CN104707619A - Graphene/Cu-Mn-Ti composite catalyst, and preparation method and application thereof - Google Patents
Graphene/Cu-Mn-Ti composite catalyst, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
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- 230000000694 effects Effects 0.000 abstract description 8
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- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000010936 titanium Substances 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000008247 solid mixture Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- 238000003915 air pollution Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- -1 aromatic hydrocarbons organic compound Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a graphene/Cu-Mn-Ti composite catalyst. An active component is supported on a supporter graphene, and the active component is a Cu-Mn-Ti composite oxide, wherein a Cu:Mn:Ti ratio is 1-3:1-3:1-3. The invention also discloses a preparation method of the graphene/Cu-Mn-Ti composite catalyst. The preparation method comprises the following steps: adding graphite oxide into water, carrying out ultrasonic stirring until uniformly, adding butyl titanate, ethanol and acetic acid under stirring to obtain a mixture, heating the mixture at 60-70DEG C for 4-8h, and separating to obtain a precipitate; adding the precipitate into an alkali solution, heating for reacting, adding a diluted acid to neutralize, washing, filtering, and drying to obtain a solid; mixing the solid with potassium permanganate, manganese nitrate and copper nitrate to form a new mixture, adding water, stirring to make the new mixture completely dissolved in water in order to form a solution, transferring the solution into a reaction kettle, and heating for reacting. The catalyst has the advantages of high low temperature activity, low price and wide source of raw materials, and very good industrial application values.
Description
Technical field
The present invention relates to the catalyst field for exhaust-gas treatment, particularly relate to a kind of Graphene/Cu-Mn-Ti composite catalyst and its preparation method and application.
Background technology
Volatile organic waste gas (VOCs) refer to boiling point 50 ~ 260 DEG C, saturated vapour pressure is more than the volatile organic compound of 133.3Pa under room temperature, its main component is hydro carbons, sulfide, ammonia etc.Organic exhaust gas is the polluter of harmful health, the NO in it and air
2reaction generates O
3photochemical fog can be formed, and be dispersed in air along with peculiar smell, stench, spread effect is had to the eye of people, nose and respiratory tract, produce adverse effect to the internal organ such as the heart, lung, liver and nervous system, some is then the allergen affecting some organ of human body and body, even causes acute and slow poisoning, can carcinogenic, mutagenesis, can crop production reduction be caused simultaneously.
Developing rapidly of the industries such as application in recent years, shoe industry, printing and fine chemistry industry, aromatic hydrocarbons organic compound emission amount increases gradually, forms very large threat to environment and human health.Therefore, VOCs process is more and more subject to the attention of various countries, and many developed countries have all promulgated that corresponding decree is to limit the discharge of VOCs, and VOCs has become a focus in Air Pollution Control.
Low-temperature catalytic burning is a kind of technology of novel process industrial waste gas, and it can process the organic pollution of low concentration at a lower temperature.Using at present more in low temperature catalyst is noble metal, and the higher and resource-constrained of cost, creates significant limitation in industrial applicability.Therefore, seek material and there is the focus that efficient catalyst is research both at home and abroad now simply simultaneously.In published catalyst formulation, multiplex noble-metal-supported metal mixing oxide, and the research of metal mixing oxide mainly concentrates on good Cu, Mn, Co composite oxides of toluene combustion catalysis performance and adds on the modified catalyst of rare earth element, and the formula of novel carriers graphene-supported metal oxide Kaolinite Preparation of Catalyst is used to yet there are no relevant bibliographical information.
Publication number is the preparation method that the Chinese patent literature of CN103157501A discloses a kind of catalyst of CWO organic pollutants, mesoporous SBA-15 molecular sieve is adopted to enter as carrier, it has good hydrothermal stability, feature that specific area is large, take CuO as active component, in preparation process, adopt ultrasonication a period of time, promote the dispersion of active component.But SBA-15 on raw material compared with Graphene complicated and specific area not have Graphene large.
