CN106732585A - A kind of VOCs catalytic burning integral types catalyst and preparation method thereof - Google Patents
A kind of VOCs catalytic burning integral types catalyst and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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Abstract
The present invention provides a kind of VOCs catalytic burning integral types catalyst, belongs to catalyst technical field.Catalyst of the present invention with cordierite honeycomb ceramic carrier, with γ Al2O3, oxides additive and active component Pd be coating, the mass fraction of the cordierite honeycomb ceramic carrier is 82~87 parts, the γ Al2O3Mass fraction be 10~14 parts, the mass fraction of the oxides additive is 0.8~1.5 part, and the mass fraction of the active component Pd is 0.01~0.05 part.The invention further relates to the preparation method of the catalyst, Pd is distributed to special γ Al first2O3On carrier, powder is obtained through drying and roasting, then adds bonding agent, lubricant and water being made slurry, be coated on cordierite honeycomb ceramic carrier, drying and roasting obtains catalyst of the present invention.Catalyst of the present invention using low content of noble metal Pd as active component, with low cost, low temperature ignition is rapid, sulfur resistive is anti-aging, adapt to Wind Volume high-speed, scattered not easy-sintering the features such as, be particularly suitable for the catalysis burning treatment of sulfur-bearing VOCs waste gas.
Description
Technical field
The invention belongs to catalyst technical field, specially a kind of VOCs catalytic burning integral types catalyst and its preparation side
Method.
Background technology
Volatile organic matter (VOCs) catalytic combustion technology is because its reaction condition is gentle, oxidation is thorough and need not change group
The advantages of part, recyclable reaction heat, received by increasing enterprise and producer, as the primary hand for the treatment of organic exhaust gas
Section.Contain more sulfide in rubber industry curing fume, oil refining, coking and coal-fired boiler tail gas, wherein having mixed many
Carcinogenic hydro carbons, aromatic hydrocarbons and polycyclic aromatic hydrocarbon PAHs compounds are planted, the more general VOCs treatment of its vent gas treatment is more multiple
Miscellaneous, the easy sulfur poisoning of catalyst, for the organic exhaust gas of this type, is needed using anti-when being processed with catalytic combustion technology
The catalyst of sulphur is improving the service life of activity stability and catalyst.
Catalyst in existing disclosed patent is using various noble metals as active component, including Pt-Pd, Pt-Rh-
Pd etc., but single Pd is not directed to as the sulfur resistance of catalytic reactive component agent, and due to existing load active component
The untreated optimization of surfaces of carrier materials, be still not clear the heat endurance of catalyst.
The content of the invention
It is an object of the invention to provide a kind of single Pd types VOCs catalytic burning integral type catalyst and preparation method thereof, this
Invention catalyst using low content of noble metal Pd as sole active agent, with low cost, low temperature ignition be rapid, sulfur resistive is anti-ageing
Change, adaptation Wind Volume high-speed, noble metal divide the features such as calculating good not easy-sintering, be particularly suitable for the catalysis burning of sulfur-bearing VOCs waste gas
Treatment.The object of the invention is realized by following technical proposals：
A kind of VOCs catalytic burning integral types catalyst, the catalyst is applied with cordierite honeycomb ceramic carrier on carrier
Catalyst coat is covered with, the coating is γ-Al2O3, oxide and active component Pd, the cordierite honeycomb ceramic carrier
Mass fraction is 82~87 parts, the γ-Al2O3Mass fraction be 10~14 parts, the mass fraction of the oxide is 0.8
~1.5 parts, the mass fraction of the active component Pd is 0.01~0.05 part.
Used as an a kind of specific embodiment of VOCs catalytic burning integral types catalyst of the invention, the catalyst is also wrapped
Containing the binding agent that mass fraction is 0.1~0.3 part, the binding agent be one kind in diaspore, colloidal sol, aluminium glue, Ludox or
It is several.
