be carried out catalysis burning.
To solve the problems such as treating capacity is big, thermal discharge is big, pressure drop is low in industry, it usually needs integral catalyst is used,
I.e. by the way that the monolith support (cordierite honeycomb ceramic, foamed metal structures) of certain shapes is loaded auxiliary agent coating by infusion process
Catalyst is made with active coating, one kind is that noble metal (palladium, platinum etc.) is coated to entirety as active component in the prior art
Above catalyst matrix.The advantages of such catalyst is active high, but poor heat resistance, easy-sintering and expensive, is unfavorable for reality
It now industrializes, another kind of is that transition metal oxide is loaded to monolithic catalyst substrates, such as manganese, copper, cobalt, although should
The activity of class catalyst is slightly below noble metal catalyst, but apparent price and resources advantage receive this kind of catalyst more
Concern.
University Of Science and Technology of the Inner Mongol uses Polymeric sponge method preparation with baiyuneboite (tailing, concentrate etc.) for raw material system
For at foamed ceramics, have preferable catalytic effect (disclosing CN109382085A see Chinese patent) for methane catalytic combustion, most
T under good operating condition10And T90Respectively can be up to 477 DEG C and 715 DEG C, though still having gap with industrialized target is realized, it is mechanical strong
Degree is higher, thermal stability is good, specific surface area is larger, but does not find the record that catalyst is prepared using it as carrier.
Summary of the invention
The object of the present invention is to provide a kind of Rare Earth Mine monolithic catalysts, preparation method and applications, are low concentration first
Alkane burning monolithic catalyst can play reduction reaction temperature for VOC catalysis burning, purifying vehicle exhaust catalysis burning, mention
The effect of high catalytic efficiency.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
A kind of Rare Earth Mine monolithic catalyst, has multilayered structure, which includes carrier, load coating, auxiliary agent, activity
Component；
Wherein: the carrier is rare-earth tailing foamed ceramics, and the load coating is Al2O3Coating, the auxiliary agent are
CeO2、ZrO2、La2O3、Y2O3、TiO2、SiO2One or more of combination, the active component be First Transition system metal
The combination of Cu, Mn, Fe, Co, Ni, Zn or one or more of precious metals pd, Au, Pt, Rh, Ru, Ir.
Further, wherein the Al2O3The load capacity of coating is 1~15wt% of foamed ceramic carrier total weight, preferably
For 3~5wt%.
Further, the auxiliary agent is the 0.1~20wt%, preferably 1~10wt% of total weight of carrier.
Further, the active component (in terms of simple substance) is 0.1~20wt% of entire total catalyst weight, preferably
0.2~10wt%.
Further, the integral catalyst is to be dipped into compound nitre using rare-earth tailing foamed ceramics as carrier
Dry in sour aluminum solutions, roasting finally obtains coating Al2O3Foamed ceramics；The wherein Al2O3Coating is as tie coat
The load of auxiliary agent and active component provides enough specific surface areas.
Further, dry drying temperature be 50~150 DEG C, 0.1~10h of drying time, maturing temperature be 400~
900 DEG C, calcining time is 2~8h.
A kind of specific preparation method of Rare Earth Mine monolithic catalyst is additionally provided, is included the following steps:
(1) preparation of monolithic catalyst support coating: a certain amount of boehmite powder being added in deionized water first,
Appropriate concentrated nitric acid is added dropwise while agitating；80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH of Aluminum sol
Value < 2 to get arrive aluminium oxide slurries coating liquid；
(2) monolithic catalyst support coating load: Rare Earth Mine foamed ceramic carrier is placed in above-mentioned aluminium oxide slurries and is soaked
5~60min of stain is dried after taking-up, is roasted, and coating Al is obtained2O3Collosol coating, this step repeat, until coating load amount
For 1~15wt% of carrier quality, drying temperature is 50~150 DEG C, 0.1~10h of drying time, and maturing temperature is 400~900
DEG C, calcining time is 2~8h；
(3) preparation of auxiliary agent colloidal sol: weighing a certain amount of auxiliary agent solid powder respectively, be dissolved in deionized water, and stirring obtains
To precursor solution, heat preservation is until forming colloidal sol after being heated to 50~120 DEG C；
(4) honeycomb ceramic carrier for having loaded aluminum oxide coating layer the load of auxiliary agent: is placed in the colloidal sol of step (3) preparation
In, dip time is 10~30min, dries, roasts after taking-up, in coating Al2O3Collosol coating surface forms colloidal sol auxiliary agent and applies
Layer, this step repeat, and until 0.1~20wt% that auxiliary agent load capacity is the carrier quality in step (2), drying temperature is
50~180 DEG C, drying time 0.1~for 24 hours, maturing temperature is 200~700 DEG C, and calcining time is 2~8h；
(5) it the dipping of active component: measures a certain amount of active component precursor solution and passes through infusion process supported active group
Point, 24~48h of dip time, 80~120 DEG C of drying temperature, drying time 0.1~2h, 200~500 DEG C of 2~5h of roasting, finally
Monolithic catalyst is made.
