CN102553348A - Filter material loaded with nanometer catalyst and preparation method and application thereof - Google Patents
Filter material loaded with nanometer catalyst and preparation method and application thereof Download PDFInfo
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- CN102553348A CN102553348A CN2012100066071A CN201210006607A CN102553348A CN 102553348 A CN102553348 A CN 102553348A CN 2012100066071 A CN2012100066071 A CN 2012100066071A CN 201210006607 A CN201210006607 A CN 201210006607A CN 102553348 A CN102553348 A CN 102553348A
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Abstract
The invention provides a filter material loaded with a nanometer catalyst and a preparation method and an application thereof. A carbon nanometer tube is used as a medium, the nanometer catalyst is firstly adsorbed on the surface of the carbon nanometer tube, and then the carbon nanometer tube is led to form a layer of compact film on the surface of the filter material. The ratio of mass sum of the nanometer catalyst and the carbon nanometer tube and the mass of the filter material is (1-20):100. The mass ratio of the nanometer catalyst and the carbon nanometer tube is (0.5-20):100. The filter material and the preparation method and the application thereof solve the problem that a tail gas purification system in the prior art is complex and high in governing cost. Especially the carbon nanometer tube is used as a nanometer catalyst carrier, and the puzzle that the catalyst is loaded on the filter material is successfully solved. By adding the carbon nanometer tube, physical properties of the filter material such as strength, corrosion resistance and dedusting efficiency of smaller particles are greatly improved, and accordingly higher filtering efficiency and well harmful gas removing capability of the filter material are achieved.
Description
Technical field
The invention belongs to the function filter material technical field, particularly a kind of filtrate of loaded with nano level catalyst.
Background technology
As everyone knows, NO
xBe one of source of atmospheric pollution, human beings'health is constituted threat greatly.Various countries are to NO
xDischarging strict restriction is all arranged, and standard is more and more tighter.Therefore, in the last few years, people had done number of research projects aspect flue-gas denitrification.In numerous denitride technologies, SCR is the highest, the most ripe denitride technology of nitric efficiency.The SCR method is under the special catalyst effect, with ammonia or other reducing agent optionally with NO
xBe reduced to N
2And H
2The method of O.Because it has high efficiency and practicality, has become the denitrogenation hot research fields at present.
300 ℃ of business-like vanadium titanium System Catalyst light-off temperatures high (>), be difficult in the smoke processing system end use application, and the installation and operation expense is higher.Therefore, economy is high and be applicable to that the terminal low-temperature SCR technology of handling becomes the focus that the researcher pays close attention to.Carrier-free MnO
x-CeO
2Catalyst is that the low-temperature SCR activity was the highest during this type of was reported at present, and temperature NOx in the time of 120 ℃ can almost completely be converted into N
2
But the present method that the general employing of control of pollutant is removed separately.Can cause the raising of the big and treatment cost of the complicacy, floor space of factory's tail flue gas cleaning system thus.
In the flue gas ash removal field; Sack cleaner has become the first-selection of flue gas ash removal; And the fiber source that filtrate has that technological process is simple, speed of production fast, output is high with labor productivity, cost is low, available is wide, advantage such as more than the technology easy master, product variety, and increase of production is very fast in worldwide in recent years.Existing deduster can only dedusting, and to the NO in the flue gas
xNo removal effect.So study the emphasis that a kind of sack cleaner that has dedusting and denitration concurrently becomes various countries' research.
CNT is owing to have unique one-dimentional structure, big specific area, superpower mechanical performance, high chemistry and heat endurance and the favorable conductive ability becomes the focus that the nearest more than ten years study in the world.Be applied in the catalyst aspect or all there has been ripe research the film forming aspect, but the composite of carbon nanotube loaded catalyst is applied to not see on the sack cleaner that report is arranged.