Used as a kind of one specific embodiment of VOCs catalytic burning integral types catalyst of the invention, the oxide is Ce-
Zr-La-Ba composite oxides, its mol ratio is CeO2：ZrO2：La2O3：BaO=(0.1~1)：(0.1~1)：0.1：0.1.
The invention further relates to the preparation method of the VOCs catalytic burning integral types catalyst, catalyst preparation of the present invention with
The precious metals pd of low content is active component, and Pd is evenly spread into γ-Al using incipient impregnation method2O3Carrier, through drying
Roasting obtains catalyst powder；Bonding agent, lubricant and water being added again catalyst powder being made slurry, even application is blue or green in violet
On the inwall of stone honeycomb ceramic carrier, drying and roasting obtains the VOCs monoblock types catalysis combustion catalysis with regular pore canal structure
Agent.The preparation of catalyst of the present invention specifically includes following steps：
1) preparation of cordierite honeycomb ceramic carrier：The cordierite honeycomb ceramic immersion of 50~200 holes/square feet is dilute
15~25h is soaked in salpeter solution, is then washed with deionized to neutrality, finally dried；
2)γ-Al2O3The preparation of carrier：With diaspore as presoma, the soluble salt of Ce, Zr, La, Ba is made into 60%
(wt%) mixed solution；During mixed solution and dust technology added into diaspore powder, with dust technology as peptizing agent, abundant ball milling
1~2h of peptization, add water the suspension for being tuned into 40%, spray-dried rear roasting；
3) preparation of catalyst powder：The soluble salt of Pd is evenly spread to by above-mentioned preparation using equi-volume impregnating
γ-Al2O3On carrier and 1~2h is aged, by 60 DEG C -70 DEG C -80 DEG C of intensification order fried drys into dry powder, then toasted, roasting
；
4) preparation of catalyst coat：Above-mentioned catalyst powder and binding agent, glacial acetic acid and water are put into ball grinder, plus zirconium
Ball, 1~5min of high speed ball milling is obtained；
5) catalyst coating：The catalyst coat of above-mentioned preparation is coated uniformly on cordierite honeycomb by the way of coating
The duct inwall of ceramic monolith, obtains final product catalyst of the present invention after drying in the shade, toasting, be calcined successively.
As a specific embodiment, step 1 of VOCs catalytic burning integral types method for preparing catalyst of the present invention) in,
The mass fraction of the dust technology is 5%, and the drying temperature is 100~120 DEG C, and the time is 3~5h.
As a specific embodiment, step 2 of VOCs catalytic burning integral types method for preparing catalyst of the present invention) in,
The mass fraction of the dust technology is 5%, and the mol ratio that the soluble salt of described Ce, Zr, La, Ba press oxide is CeO2：ZrO2：
La2O3：BaO=(0.1~1)：(0.1~1)：0.1：0.1；More preferably 0.3:0.7:0.1:0.1,0.5:0.5:0.1:
0.1,0.7:0.3:0.1:0.1,0.9:0.1:0.1:0.1；The EAT of the spray drying is 180~200 DEG C, feed liquor stream
Speed is 0.1~0.2L/min；The sintering temperature is 550~750 DEG C, and the time is 3~5h.
As a specific embodiment, step 3 of VOCs catalytic burning integral types method for preparing catalyst of the present invention) in institute
It is 100~120 DEG C to state baking temperature, and the time is 3~5h, and the sintering temperature is 500~600 DEG C, and the time is 3~5h.