Further, it is dilute to include at least Bayan Obo tailing, Bayan Obo concentrate and richness for the rare-earth tailing foamed ceramics
One of unmanufactured iron mine.
Further, auxiliary agent precursor solution is nitrate solution in step (3)；The transition of active component in step (5)
Metal front liquid solution is nitrate solution, and noble metal precursor solution is nitrate solution, Acetate Solution or chlorination salting liquid；
Step (2), (4), the drying mode forced air drying in (5) perhaps micro-wave vacuum baking modes be Muffle furnace roast or
Microwave calcining.
The catalysis that the present invention also provides Rare Earth Mine monolithic catalyst NOx in CO, VOC gas and vehicle exhaust is de-
The application removed.
Compared with prior art, advantageous effects of the invention:
1, catalyst carrier is that Bayan Obo tailing is prepared into porous ceramics by Polymeric sponge method, is belonged to solid
Body waste secondary recovery recycles, and raw material is cheap, simple process, not only can solve environmental issue but also can achieve energy-efficient mesh
's.
2, catalyst is prepared using traditional infusion process, and active component is mainly based on transition metal element, with a small amount of expensive
Metal does not have to, and prepared catalyst has the advantages that morphological rules, high mechanical strength, methane catalytic combustion activity is high.
Detailed description of the invention
The invention will be further described for explanation with reference to the accompanying drawing.
Fig. 1 (a) is the schematic diagram of foamed ceramics monolithic catalyst；(b) pictorial diagram after foamed ceramics Supported CuO；
Fig. 2 is the XRD diffracting spectrum of rare-earth tailing foamed ceramic carrier and loaded copper oxide sample；
Fig. 3 is integral catalyzer A (loaded Cu), the methane catalytic combustion of B (loaded Cu-Pd), C (loaded Cu-Mn) are living
Property test curve；
The scanning electron microscope (SEM) photograph that Fig. 4 (a) and (b) are monolithic catalyst A；
The scanning electron microscope (SEM) photograph of Fig. 5 (a) and (b) monolithic catalyst C.
Specific embodiment
The evaluation method of embodiment 1-5 are as follows:
The methane (one of hydrocarbon or volatile organic compounds except carbon monoxide or methane) of the catalyst is catalyzed burning
Active testing is carried out in micro fixed-bed reactor.The pressure of test is normal pressure, and the group of reaction gas becomes 2%CH4、
18%O2, 80%N2.Catalyst amount 200mg, air speed 48000mL/h/g.Wherein reactor is quartz tube reactor, internal diameter
16mm, high 700mm, underfill quartz sand are fixed.Reaction atmosphere is air, and the measurement of temperature uses two thermocouples, respectively
The temperature of test reactor and catalyst bed.Before sample test, first under the gaseous mixture atmosphere of 50mL/min, with 10 DEG C/
Catalyzer temperature-elevating to 500 DEG C, is kept the temperature 1h, then drops to room temperature in He atmosphere by the heating rate of min.Sample carries out active survey
When examination, heating rate is 5 DEG C/min, and keeps 30min in each temperature spot to be measured.Reactants and products gas-chromatography is online
Analysis, is detected simultaneously using hydrogen flame detector (FID) and thermal conductivity detector (TCD) (TCD), and conversion ratio is defined as the mixing of reaction front and back
The change rate of methane concentration in gas.
Calculation formula:
C0And C1Respectively indicate the concentration of mixing solid/liquid/gas reactions front and back gas.
By monolithic catalyst obtained using the activity rating for carrying out catalyst in above-mentioned fixed-bed quartz reactor, wherein
T10、T50And T90Corresponding temperature respectively indicate conversion ratio reach 10%, 50% and 90% corresponding to temperature.