Summary of the invention
The object of the present invention is to provide a kind of filtrate of loaded with nano level catalyst, solve in the prior art shortcomings such as the complicated and treatment cost height of tail flue gas cleaning system.Be the nano-catalytic agent carrier with the CNT particularly, successfully solved the difficult problem of catalyst cupport on filtrate.Owing to added CNT, the physical property of filtrate such as intensity, corrosion resistance and all can be greatly improved, thereby the ability that makes filtrate higher filter efficiency arranged and well take off pernicious gas to the efficiency of dust collection of small particle more.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of filtrate of loaded with nano level catalyst is to be media with the CNT, earlier nanocatalyst is adsorbed on carbon nano tube surface, makes CNT form one deck dense film at filter material surface then; Described nanocatalyst and CNT quality sum are 1-20:100 with the ratio of filtrate quality; The mass ratio of described nanocatalyst and CNT is 0.5-20:100.
Described nanocatalyst is the nano level carrier-free MnO of homemade or commercial purchase
x-CeO
2Catalyst, MnO
xBe MnO
2, Mn
2O
3, Mn
3O
4In one or more mixture, particle diameter is less than 100nm.
The multi-walled carbon nano-tubes that described CNT is bought from commerce, diameter is 10-80nm, and length is 1-20 μ m, and purity is greater than 80%, and without peracid or oxidation processes.
Described filtrate is a polyphenylene sulfide Nomex filtrate, is to be raw material with the polyphenylene sulfide fibre, is prepared from through shredding, compound batch mixing, combing, lapping, acupuncture, thermal finalization and the press polish of singing.
The preparation method's of the filtrate of loaded with nano level catalyst concrete steps are following:
(1) is that 1:1-2:1 adds ultrasonic 1-24h in the absolute ethyl alcohol with nanocatalyst and CNT by mass ratio, forms the suspension of black; Leave standstill 1-20min again, nanocatalyst is adsorbed onto on the carbon nano tube surface;
(2) with the filtrate be filter, and connect vacuumfilter, the suspension of step (1) is cast in filter material surface; The open vacuum nutsch filter filters out solvent, lets CNT adhere to and becomes entangled in the surface of filtrate; Form one deck dense film, catalyst also and then loads on the filtrate;
(3) filtrate of step (2) is put into the 40-60 ℃ of dry 1-24h of vacuum drying chamber, promptly get the filtrate of described loaded with nano level catalyst.
The application of the filtrate of loaded with nano level catalyst is that the filtrate of loaded with nano level catalyst is used as dedusting agent and denitrfying agent.Temperature is under 80-160 ℃, and load capacity all has denitration rate preferably in 5% ~ 20% scope.
Remarkable advantage of the present invention is: the present invention solves shortcoming such as tail flue gas cleaning system complicacy and treatment cost height in the prior art.Be the nano-catalytic agent carrier with the CNT particularly, successfully solved the difficult problem of catalyst cupport on filtrate.Owing to added CNT, the physical property of filtrate such as intensity, corrosion resistance and all can be greatly improved, thereby the ability that makes filtrate higher filter efficiency arranged and well take off pernicious gas to the efficiency of dust collection of small particle more.
Description of drawings
Fig. 1 is in the catalyst activity property testing, self-control tubular type SCR reactor assembly figure.Among the figure, 1 is N
2, 2 is O
2, 3 is NH
3, 4 is NO, and 5 is mass flowmenter, and 6 is triple valve, and 7 is thermocouple, and 8 is digital temperature programmer, and 9 is reactor, and 10 is analytical instrument, 11 is exhaust apparatus.
Fig. 2 is the process of preparing filter material flow chart of loaded with nano level catalyst.
The specific embodiment
Below be several specific embodiment of the present invention, further specify the present invention, but the present invention be not limited only to this.
PPS Nomex filtrate in the following example prepares by following method: with polyphenylene sulfide (PPS) fiber is raw material, prepares the Nomex filtrate through shredding, compound batch mixing, combing, lapping, acupuncture, thermal finalization and the press polish of singing.