As a specific embodiment, step 4 of VOCs catalytic burning integral types method for preparing catalyst of the present invention) in institute
It is (33~44) to state catalyst powder, binding agent, glacial acetic acid, the mass ratio of water：(1~3)：(1~3)：(50~65)
As a specific embodiment, step 5 of VOCs catalytic burning integral types method for preparing catalyst of the present invention) in institute
The time of drying in the shade is stated for 22~26h, the baking temperature is 70~90 DEG C, the time is 8~12h, the sintering temperature is 450~
550 DEG C, the time is 3~5h.
The detailed process of catalyst slurrying of the present invention and coating is as follows：By obtained catalyst powder and bonding agent, ice vinegar
The mixed solution of acid and water is put into be sufficiently mixed in ball grinder according to the ratio of mass fraction of solids 35%~50% and (is wherein bonded
Agent accounts for overall 1~3%, and glacial acetic acid accounts for overall 1~3%), 5~10min of ball milling is to form uniform fluffy suspension
Preferably.During above-mentioned slurries are uniformly poured into cordierite honeycomb ceramic carrier carrier (weighing and be designated as M0 in advance) using cladding process, or
Be dipped vertically into above-mentioned slurries for one end of cordierite honeycomb ceramic carrier channel openings by person, keeps 3s, takes out and overturn 180
Degree, makes internal slurry be flowed out from the other end of channel openings, then immerses in slurries, this step is repeated, until slurry makes pottery honeycomb
Porcelain is all stained with duct, stops soaking paste.Unnecessary slurry is blown out with the air knife of connection compressed air, repeatedly upset purging,
And weigh (be designated as M1), recording quality is poor (M1-M0), this is of poor quality be exactly coating weight in wet base, according to slurry solids mass fraction
Be multiplied by this it is of poor quality can substantially estimate roasting after coating dry weight.Above-mentioned coating step is repeated until the weight in wet base of coating reaches rule
Definite value (makes coated weight 10%~12%).The moist catalysis that will be coated keeps flat 24h and dries in the shade by the direction parallel with duct, then puts
Enter 80 DEG C of baking 10h of constant temperature oven, be finally calcined 4h at 450~550 DEG C and can be prepared by catalyst of the present invention.
Beneficial effects of the present invention：
1st, the preparation method due to changing carrier of the invention, γ-Al are prepared using boehmite medium temperature roast2O3Make
Its specific surface area is bigger, and auxiliary agent is added using peptisation, and auxiliary agent ion can be made more to be combined closely with support crystal lattice, is more beneficial for
Promoter effect is played, and active component is dispersed in by carrier surface using process for dispersing-equi-volume impregnating evenly, carried
The anti-sintering property of Pd high.Therefore the catalysis that can reach even better than dipping Pd catalyst with the precious metals pd of lower loading is lived
Property.
2 and the addition of alkaline-earth metal Ba and rare-earth metal La improves γ-Al2O3The surface acidity of carrier makes it more favourable
In the load and dispersion of active component Pd, the addition of rare earth metal Ce, Zr forms Ce-Zr-O solid solution and is conducive to after baking
Suppress the anti-SO2 Poisonings of catalyst, and be conducive to maintaining the chemical stability of catalyst to improve service life.
Brief description of the drawings
Fig. 1 is catalyst activity test device schematic diagram of the present invention；
Fig. 2 is the toluene catalytic combustion temperature profile of catalyst I, II, III and comparative catalyst.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.All features disclosed in this specification, or disclosed all methods or during the step of, except
Beyond mutually exclusive feature and/or step, can be combined in any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent or with similar purpose by other
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature be one in a series of equivalent or similar example and
.
Embodiment 1
The preparation process of the present embodiment catalyst is as follows：
1) the commercially available cordierite honeycomb carrier that hole count is 200 holes/square inch is cut into Φ 20*40mm sample (quality
About 10g) be dipped in 200mL, the dilute nitric acid solution of 0.5% (wt%) soak 20h after take out, be washed with deionized several times into
Neutrality, takes out standby after drying 4h in 110 DEG C of baking ovens.