Main idea according to the present invention and the introduction for combining several prior arts, present inventors appreciate that, in addition to first
Alkane catalysis burning is outer, and catalyst of the invention also can apply to the methyl hydride catalyzed deoxidation of fuel-rich oxygen deprivation operating condition, volatile organic compound
NOx in the catalytic combustion elimination and vehicle exhaust of hydro carbons except the removal of object (VOC), CO catalytic combustion elimination, methane
It eliminates.
Rare Earth Mine foamed ceramics (patent publication No. CN109382085A in the present invention of Polymeric sponge method preparation
Patent of invention) the preparation method is as follows:
Catalyst preparation uses Polymeric sponge method, and experimental raw is dilute using Baotou Bayan Obo Ore District
Additive is added in Tu Kuang in Rare Earth Mine, is prepared into porous foam ceramic.The polyurethane foam that hole count is 20ppi is cut into directly
Diameter is 15mm, and length is the cylindric of 25mm, is then immersed in progress surface in the NaOH solution that mass fraction is 15% and is modified,
Hydrolyze 4h in 60 DEG C of water, clean, dry it is spare；The polyurethane foam dried is immersed in poly-vinyl alcohol solution again, places 6h,
Room temperature dries, is spare again.
By rare-earth tailing planetary ball mill fine grinding 4h, sieving becomes D50For 45 μm of single-size, tailing raw material is taken
65wt%, sodium carboxymethylcellulose 1wt%, neopelex 1wt%, dehydrated alcohol 3wt%, mass fraction are
35% silicon sol solution 30wt% is added deionized water, liquid-solid ratio is made to reach 3:1, is sufficiently mixed and uniformly obtains ceramic slurry.
The polyurethane foam being modified is immersed in ceramic slurry after sufficiently squeezing midge, extra slurry is excluded using glass plate extrusion
Material at room temperature after natural drying, then is placed in air dry oven dry 6h and takes out, by the foamed ceramics precast body in sky
Atmosphere is enclosed to be sintered in lower Muffle furnace.200 DEG C are risen to from room temperature under 5 DEG C/min heating rate first, is then heated up in 2 DEG C/min
500 DEG C are risen under rate and keeps the temperature 60min, then rises to 950 DEG C under 8 DEG C/min heating rate and keeps the temperature 60min, obtain rare earth
Mine foamed ceramics is the carrier of monolithic catalyst.
Embodiment 1
A kind of catalyst of low-temperature catalytic burning integral type, including rare-earth tailing foamed ceramic carrier, catalyst coat Al2O3,
Catalyst promoter CeO2-ZrO2Colloidal sol, active component Cu (in terms of simple substance).Al2O3Collosol coating load capacity is carrier quality
10wt%, CeO2-ZrO2Colloidal sol auxiliary agent load capacity is the 8wt% of carrier quality, and Cu (counts) content as catalyst using simple substance
5wt%.
(1) 10g boehmite powder is added in 280mL deionized water first, appropriate dense nitre is added dropwise while agitating
Acid.80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH value < 2 of Aluminum sol, the aluminium paste liquid finally obtained is i.e.
For carrier coating coating liquid.It is 15mm by diameter, the foamed ceramic carrier that length is 25mm is immersed in aluminium paste liquid, taken after 30min
Out, the raffinate on foamed ceramics is blown off with ear washing bulb；It is put into baking oven, it is 2 hours dry at a temperature of 120 DEG C, 450 in Muffle furnace
DEG C roasting 3h, this step repeats, until the 8wt% that coating load amount is carrier quality.
(2) Ce (NO that cerium zirconium molar ratio is 1: 1 is prepared3)3·6H2O and Zr (NO3)4·5H2O mixed solution, is again heated to
Heat preservation is until forming colloidal sol after 50~120 DEG C.The carrier of Supported alumina coating made from step (1) is placed in sol impregnation
Baking oven is put into after 5min, dry 2h, finally roasts 2h under the conditions of 500 DEG C at a temperature of 120 DEG C.This step repeats, directly
It is 8wt% to auxiliary agent load capacity.
(3) Cu (NO is weighed3)2·3H2O particle is dissolved in deionized water, stirs evenly the solution for being configured to concentration 3mg/mL,
As activity component impregnation liquid, the carrier that step (2) obtains is impregnated in activity component impregnation liquid and is taken out afterwards for 24 hours, with compression
Air blows away residual solution in hole, in an oven 100 DEG C of dryings, and 500 DEG C of roasting 2h of Muffle furnace obtain Cu (in terms of simple substance) and contain
Amount is the monolithic catalyst A of 6wt%.