In Kaolinite Preparation of Catalyst, carrier many employings noble metal or rare earth just can reach low-temperature catalyzed effect, are unfavorable for commercial Application like this, and the catalyst therefore seeking low cost low temperature burning causes vast concern.Employing Co deposited synthesis Cu-Mn composite oxides on the books in existing document, after adding rare earth element, have good catalytic activity to toluene burning.When bed temperature is 170 DEG C, catalyst has just had good activity; When 185 DEG C, conversion ratio reaches 50%; When 235 DEG C, toluene conversion reaches more than 99%.And do not add the catalyst of rare earth element, when other conditions are identical, reach the conversion ratio of 99%, beds must be raised to more than 285 DEG C, exceeds about 50 DEG C than the catalyst adding rare earth.
Nowadays, the appearance of new and effective carrier Graphene, the specific area having super large can improve load capacity and its burning-point (650 ~ 700 DEG C) of catalyst, and raw material obtains conveniently simultaneously, attract wide attention, but it is not also applied in catalyst for catalytic combustion preparation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Graphene/Cu-Mn-Ti composite catalyst, catalytic activity is high, and reaction temperature is low, and low in raw material price and acquisition are conveniently.
A kind of Graphene/Cu-Mn-Ti composite catalyst of the present invention, take Graphene as carrier, and has active component at Graphene supported on carriers, described active component is Cu-Mn-Ti composite oxides, wherein Cu:Mn:Ti=1 ~ 3:1 ~ 3:1 ~ 3.
The flat film of Graphene to be a kind of hexangle type be honeycomb lattice, only have the two-dimensional material of a carbon atom thickness, its excellent carrier mobility, high specific area and the good transparency are as the excellent character of carrier.Therefore, Graphene can improve material by adsorption efficiency when catalyst, and the stronger Cu-Mn-Ti composite oxides of activity are the keys improving low-temperature catalytic activity.
Inventor finds that the low temperature active of the ratio of copper atom, manganese atom and titanium atom in Cu-Mn-Ti composite oxides on catalyst has obvious impact, inventor confirms active higher ratio through overtesting, preferably, described Cu:Mn:Ti=1 ~ 2:1 ~ 3:1 ~ 3.
As copper atom, manganese atom and titanium atom ratio in Cu-Mn-Ti composite oxides further preferably, described Cu:Mn:Ti=1:1 ~ 3:1 ~ 3.
Present invention also offers the preparation method of above-mentioned Graphene/Cu-Mn-Ti composite catalyst, comprise the following steps:
(1) graphite oxide is added to the water also ultrasonic agitation evenly, to add butyl titanate, ethanol and acetic acid under agitation and obtain mixture, be separated after then mixture being heated 4 ~ 8h at 60 ~ 70 DEG C and be precipitated;
(2) add in alkali lye by the precipitation that step (1) obtains, add diluted acid neutralization after adding thermal response, last washing and filtering post-drying obtains solid;
(3) solid step (2) obtained and potassium permanganate, manganese nitrate and copper nitrate are mixed to form mixture, adding water and stirring makes mixture be dissolved in the water completely formation solution, then solution is transferred in reactor and heat and react, finally successively through filtration, washing, the dry and obtained Graphene/Cu-Mn-Ti composite catalyst of calcining.
Wherein the ratio of butyl titanate, potassium permanganate, manganese nitrate and copper nitrate is allocated according to the ratio of copper atom, manganese atom and titanium atom in final products.
In step (1) and (3), water used is preferably deionized water or distilled water.Olefin(e) acid used in step (2) can adopt watery hydrochloric acid, dilute sulfuric acid or dust technology.Diluted alkaline used in step (2) can adopt the NaOH or potassium hydroxide that concentration is lower.
In step (1), ultrasonic agitation process not only makes graphite oxide peel off into the graphene oxide with single atomic layer, and makes graphene oxide stablize in water, disperse equably.
Step has TiO in (2)
2generate with Graphene simultaneously.As preferably, in step (2), heating condition is: circulating-heating 12 ~ 16h at 130 ~ 180 DEG C.
Step (3) potassium permanganate, manganese nitrate and copper nitrate used is solid, and described mixture is solid mixture.As preferably, in step (3), mixture also carries out sonic oscillation 20 ~ 40min before adding distilled water.Carrying out sonic oscillation not only can make solid particle become thinner, fully fully can also be mixed with potassium permanganate, manganese nitrate and copper nitrate by the solid that step (2) obtains, be conducive to Cu-Mn-Ti composite oxides and be uniformly distributed on Graphene.