2)γ-Al2O3The preparation of carrier：By the commercially available boehmites of 100g (preferably Shandong Aluminum Co., Ltd. model A-AS-HC-PHP-
08) add in ball grinder, be CeO by the mol ratio that the nitrate of Ce, Zr, La, Ba presses oxide2：ZrO2：La2O3：BaO=
0.3:0.7:0.2:0.1 aqueous solution for being made into 38.25g 60% (wt%), the consumption of soluble salt is counted according to total oxide 10g,
Add in this ball grinder, be then slowly added into the dilute nitric acid solution of 300ml 5% (wt%), seal ball milling 1h, take out slurry old
Change 2h, add deionized water to be made 40% solid content slurries, mist projection granulating, the powder for taking rewinding cylinder is put into 650 DEG C of Muffle furnace and forges
Burn 4h and the modified γ-Al in surface are obtained2O3Carrier, specific surface area 220m2/g。
3) prepared by catalyst powder：Weigh the above-mentioned carrier materials of 40g, then the H for measuring 1.4ml 0.2g/ml2PdCl4Solution,
30ml solution is diluted to deionized water, γ-Al are immersed in using equi-volume impregnating2O3(Pd accounts for gross mass in carrier material
0.3%), still aging 1h, 60 DEG C of fried drys are gradually heating to 110 DEG C of drying, will be forged at 550 DEG C of catalyst powder after drying
4h is burnt, the catalyst activity powder stablized, the wherein mass ratio of Pd are 0.3%.
4) preparation of catalyst coat：Weigh 3g viscous boehmite (preferably Shandong Aluminum Co., Ltd. model A-AS-HC-PD- high
08) it is, viscous by height：Glacial acetic acid：Water=1：0.5：1 mass ratio mixing and ball milling in corundum ball grinder, time about 5min, is glued
Agent colloidal sol is connect, ball milling, ball are carried out after taking catalyst activity component powder 20g, the mixing of bonding agent 1.05g and 22.8ml deionized water
The catalyst slurry that solids content is 48.7% is obtained after mill 30min.
5) catalyst coating：Second support 10g after weighing is immersed in above-mentioned catalyst slurry after 3s, 180 degree upset
3s is soaked again, this step is repeated until slurry is impregnated with carrier, is taken out cordierite carrier and is blown out additional size in duct.Catalyst
Dried in the shade through 24h, 10h is dried in 80 DEG C, 500 DEG C of calcining 4h obtain final product the present embodiment catalyst I (Cat.I).
The present embodiment catalyst I (Cat.I) is constituted：84 parts of cordierite honeycomb ceramic carrier, γ-Al2O314 parts, oxidation
1.5 parts of thing auxiliary agent, 0.04 part of active component Pd.
Embodiment 2
The present embodiment is standby using the cordierite honeycomb carrier that method same as Example 1 is obtained same size.
γ-Al2O3The preparation of carrier：Preparation method is same as Example 1, and difference is the nitric acid of wherein Ce, Zr, La, Ba
The mol ratio that salt presses oxide is CeO2：ZrO2：La2O3：BaO=0.5:0.5:0.2:0.1 is made into 36.12g 60% (wt%)
The aqueous solution, the consumption of soluble salt counts according to total oxide 10g, and specific surface area 215m is obtained2γ-the Al of/g2O3Carrier.
It is prepared by catalyst powder：Preparation method and active component consumption are same as Example 1, the catalyst that must finally stablize
The mass ratio that active powder material, wherein Pd account for carrier material is 0.3%.
The preparation of catalyst coat and painting method are same as Example 1, finally give catalyst and are denoted as catalyst II
(Cat.II)。
The composition of the present embodiment catalyst II (Cat.II) is：85 parts of cordierite honeycomb ceramic carrier, γ-Al2O313 parts,
1.5 parts, active component Pd0.04 parts of the oxides additive.
Embodiment 3
The present embodiment is standby using the cordierite honeycomb carrier that method same as Example 1 is obtained same size.