(4) activity rating that methane catalytic combustion is carried out in fixed-bed quartz reactor, T are loaded on10It is 490 DEG C,
T90It is 677 DEG C, fully achieves the requirement of methane catalytic combustion.
Embodiment 2
A kind of catalyst of low-temperature catalytic burning integral type, including rare-earth tailing foamed ceramic carrier, catalyst coat Al2O3,
Catalyst promoter CeO2-ZrO2Colloidal sol, active component Cu and Pd (in terms of simple substance).Al2O3Collosol coating load capacity is carrier quality
10wt%, CeO2-ZrO2Colloidal sol auxiliary agent load capacity is the 8wt% of carrier quality, and Cu, Pd (count) content as catalyst using simple substance
10wt%.
(1) 10g boehmite powder is added in 280mL deionized water first, appropriate dense nitre is added dropwise while agitating
Acid.80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH value < 2 of Aluminum sol, obtained aluminium paste liquid is to carry
Body coating coating liquid.It is 15mm by diameter, the foamed ceramic carrier that length is 25mm is immersed in aluminium paste liquid, taken out after 30min, uses
Ear washing bulb blows off the raffinate on foamed ceramics；It is put into baking oven, 2 hours dry at a temperature of 120 DEG C, 450 DEG C of Muffle furnace roastings
3h, this step repeat, until the 10wt% that coating load amount is carrier quality.
(2) Ce (NO that cerium zirconium molar ratio is 1: 1 is prepared3)3·6H2O and Zr (NO3)4·5H2O mixed solution, is again heated to
Heat preservation is until forming colloidal sol after 50~120 DEG C.It will be impregnated in the carrier merging colloidal sol of Supported alumina coating made from step (1)
Baking oven is put into after 5min, dry 2h, 500 DEG C of roasting 2h of Muffle furnace at a temperature of 120 DEG C.This step repeats, until auxiliary agent
Load capacity is 8wt%.
(3) Cu (NO is weighed by Cu and Pd molar ratio 5:13)2·3H2O solid and PdCl2Solution is dissolved in deionized water, stirring
It is uniformly configured to the solution of concentration 2mg/mL, as activity component impregnation liquid, the carrier that step (2) is obtained is in active group sub-dip
It impregnates in stain liquid and takes out afterwards for 24 hours, blow away residual solution in hole with compressed air, in an oven 100 DEG C of dryings, 480 DEG C of Muffle furnace
2h is roasted, the monolithic catalyst B that Cu, Pd (in terms of simple substance) total content are 10wt% is obtained.
(4) activity rating that methane catalytic combustion is carried out in fixed-bed quartz reactor, T are loaded on10It is 355 DEG C,
T90It is 648 DEG C, fully achieves the requirement of methane catalytic combustion.
Embodiment 3
A kind of catalyst of low-temperature catalytic burning integral type, including rare-earth tailing foamed ceramic carrier, catalyst coat Al2O3,
Catalyst promoter CeO2-La2O3Colloidal sol, active component Cu, Mn (in terms of simple substance).Al2O3Collosol coating load capacity is carrier quality
10wt%, CeO2-La2O3Colloidal sol auxiliary agent load capacity is the 8wt% of carrier quality, and Cu, Mn (count) content as catalyst using simple substance
6wt%.
(1) 10g boehmite powder is added in 280mL deionized water first, appropriate dense nitre is added dropwise while agitating
Acid.80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH value < 2 of Aluminum sol, obtained aluminium paste liquid is to carry
Body coating coating liquid.It is 15mm by diameter, the foamed ceramic carrier that length is 25mm is immersed in aluminium paste liquid, taken out after 30min, uses
Ear washing bulb blows off the raffinate on foamed ceramics；It is put into baking oven, dry 4h, 500 DEG C of roasting 3h of Muffle furnace at a temperature of 120 DEG C,
This step repeats, until the 10wt% that coating load amount is carrier quality.
(2) Ce (NO that cerium lanthanum molar ratio is 2: 1 is prepared3)3·6H2O and La (NO3)3·6H2O mixed solution is simultaneously heated to
Heat preservation is until forming colloidal sol after 100 DEG C.5min will be impregnated in the carrier merging colloidal sol of Supported alumina coating made from step (1)
After be put into baking oven, dry 2h, 500 DEG C of roasting 2h of Muffle furnace at a temperature of 120 DEG C.This step repeats, until auxiliary agent loads
Amount is 8wt%.