Cutting a diameter is the circular PPS filtrate of 7.40cm, on electronic balance, claims to such an extent that its quality is 2.2770g.Take by weighing 0.0759gMnO respectively
x-CeO
2And 0.0380gMWTNs, put into the 50ml beaker, add 30ml ethanol, ultrasonic 1h on ultrasonic device forms opaque suspension, leaves standstill 5min (deposition or layering not occurring) then.
With above-mentioned cut filtrate be contained in and be used as filter in the Buchner funnel, pour suspension in funnel suction filtration, treat that filtrating is drained after; The gained filtrate is put into the dry 2h of vacuum drying chamber, and temperature is made as 50 ℃, take out then weigh 2.3894g; Calculate to such an extent that load capacity is 4.9%, theoretical value is 5%.
Catalyst is estimated in self-control tubular type SCR reactor.NO and NH
3Volume fraction is 0.05%, O
2Volume fraction is 5%, and all the other are N
2, gas flow rate is 226mLmin
-1, temperature is set to 160 ℃, and using Britain's KM940 flue gas analyzer to record the denitration rate then is 60%.
Cutting a diameter is the circular PPS filtrate of 7.40cm, on electronic balance, claims to such an extent that its quality is 2.1050g.Take by weighing 0.2807gMnO respectively
x-CeO
2And 0.1403gMWTNs, put into the 150ml beaker, add 80ml ethanol, ultrasonic 12h on ultrasonic device forms opaque suspension, leaves standstill 10min (deposition or layering not occurring) then.
With above-mentioned cut filtrate be contained in and be used as filter in the Buchner funnel, pour suspension in funnel suction filtration, treat that filtrating is drained after; The gained filtrate is put into the dry 4h of vacuum drying chamber, and temperature is made as 60 ℃, take out then weigh 2.5211g; Calculate to such an extent that load capacity is 19.8%, theoretical value is 20%.
Catalyst is estimated in self-control tubular type SCR reactor.NO and NH
3Volume fraction is 0.05%, O
2Volume fraction is 5%, and all the other are N
2, gas flow rate is 226mLmin
-1, temperature is set to 160 ℃, and using Britain's KM940 flue gas analyzer to record the denitration rate then is 96%.
Cutting a diameter is the circular PPS filtrate of 7.40cm, on electronic balance, claims to such an extent that its quality is 2.1558g.Take by weighing 0.1437gMnO respectively
x-CeO
2And 0.0719gMWTNs, put into the 100ml beaker, add 50ml ethanol, ultrasonic 10h on ultrasonic device forms opaque suspension, leaves standstill 15min (deposition or layering not occurring) then.
With above-mentioned cut filtrate be contained in and be used as filter in the Buchner funnel, pour suspension in funnel suction filtration, treat that filtrating is drained after; The gained filtrate is put into the dry 2h of vacuum drying chamber, and temperature is made as 50 ℃, take out then weigh 2.3701g; Calculate to such an extent that load capacity is 9.9%, theoretical value is 10%.
Catalyst is estimated in self-control tubular type SCR reactor.NO and NH
3Volume fraction is 0.05%, O
2Volume fraction is 5%, and all the other are N
2, gas flow rate is 226mLmin
-1, temperature is set to 130 ℃, and using Britain's KM940 flue gas analyzer to record the denitration rate then is 86%.
Cutting a diameter is the circular PPS filtrate of 7.40cm, on electronic balance, claims to such an extent that its quality is 2.3619g.Take by weighing 0.1575g MnO respectively
x-CeO
2And 0.0787gMWTNs, put into the 100ml beaker, add 70ml ethanol, ultrasonic 24h on ultrasonic device forms opaque suspension, leaves standstill 20min (deposition or layering not occurring) then.
With above-mentioned cut filtrate be contained in and be used as filter in the Buchner funnel, pour suspension in funnel suction filtration, treat that filtrating is drained after; The gained filtrate is put into the dry 24h of vacuum drying chamber, and temperature is made as 70 ℃, take out then weigh 2.3701g; Calculate to such an extent that load capacity is 10%, theoretical value is 10%.