The preparation method of first vector：γ-Al2O3The preparation of carrier：Preparation method is same as Example 1, and difference is it
The mol ratio that the nitrate of middle Ce, Zr, La, Ba presses oxide is CeO2：ZrO2：La2O3：BaO=0.9:0.1:0.2:0.1 matches somebody with somebody
Into the aqueous solution of 32.43g 60% (wt%), the consumption of soluble salt is counted according to total oxide 10g, and specific surface area 225m is obtained2/g
γ-Al2O3Carrier.
Catalyst powder, coating and coating are same as Example 1, finally give catalyst and are denoted as catalyst III
(Cat.III)。
The composition of the present embodiment catalyst III (Cat.III) is：84.4 parts of cordierite honeycomb ceramic carrier, γ-Al2O3
13.6 parts, 1.5 parts of oxides additive, 0.04 part of active component Pd.
Embodiment 4
The present embodiment is the comparative example of the catalyst of embodiment 1 to 3
The present embodiment uses infusion process to prepare the integral catalyzer that mass fraction containing Pd is for 0.045.Specific preparation method
For：Measure the appropriate H for preparing2PdCl4Solution, using impregnation in common γ-Al2O3It is aged, low on carrier material
Temperature dry, 500 DEG C roasting 4h, be then coated uniformly in the duct of ceramic honeycomb carrier using cladding process, through drying, low temperature dry
It is dry, 500 DEG C of calcining 4h.
Embodiment 5
Catalyst performance prepared by embodiment 1-4 is detected, test device as shown in figure 1, specific test process and
Condition is as follows：
Catalyst uses volume ratio 5%H2/N2Gaseous mixture is down to room temperature after 150 DEG C of prereduction 1h.The test gas of use
Component is：Toluene entrance concentration 4107mg/m3, oxygen content 21%, SO2Content 100ppm, H2O (g) contents are 5%, and Balance Air is
N2, it is 20,000h by total air speed of catalyst-1。
Component analysis：
Using toluene concentration in Agilent-7820A gas-chromatography FID hydrogen flame detectors detection gas.
The conversion ratio computing formula of toluene is as follows：
Wherein：
η toluene is toluene conversion；
C imports are toluene inlet concentration；
C outlets are toluene exit concentration；
Micro-reaction, Volume Changes are ignored.
Dependence test result is as follows：
The toluene catalytic combustion temperature profile of catalyst I, II, III and comparative catalyst is as shown in Figure 2.In reaction
Temperature is 300 DEG C, SO2Under conditions of 100ppm, the toluene conversion of catalyst I is 98.0% to content；The first of catalyst II
Benzene conversion ratio is 98.3%；The toluene conversion of catalyst III is 99.5%, and the toluene conversion of the catalyst of embodiment 4 is
60%.
From test result：Under the same terms, the organic exhaust gas catalyst prepared using the present invention has good low
Warm activity；And catalyst prepared by carrier impregnation method is used because active component decentralization is not high, and without resistance to SO2Composition,
Ignition is slow, and toluene conversion ratio is only 60%, and uses the organic exhaust gas catalyst of preparation of the invention, toluene conversion ＞
98%.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (9)
1. a kind of VOCs catalytic burning integral types catalyst, the catalyst is coated with cordierite honeycomb ceramic carrier on carrier
There is catalyst coat, the coating is γ-Al2O3, oxide and active component Pd, it is characterised in that the cordierite honeycomb pottery
The mass fraction of ceramic carrier is 82~87 parts, the γ-Al2O3Mass fraction be 10~14 parts, the mass parts of the oxide
Number is 0.8~1.5 part, and the mass fraction of the active component Pd is 0.01~0.05 part.
2. as claimed in claim 1 a kind of VOCs catalytic burning integral types catalyst, it is characterised in that the catalyst is also included
Mass fraction is 0.1~0.3 part of binding agent, and the binding agent is the one kind or several in diaspore, colloidal sol, aluminium glue, Ludox
Kind.