As preferably, in step (3), heating condition is: at 130 ~ 180 DEG C, heat 10 ~ 15h.
As preferably, in step (3), drying condition is dry 20 ~ 50min at 90 ~ 120 DEG C, and calcination condition is 300 ~ 500 DEG C of calcining 3 ~ 5h.
Graphite oxide described in step (1) directly can buy acquisition, also can adopt and prepare with the following method:
Graphite powder is under agitation slowly added the concentrated sulfuric acid, holding temperature is below 5 DEG C, then sodium nitrate and potassium permanganate is added, below 10 DEG C after stirring reaction at 35 DEG C of water bath with thermostatic control 30min, then bath temperature is slowly risen to 98 DEG C, dilute with the water of same temperature maintain 15min at 98 DEG C after, then add the H that concentration is 30%
2o
2, filter, with dry 24h after 5% watery hydrochloric acid washing, obtained graphite oxide.
Because graphite oxide hygroscopicity is strong, need to dry if buy before acquisition uses, it is preferable that in situ preparation graphite oxide.Present invention also offers a kind of method of degradation organic waste gas, above-mentioned Graphene/Cu-Mn-Ti composite catalyst is put into fixed bed quartz tube reactor catalysis organic exhaust gas and carry out degradation reaction, the reaction temperature of described degradation reaction is 50 ~ 400 DEG C, air speed is 30000 ~ 80000h
-1.
Beneficial effect of the present invention is: ensure that simultaneous temperature at catalytic combustion degrading benzene thing is lower than the industrial most of catalyst come into operation, by different titaniums, copper, manganese atom ratio, obtain the most applicable catalyst compared with low-temperature catalytic burning, dropping into actual production will have very large using value and wide application prospect.
Accompanying drawing explanation
Fig. 1 is that the Graphene/Cu-Mn-Ti composite catalyst adopting embodiment 1 to obtain is degraded the curve map of toluene at different temperatures.
Fig. 2 is that the Graphene/Cu-Mn-Ti composite catalyst adopting embodiment 2 to obtain is degraded the curve map of toluene at different temperatures.
Fig. 3 is the SEM figure of Graphene/Cu-Mn-Ti composite catalyst that embodiment 1 obtains.
Fig. 4 is the TEM figure of Graphene/Cu-Mn-Ti composite catalyst that embodiment 1 obtains.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
In following examples agents useful for same be analyze pure.
Graphite oxide can be bought or be prepared by following methods:
1g8000 object graphite powder is under agitation slowly added the 15ml concentrated sulfuric acid in 500ml beaker, holding temperature is below 5 DEG C, then 0.5 sodium nitrate and 3g potassium permanganate is added, below 10 DEG C after stirring reaction at 35 DEG C of water bath with thermostatic control 30min, then bath temperature is slowly risen to 98 DEG C, be diluted to 160ml with the water of same temperature maintain 15min at 98 DEG C after, add the H that 10ml concentration is 30%
2o
2, filter, with dry 24h after 5% watery hydrochloric acid washing, obtained graphite oxide.
Embodiment 1
(1) 25mg graphite oxide is added 14ml deionized water ultrasonic agitation even, under the condition stirred, add 3.4ml butyl titanate, 46.6ml ethanol, 17ml acetic acid, be separated after mixture heats 6h at 65 DEG C and be precipitated;
(2) step (1) is precipitated adds 100ml concentration 10mol/l sodium hydroxide solution, and in anticorrosion container circulating-heating 14h under 160 DEG C of conditions, then add watery hydrochloric acid neutralization, finally spend deionized water filtration post-drying and obtain solid;
(3) solid step (2) obtained and 3.2mmol potassium permanganate, 1.2mmol manganese nitrate and 1.0mmol copper nitrate are mixed to form solid mixture, to solid mixture sonic oscillation 30min, add 70ml distilled water and stir and solid mixture is dissolved in distilled water completely form solution, then solution is transferred to 160 DEG C of heating 12h in stainless steel cauldron, after filtration washing at 105 DEG C dry 30mim, at 400 DEG C, finally calcine 4h obtain Graphene/Cu-Mn-Ti (active component mol ratio is 1:1:1) composite catalyst.