Catalyst is estimated in self-control tubular type SCR reactor.NO and NH
3Volume fraction is 0.05%, O
2Volume fraction is 5%, and all the other are N
2, gas flow rate is 226mLmin
-1, temperature is set to 80 ℃, and using Britain's KM940 flue gas analyzer to record the denitration rate then is 68%.
Activity rating: catalyst is estimated in self-control tubular type SCR reactor.Reactor is an external electric, the other thermocouple measuring temperature of placing of reaction tube beds, and the experimental provision flow process is as shown in Figure 1.Form with steel gas cylinder simulated flue gas, comprise NO, O in the flue gas
2, N
2, NH
3Be reducing gas, NO and NH
3Volume fraction is 0.04-0.06%, O
2Volume fraction is 4-6%, and all the other are N
2, gas flow rate is 226mLmin
-1, temperature is controlled between 80-160 ℃, and gas flow, composition are regulated and control by mass flowmenter.Britain KM940 flue gas analyzer is adopted in gas analysis, and in order to guarantee data stability and accuracy, each operating mode is stablized 60min at least.
Table 1 different loads amount and temperature are to the influence of denitration rate
Annotate: load capacity is nanocatalyst and CNT quality sum and the ratio of filtrate quality.
Can find out that from table 1 data this product has improved the denitration rate of filtrate greatly, and catalyst loadings is big more, the denitration rate is high more; And along with temperature rising denitration efficiency also improves, but after temperature surpassed 130 ℃, it is not obvious that denitration efficiency raises, and catalytic amount plays a major role.
The above is merely preferred embodiment of the present invention, and all equalizations of doing according to claim of the present invention change and modify, and all should belong to covering scope of the present invention.
Claims (6)
1. the filtrate of a loaded with nano level catalyst; It is characterized in that: the filtrate of described loaded with nano level catalyst; Be to be media with the CNT, earlier nanocatalyst be adsorbed on carbon nano tube surface, make CNT form one deck dense film then at filter material surface; Described nanocatalyst and CNT quality sum are 1-20:100 with the ratio of filtrate quality; The mass ratio of described nanocatalyst and CNT is 0.5-20:100.
2. the filtrate of loaded with nano level catalyst according to claim 1 is characterized in that: described nanocatalyst is the nano level carrier-free MnO of homemade or commercial purchase
x-CeO
2Catalyst, MnO
xBe MnO
2, Mn
2O
3, Mn
3O
4In one or more mixture, particle diameter is less than 100nm.
3. the filtrate of loaded with nano level catalyst according to claim 1 is characterized in that: the multi-walled carbon nano-tubes that described CNT is bought from commerce, and diameter is 10-80nm, and length is 1-20 μ m, and purity is greater than 80%, and without peracid or oxidation processes.
4. the filtrate of loaded with nano level catalyst according to claim 1; It is characterized in that: described filtrate is a polyphenylene sulfide Nomex filtrate; Be to be raw material with the polyphenylene sulfide fibre, be prepared from through shredding, compound batch mixing, combing, lapping, acupuncture, thermal finalization and the press polish of singing.
5. the preparation method of the filtrate of a loaded with nano level catalyst as claimed in claim 1, it is characterized in that: described preparation method's concrete steps are following:
Is that 1:1-2:1 adds ultrasonic 1-24h in the absolute ethyl alcohol with nanocatalyst and CNT by mass ratio, forms the suspension of black; Leave standstill 1-20min again, nanocatalyst is adsorbed onto on the carbon nano tube surface;
With the filtrate is filter, and connects vacuumfilter, and the suspension of step (1) is cast in filter material surface; The open vacuum nutsch filter filters out solvent, lets CNT adhere to and becomes entangled in the surface of filtrate; Form one deck dense film, catalyst also and then loads on the filtrate;
The filtrate of step (2) is put into the 40-60 ℃ of dry 1-24h of vacuum drying chamber, promptly get the filtrate of described loaded with nano level catalyst.