3. as claimed in claim 1 a kind of VOCs catalytic burning integral types catalyst, it is characterised in that the oxide be Ce-
Zr-La-Ba composite oxides, its mol ratio is CeO2：ZrO2：La2O3：BaO=(0.1~1)：(0.1~1)：0.1：0.1.
4. a kind of preparation method of VOCs catalytic burning integral types catalyst a kind of as described in any one of claims 1 to 3, it is special
Levy and be, comprise the following steps：
1) preparation of cordierite honeycomb ceramic carrier：The cordierite honeycomb ceramic of 50~200 holes/square feet is immersed into dust technology
15~25h is soaked in solution, is then washed with deionized to neutrality, finally dried；
2)γ-Al2O3The preparation of carrier：With diaspore as presoma, the soluble salt of Ce, Zr, La, Ba is made into 60% (wt%)
Mixed solution；During mixed solution and dust technology added into diaspore powder, with dust technology as peptizing agent, abundant ball milling peptization 1
~2h, add water the suspension for being tuned into 40%, spray-dried rear roasting；
3) preparation of catalyst powder：Using equi-volume impregnating by the soluble salt of Pd evenly spread to the γ of above-mentioned preparation-
Al2O3On carrier and be aged 1~2h, by 60 DEG C -70 DEG C -80 DEG C of intensification order fried drys into dry powder, it is then toasted, roasting be
Can；
4) preparation of catalyst coat：Above-mentioned catalyst powder and binding agent, glacial acetic acid and water are put into ball grinder, plus zirconium ball,
1~5min of high speed ball milling is obtained；
5) catalyst coating：The catalyst coat of above-mentioned preparation is coated uniformly on cordierite honeycomb ceramic by the way of coating
The duct inwall of carrier, obtains final product catalyst of the present invention after drying in the shade, toasting, be calcined successively.
5. as claimed in claim 4 a kind of preparation method of VOCs catalytic burning integral types catalyst, it is characterised in that step 1)
In, the mass fraction of the dust technology is 5%, and the drying temperature is 100~120 DEG C, and the time is 3~5h.
6. as claimed in claim 4 a kind of preparation method of VOCs catalytic burning integral types catalyst, it is characterised in that step 2)
In, the mass fraction of the dust technology is 5%, and the mol ratio that the soluble salt of described Ce, Zr, La, Ba press oxide is CeO2：
ZrO2：La2O3：BaO=(0.1~1)：(0.1~1)：0.1：0.1；The EAT of the spray drying is 180~200 DEG C,
Enter flow velocity for 0.1~0.2L/min；The sintering temperature is 550~750 DEG C, and the time is 3~5h.
7. as claimed in claim 4 a kind of preparation method of VOCs catalytic burning integral types catalyst, it is characterised in that step 3)
Described in baking temperature be 100~120 DEG C, the time be 3~5h, the sintering temperature be 500~600 DEG C, the time be 3~5h.
8. as claimed in claim 4 a kind of preparation method of VOCs catalytic burning integral types catalyst, it is characterised in that step 4)
Described in catalyst powder, binding agent, glacial acetic acid, water mass ratio be (33~44)：(1~3)：(1~3)：(50~65).
9. as claimed in claim 4 a kind of preparation method of VOCs catalytic burning integral types catalyst, it is characterised in that step 5)
Described in dry in the shade the time for 22~26h, the baking temperature is 70~90 DEG C, and the time is 8~12h, and the sintering temperature is 450
~550 DEG C, the time is 3~5h.
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| CN107913719A (en) * | 2017-12-06 | 2018-04-17 | 江苏安琪尔废气净化有限公司 | Catalyst and preparation method for the noble metal low-load amount of VOCs catalysis burnings |
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| CN112246250A (en) * | 2020-10-12 | 2021-01-22 | 中国石油大学(北京) | Integral catalytic combustion catalyst and preparation method and application thereof |
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