Embodiment 2
(1) 25mg graphite oxide is added 14ml deionized water ultrasonic agitation even, under the condition stirred, add 3.4ml butyl titanate, 46.6ml ethanol, 17ml acetic acid, be separated after mixture heats 6h at 65 DEG C and be precipitated;
(2) step (1) is precipitated adds 100ml concentration 10mol/l sodium hydroxide solution, and in anticorrosion container circulating-heating 14h under 160 DEG C of conditions, then add watery hydrochloric acid neutralization, finally spend deionized water filtration post-drying and obtain solid;
(3) solid step (2) obtained and 3.2mmol potassium permanganate, 1.2mmol manganese nitrate and 0.5mmol copper nitrate are mixed to form solid mixture, to solid mixture sonic oscillation 30min, add 70ml distilled water and stir and solid mixture is dissolved in distilled water completely form solution, then solution is transferred to 160 DEG C of heating 12h in stainless steel cauldron, after filtration washing at 105 DEG C dry 30mim, at 400 DEG C, finally calcine 4h obtain Graphene/Cu-Mn-Ti (active constituent mol ratio is 1:2:2) composite catalyst.
Performance test
Method of testing is: each 100mg of catalyst that Example 1 and embodiment 2 obtain, be placed in respectively in the quartz ampoule of continuous fixed bed reactor, the concentration of quartz ampoule inlet end and outlet side toluene is detected respectively with Shimadzu GC2010, concentration before the concentration of quartz ampoule inlet end and outlet side toluene that is to say degradation of toluene and after degraded, can obtain the degradation rate of toluene by the concentration calculated before and after degradation of toluene.Wherein reaction gas consists of: 200 ~ 300ppm toluene and 21% oxygen and 79% nitrogen, wherein do Balance Air with nitrogen, the flow velocity of reaction gas is 350mL/min, and air speed is 50000h
-1.Activity rating temperature is 100 ~ 350 DEG C, under different temperatures, and the conversion ratio of catalyst reduction toluene, is shown in Table 1:
Table 1. Graphene/Cu-Mn-Ti composite catalyst is to the degradation rate of toluene
As can be seen from Table 1, the Graphene that embodiment 1 and embodiment 2 obtain/Cu-Mn-Ti composite catalyst still has higher catalytic activity when low temperature (lower than 200 DEG C), and when temperature is low to moderate 50 DEG C, the degradation rate of toluene can remain on more than 60%.Particularly Graphene/Cu-Mn-Ti composite catalyst activity of obtaining of embodiment 1 is the highest, and in Graphene/Cu-Mn-Ti composite catalyst that corresponding embodiment 1 obtains, the ratio of Cu-Mn-Ti is best.
In addition can very intuitively be arrived by Fig. 1 and Fig. 2, the Graphene that embodiment 1 obtains/Cu-Mn-Ti composite catalyst has more outstanding low temperature active.
The BET of table 2. Graphene/Cu-Mn-Ti composite catalyst measures
| Specific area | Total pore volume | Aperture | |
| GS-Ti/Cu/Mn(1:1:1) | 15.895m 3/g | 0.5842cm 3/g | 90.95nm |
The BET test data of the Graphene that table 2 obtains for embodiment 1/Cu-Mn-Ti composite catalyst, catalyst has larger specific area as can be seen from Table 2, is conducive to the contact of organic exhaust gas and active component, improves degradation rate.
Claims (8)
1. Graphene/Cu-Mn-Ti composite catalyst, take Graphene as carrier, and has active component at Graphene supported on carriers, it is characterized in that, described active component is Cu-Mn-Ti composite oxides, wherein Cu:Mn:Ti=1 ~ 3:1 ~ 3:1 ~ 3.
2. Graphene/Cu-Mn-Ti composite catalyst as claimed in claim 1, is characterized in that, described Cu:Mn:Ti=1 ~ 2:1 ~ 3:1 ~ 3.
3. Graphene/Cu-Mn-Ti composite catalyst as claimed in claim 1, is characterized in that, described Cu:Mn:Ti=1:1 ~ 3:1 ~ 3.