6. the application of the filtrate of a loaded with nano level catalyst as claimed in claim 1 is characterized in that: the filtrate of described loaded with nano level catalyst uses as dedusting agent and denitrfying agent.
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| CN201210006607.1A CN102553348B (en) | 2012-01-11 | 2012-01-11 | Filter material loaded with nanometer catalyst and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102772953A (en) * | 2012-07-17 | 2012-11-14 | 福州大学 | Preparation method of compound filtering material loaded with efficient denitrification catalyst |
| CN103212245A (en) * | 2013-04-25 | 2013-07-24 | 福州大学 | Dedusting filter material containing MnO2 catalyst, and preparation method and application thereof |
| CN104014200A (en) * | 2014-05-29 | 2014-09-03 | 南京工业大学 | Preparation method of dedusting-denitration integrated filter material |
| CN105435534A (en) * | 2015-11-17 | 2016-03-30 | 安徽省元琛环保科技有限公司 | Modified functional filter material loaded with low temperature denitration catalyst and preparation method thereof |
| CN105983273A (en) * | 2015-02-17 | 2016-10-05 | 刘朝南 | Active suspension filtering material and preparation method thereof |
| CN106215516A (en) * | 2016-08-19 | 2016-12-14 | 安徽元琛环保科技股份有限公司 | A kind of filtrate method for sorting having multi-functions |
| CN106215515A (en) * | 2016-08-19 | 2016-12-14 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of Electrospun nano-fibers glass woven felt filter material |
| CN106334372A (en) * | 2016-09-21 | 2017-01-18 | 福州大学 | Ferromanganese compound filter material in-situ coated by thiophene conducting polymer and preparation of ferromanganese compound filter material |
| CN109174205A (en) * | 2018-09-12 | 2019-01-11 | 广州优润合成材料有限公司 | A kind of compound and preparation method thereof for organo-metallic catalyst |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102772953A (en) * | 2012-07-17 | 2012-11-14 | 福州大学 | Preparation method of compound filtering material loaded with efficient denitrification catalyst |
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| CN103212245A (en) * | 2013-04-25 | 2013-07-24 | 福州大学 | Dedusting filter material containing MnO2 catalyst, and preparation method and application thereof |
| CN104014200A (en) * | 2014-05-29 | 2014-09-03 | 南京工业大学 | Preparation method of dedusting-denitration integrated filter material |
| CN104014200B (en) * | 2014-05-29 | 2015-10-28 | 南京工业大学 | A kind of preparation method of dedusting denitrification integral filtrate |
| CN105983273A (en) * | 2015-02-17 | 2016-10-05 | 刘朝南 | Active suspension filtering material and preparation method thereof |
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| CN105435534A (en) * | 2015-11-17 | 2016-03-30 | 安徽省元琛环保科技有限公司 | Modified functional filter material loaded with low temperature denitration catalyst and preparation method thereof |
| CN106215516A (en) * | 2016-08-19 | 2016-12-14 | 安徽元琛环保科技股份有限公司 | A kind of filtrate method for sorting having multi-functions |
| CN106215515A (en) * | 2016-08-19 | 2016-12-14 | 安徽元琛环保科技股份有限公司 | A kind of preparation method of Electrospun nano-fibers glass woven felt filter material |
| CN106334372A (en) * | 2016-09-21 | 2017-01-18 | 福州大学 | Ferromanganese compound filter material in-situ coated by thiophene conducting polymer and preparation of ferromanganese compound filter material |
| CN106334372B (en) * | 2016-09-21 | 2018-06-15 | 福州大学 | The ferromanganese composite filtering material of thiophene-based conductive polymer in-stiu coating and its preparation |
| CN109174205A (en) * | 2018-09-12 | 2019-01-11 | 广州优润合成材料有限公司 | A kind of compound and preparation method thereof for organo-metallic catalyst |
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