(3) Cu (NO is weighed by Cu and Mn molar ratio 2:13)2·3H2O and Mn (NO3)2·4H2O is dissolved in deionized water, stirs
The solution for being uniformly configured to concentration 5mg/mL is mixed, as activity component impregnation liquid, the carrier that step (2) is obtained is in active component
It impregnates in maceration extract and takes out afterwards for 24 hours, blow away residual solution in hole with compressed air, in an oven 100 DEG C of dryings, Muffle furnace 450
DEG C roasting 3h, obtain Cu, Mn (in terms of simple substance) total content be 6wt% monolithic catalyst C.
(4) activity rating that methane catalytic combustion is carried out in fixed-bed quartz reactor, T are loaded on10It is 472 DEG C,
T90It is 658 DEG C, fully achieves the requirement of methane catalytic combustion.
Embodiment 4
A kind of catalyst of low-temperature catalytic burning integral type, including rare earth ore concentrate foamed ceramic carrier, catalyst coat Al2O3,
Catalyst promoter CeO2-Y2O3Colloidal sol, active component Co, Pd (in terms of simple substance).Al2O3Collosol coating load capacity is carrier quality
10wt%, CeO2-Y2O3Colloidal sol auxiliary agent load capacity is the 8wt% of carrier quality, and Co, Pd (count) content as catalyst using simple substance
8wt%.
(1) 10g boehmite powder is added in 280mL deionized water first, appropriate dense nitre is added dropwise while agitating
Acid.80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH value < 2 of Aluminum sol, obtained aluminium paste liquid is to carry
Body coating coating liquid.It is 15mm by diameter, the foamed ceramic carrier that length is 25mm is immersed in aluminium paste liquid, taken out after 10min, uses
Ear washing bulb blows off the raffinate on foamed ceramics；In an oven dry 0.3h, 500 DEG C of roasting 2h of Muffle furnace, this step repeatedly into
Row, until the 6wt% that coating load amount is carrier quality.
(2) Ce (NO that cerium lanthanum molar ratio is 2: 1 is prepared3)3·6H2O and Y (NO3)3·6H2O mixed solution is simultaneously heated to
Heat preservation is until forming colloidal sol after 100 DEG C.After the carrier of Supported alumina coating made from step (1) is placed in sol impregnation 5min
It is put into baking oven, dry 2h, 500 DEG C of roasting 2h of Muffle furnace at a temperature of 120 DEG C.This step repeats, until auxiliary agent load capacity
For 8wt%.
(3) Co (NO is weighed by Co and Pd molar ratio 4:13)2·6H2O solid and Pd (NO3)2Solution is dissolved in deionized water, molten
In deionized water, the solution for being configured to concentration 10mg/mL is stirred evenly, as activity component impregnation liquid, step (2) is obtained
Carrier impregnates in activity component impregnation liquid to be taken out afterwards for 24 hours, blows away residual solution in hole, drying in baking oven with compressed air
0.5h, 430 DEG C of roasting 2h of Muffle furnace obtain the monolithic catalyst D that Co, Pd (in terms of simple substance) total content are 8wt%.
(4) activity rating that methane catalytic combustion is carried out in fixed-bed quartz reactor, T are loaded on10It is 480 DEG C,
T90It is 710 DEG C, fully achieves the requirement of methane catalytic combustion.
Embodiment 5
A kind of catalyst of low-temperature catalytic burning integral type, including rare-earth tailing foamed ceramic carrier, catalyst coat Al2O3,
Catalyst promoter CeO2-ZrO2Colloidal sol, active component Cu, Mn (in terms of simple substance).Al2O3Collosol coating load capacity is carrier quality
10wt%, CeO2-ZrO2Colloidal sol auxiliary agent load capacity is the 8wt% of carrier quality, and Cu, Mn (count) content as catalyst using simple substance
7wt%.
(1) 10g boehmite powder is added in 280mL deionized water first, appropriate dense nitre is added dropwise while agitating
Acid.80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH value < 2 of Aluminum sol, obtained aluminium paste liquid is to carry
Body coating coating liquid.It is 15mm by diameter, the foamed ceramic carrier that length is 25mm is immersed in aluminium paste liquid, taken out after 30min, uses
Ear washing bulb blows off the raffinate on foamed ceramics；It is put into micro-wave vacuum case, 100 DEG C of dry 0.4h, 500 DEG C of microwave calcinings
1h.This step repeats, until the 10wt% that coating load amount is carrier quality.