4. a preparation method for the Graphene as described in any one of claims 1 to 3/Cu-Mn-Ti composite catalyst, is characterized in that, comprise the steps:
(1) graphite oxide is added to the water also ultrasonic agitation evenly, to add butyl titanate, ethanol and acetic acid under agitation and obtain mixture, be separated after then mixture being heated 4 ~ 8h at 60 ~ 70 DEG C and be precipitated;
(2) add in alkali lye by the precipitation that step (1) obtains, add diluted acid neutralization after adding thermal response, last washing and filtering post-drying obtains solid;
(3) solid step (2) obtained and potassium permanganate, manganese nitrate and copper nitrate are mixed to form mixture, adding water and stirring makes mixture be dissolved in the water completely formation solution, then solution is transferred in reactor and heat and react, finally successively through filtration, washing, the dry and obtained Graphene/Cu-Mn-Ti composite catalyst of calcining.
5. preparation method as claimed in claim 4, is characterized in that, in step (2), heating condition is: circulating-heating 12 ~ 16h at 130 ~ 180 DEG C.
6. preparation method as claimed in claim 4, is characterized in that, in step (3), mixture also carries out sonic oscillation 20 ~ 40min before adding water.
7. preparation method as claimed in claim 4, is characterized in that, in step (3), heating condition is: at 130 ~ 180 DEG C, heat 10 ~ 15h.
8. the method for a degradation organic waste gas, it is characterized in that, Graphene as described in claims 1 to 3/Cu-Mn-Ti composite catalyst is put into fixed bed quartz tube reactor catalysis organic exhaust gas and carry out degradation reaction, the reaction temperature of described degradation reaction is 50 ~ 400 DEG C, air speed is 30000 ~ 80000h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510057844.4A CN104707619B (en) | 2015-02-04 | 2015-02-04 | Graphene/Cu-Mn-Ti composite catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510057844.4A CN104707619B (en) | 2015-02-04 | 2015-02-04 | Graphene/Cu-Mn-Ti composite catalyst, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN104707619A true CN104707619A (en) | 2015-06-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105597775A (en) * | 2015-11-02 | 2016-05-25 | 浙江工商大学 | Graphene /Cu-Mn-Ce compound catalyst, and preparation method and applications thereof |
| CN106238065A (en) * | 2016-07-08 | 2016-12-21 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst being catalyzed Formaldehyde decomposition and preparation method thereof |
| CN106607056A (en) * | 2016-12-30 | 2017-05-03 | 北京化工大学常州先进材料研究院 | Graphene supported noble metal composite oxide VOCs catalyst and preparation method thereof |
| CN108914085A (en) * | 2018-07-17 | 2018-11-30 | 华南理工大学 | Porous micro-fiber loaded graphene film of one kind and preparation method thereof |
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| CN104190409A (en) * | 2014-08-19 | 2014-12-10 | 南京师范大学 | Graphene-loaded titanium-based core-shell-structured low-temperature SCR sulfur-resisting catalyst and preparation method thereof |
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| WO2014005598A1 (en) * | 2012-07-06 | 2014-01-09 | Teknologisk Institut | Method of preparing a catalytic structure |
| CN103331159A (en) * | 2013-07-10 | 2013-10-02 | 中南大学 | Cu2O-TiO2/reduced graphene oxide ternary complex, and preparation method and applications thereof |
| CN103721510A (en) * | 2013-12-13 | 2014-04-16 | 江苏中科睿赛污染控制工程有限公司 | VOCs high-efficiency processing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105597775A (en) * | 2015-11-02 | 2016-05-25 | 浙江工商大学 | Graphene /Cu-Mn-Ce compound catalyst, and preparation method and applications thereof |
| CN106238065A (en) * | 2016-07-08 | 2016-12-21 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst being catalyzed Formaldehyde decomposition and preparation method thereof |
| CN106238065B (en) * | 2016-07-08 | 2018-10-16 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst and preparation method thereof of catalysis Formaldehyde decomposition |
| CN106607056A (en) * | 2016-12-30 | 2017-05-03 | 北京化工大学常州先进材料研究院 | Graphene supported noble metal composite oxide VOCs catalyst and preparation method thereof |
| CN108914085A (en) * | 2018-07-17 | 2018-11-30 | 华南理工大学 | Porous micro-fiber loaded graphene film of one kind and preparation method thereof |
| CN108914085B (en) * | 2018-07-17 | 2020-12-22 | 华南理工大学 | Porous microfiber-loaded graphene film and preparation method thereof |
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