(2) Ce (NO that cerium lanthanum molar ratio is 2: 1 is prepared3)3·6H2O and La (NO3)3·6H2O mixed solution is simultaneously heated to
Heat preservation is until forming colloidal sol after 100 DEG C.After the carrier of Supported alumina coating made from step (1) is placed in sol impregnation 5min
It is put into micro-wave vacuum case, microwave drying 1h at a temperature of 120 DEG C, finally in 500 DEG C of microwave calcining 2h.This step repeat into
Row, until auxiliary agent load capacity is 8wt%.
(3) by Cu (NO3)3·3H2O and Mn (NO3)2·4H2O solid particle, is dissolved in deionized water, stirs evenly and is configured to
The solution of concentration 8mg/mL impregnates the carrier that step (2) obtains as activity component impregnation liquid in activity component impregnation liquid
It is taken out after 12h, blows away residual solution in hole with compressed air, microwave drying 0.5h, 480 DEG C of microwave calcining 2h obtain Cu, Mn
(in terms of simple substance) total content is the monolithic catalyst E of 7wt%.
(4) activity rating that methane catalytic combustion is carried out in fixed-bed quartz reactor, T are loaded on10It is 484 DEG C,
T90It is 717 DEG C, fully achieves the requirement of methane catalytic combustion.
It is the schematic diagram of foamed ceramics monolithic catalyst as shown in (a) of Fig. 1, which has multilayered structure, this is urged
Agent includes carrier, coating, auxiliary agent, active component totally four part；It is the pictorial diagram of monolithic catalyst A as shown in (b) of Fig. 1,
The stomata for largely communicating with each other or being closed is formed in material forming and high-temperature sintering process.
As shown in Fig. 2, being XRD diffracting spectrum: wherein (a) is the XRD of monolithic catalyst A, (b) is made pottery for rare-earth tailing foam
The XRD of ceramic carrier；
Main component is CeO in rare-earth tailing foamed ceramic carrier2、CaF2、Fe2O3、SiO2, there is CuO in monolithic catalyst A
The corresponding characteristic peak of (111) and (220) crystal face, the XRD diffraction maximum of remaining diffraction maximum and ceramic monolith is almost the same, illustrates whole
There is no success load active component CuO under conditions of variation in overall structure for body catalyst.
As shown in figure 3, for integral catalyzer A (loaded Cu), B (loaded Cu-Pd), C (loaded Cu-Mn) it is methyl hydride catalyzed
Combustion activity test curve；Catalytic activity: B > C > A
As shown in figure 4, being the scanning electron microscope (SEM) photograph of monolithic catalyst A: wherein (a) amplifies 10000 times, (b) amplifies 20000
Times；As it can be seen that the rodlike two-dimensional structure of prism is presented in skeleton carrier, cross-sectional length is 1-3 μm, and length is 5-10 μm, and spherical substance is
The CuO active component of load.
As shown in figure 5, being the scanning electron microscope (SEM) photograph of monolithic catalyst C: wherein (a) amplifies 10000 times, (b) amplifies 20000
Times.As it can be seen that the rodlike two-dimensional structure of prism is presented in skeleton carrier, cross-sectional length is 1-3 μm, and length is 5-10 μm, petal-shaped substance
For the active component of the CuO-MnO mixture of load.
The catalytic property of sample such as the following table 1:
Table 1
Table 1 lists the T of integral catalyzer A (loaded Cu), B (loaded Cu-Pd), C (loaded Cu-Mn)10、T50And T90Three
A performance indicator.The activity of usual methyl hydride combustion catalyst can be evaluated with these three performance indicators, namely for methane conversion 10%,
Temperature when 50% and 90% uses T respectively10、T50And T90It indicates, conversion temperature is lower, and methane catalytic combustion activity is better.
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, without departing from the spirit of the design of the present invention, those of ordinary skill in the art make technical solution of the present invention
Various changes and improvements, should all fall into claims of the present invention determine protection scope in.
Claims (10)
1. a kind of Rare Earth Mine monolithic catalyst, it is characterised in that: have multilayered structure, the catalyst include carrier, load coating,
Auxiliary agent, active component；
Wherein: the carrier is rare-earth tailing foamed ceramics, and the load coating is Al2O3Coating, the auxiliary agent are CeO2、
ZrO2、La2O3、Y2O3、TiO2、SiO2One or more of combination, the active component be First Transition system Ni metal,
The combination of Mn, Fe, Co, Ni, Zn or one or more of precious metals pd, Au, Pt, Rh, Ru, Ir.
2. Rare Earth Mine monolithic catalyst according to claim 1, it is characterised in that: the wherein Al2O3The load capacity of coating
For 1~15wt% of foamed ceramic carrier total weight.
3. Rare Earth Mine monolithic catalyst according to claim 1, it is characterised in that: the auxiliary agent is total weight of carrier
0.1~20wt%.
4. Rare Earth Mine monolithic catalyst according to claim 1, it is characterised in that: the active component is entire catalyst
0.1~20wt% of total weight.
5. Rare Earth Mine monolithic catalyst according to any one of claims 1-4, which is characterized in that the rare-earth tailing bubble
Foam ceramics are made by including at least one of Bayan Obo tailing, Bayan Obo concentrate and rich rare-earth iron ore.
6. the preparation method of Rare Earth Mine monolithic catalyst according to claim 1, it is characterised in that: the monolithic devices catalysis
Agent is to be dipped into compound aluminum nitrate solution dry, roasting using rare-earth tailing foamed ceramics as carrier, finally obtain coating
Al2O3Foamed ceramics；The Al2O3Coating provides enough specific surfaces as tie coat, for the load of auxiliary agent and active component
Product.
7. preparation method according to claim 6, it is characterised in that: its it is specific the preparation method is as follows:
(1) preparation of monolithic catalyst support coating: a certain amount of boehmite powder is added in deionized water first, is being stirred
Appropriate concentrated nitric acid is added dropwise while mixing；80 DEG C are then heated to, then nitric acid is added dropwise to being completely dissolved, controls the pH value < of Aluminum sol
2 to get arrive aluminium oxide slurries coating liquid；
(2) monolithic catalyst support coating load: by Rare Earth Mine foamed ceramic carrier be placed in above-mentioned aluminium oxide slurries dipping 5~
60min is dried after taking-up, is roasted, and coating Al is obtained2O3Collosol coating, this step repeat, until coating load amount is to carry
1~15wt% of weight, drying temperature are 50~150 DEG C, 0.1~10h of drying time, and maturing temperature is 400~900 DEG C,
Calcining time is 2~8h；
(3) preparation of auxiliary agent colloidal sol: weighing a certain amount of auxiliary agent solid powder respectively, be dissolved in deionized water, stirring, before obtaining
Liquid solution is driven, heat preservation is until forming colloidal sol after being heated to 50~120 DEG C；
(4) load of auxiliary agent: the honeycomb ceramic carrier for having loaded aluminum oxide coating layer being placed in the colloidal sol of step (3) preparation, leaching
The stain time is 10~30min, dries, roasts after taking-up, in coating Al2O3Collosol coating surface forms colloidal sol auxiliary agent coating, this step
Suddenly repeat, until 0.1~20wt% that auxiliary agent load capacity is the carrier quality in step (2), drying temperature is 50~180
DEG C, drying time 0.1~for 24 hours, maturing temperature is 200~700 DEG C, and calcining time is 2~8h；
(5) it the dipping of active component: measures a certain amount of active component precursor solution and passes through infusion process load active component, leaching
24~48h of stain time, it is 80~120 DEG C of drying temperature, drying time 0.1~2h, 200~500 DEG C of 2~5h of roasting, final to be made
Monolithic catalyst.
8. preparation method according to claim 7, which is characterized in that auxiliary agent precursor solution is nitrate in step (3)
Solution；The transition metal precursor solution of active component is nitrate solution in step (5), and noble metal precursor solution is nitrate
Solution, Acetate Solution or chlorination salting liquid；Step (2), (4), the drying mode in (5) are that air dry oven is dry or micro-
Wave vacuum drying, baking modes are Muffle furnace roasting or microwave calcining.
9. Rare Earth Mine monolithic catalyst according to any one of claims 1-4 is in CO, VOC gas and vehicle exhaust
The application of the catalytic eliminating of NOx.
10. Rare Earth Mine monolithic catalyst prepared by the preparation method of according to claim 6 or 7 is in CO, VOC gas and car tail
The application of the catalytic eliminating of NOx in gas.
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