CN104088135A - Method for utilizing graphene to modify filter-material fiber of bag-type deduster - Google Patents
Method for utilizing graphene to modify filter-material fiber of bag-type deduster Download PDFInfo
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- CN104088135A CN104088135A CN201410242277.5A CN201410242277A CN104088135A CN 104088135 A CN104088135 A CN 104088135A CN 201410242277 A CN201410242277 A CN 201410242277A CN 104088135 A CN104088135 A CN 104088135A
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Abstract
A related method for utilizing graphene to modify filter-material fiber of a bag-type deduster comprises the following steps: 1) taking graphite as a raw material, using an oxidation-reduction method to prepare graphene, dispersing graphene in water or an organic solvent; 2) mixing 3-aminopropyltriethoxysilane and the like as a coupling agent with ethanol according to a volume ratio of 1:3, and uniformly spraying the mixture on the surface of the filter-fiber filter material; 3) employing an immersing or spraying manner to coat the surface of the filter-fiber filter material obtained in the step (2) with the graphene sol prepared in the step (1); and 4) performing natural-placing stabilization on the filter-material fiber obtained in the step (3) for 24 h, then utilizing water or a light solvent to clean, and putting the filter-fiber filter material in a vacuum drying box and baking at 110 DEG C for 10 h. Compared with the prior art, the method helps to substantially improve performances of the filter-material fiber by utilizing modification of graphene to the filter material of the bag-type deduster, and has extremely good industrial utilization value.
Description
Technical field
The present invention relates to a kind of environmental protection technology, particularly a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber in the industries such as coal-fired and nonferrous smelting.
Background technology
In recent years, there has been the development of very fast level in China in industries such as coal-fired and nonferrous smeltings, and in these industry developments, also with huge environmental pressure, the particulate in air pollution problem occurring especially has in recent years been subject to people's extensive concern.The haze problem of being brought by particle, urgently to be resolved hurrily with the problems such as acid rain that acidic gas in air and hydrogenesis bring.Along with the reinforcement of country to the substantial pollution industry particles such as coal-fired and nonferrous smelting and toxic and harmful emission control, on existing dust arrester, develop and have intensified dust removal device dust removing effects, Collaborative Control oxysulfide, it is particularly important that the novel deduster of the advantages such as nitrogen oxide, long service life seems.
The main deduster using has electrostatic precipitator, cyclone dust collectors, inertial dust separator, wet scrubber, sack cleaner etc. at present.The mechanical type such as inertial dust separator, cyclone dust collectors cleaner is because the factors such as efficiency of dust collection and equipment investment do not re-use substantially in high-effective dust-removing occasion, and the application of wet scrubber also compares less.Electrostatic precipitation with bag type dust removing technology due to its efficiency of dust collection dedusting technology high and that more and more become to take as the leading factor.Wherein sack cleaner has obtained application more widely because have efficiency of dust collection advantage high, stable and reliable for performance, simple to operate again.Sack cleaner structure is mainly partly comprised of upper box body, middle part casing, lower part box (ash bucket), soot cleaning system and ash exhauster etc., wherein filtrate is the core component that forms sack cleaner, and to bag-type dusting, operation has a great impact its performance.Good filtrate answers that dust containing capacity is large, efficiency is high, resistance is low, hygroscopicity is little, long service life, also should have wear-resisting resistance to, high temperature, corrosion resistant feature simultaneously.The character of filtrate, except outside the Pass having with fiber itself, has very large relation with the surface texture of filtrate.Along with the development of chemical industry, also there is larger variation in the kind of filtrate, by structure, can be divided into filter cloth and felt two classes, by filtrate material, can be divided into natural fabric, inorfil and synthetic fiber etc.The deficiency that a lot of scholar both domestic and external exists for existing filtrate, the particularly surface texture modification to filtrate, carried out a large amount of work, but at present filtrate still exists that bad mechanical strength, non-oxidizability are poor, the easy defect such as water suction and poorly conductive, filtrate is carried out to modification and can develop a kind of physical imperfection that simultaneously solves filtrate and associated treatment mercury, NO
2deng the novel filtrate of sour gas, seem particularly important.
Graphene be the thinnest be in the world the hardest nano material also, this is a kind of new material of the individual layer laminated structure consisting of carbon atom.This be a kind of by carbon atom with sp
2hybridized orbit forms the flat film that hexangle type is honeycomb lattice, only has the two-dimensional material of a carbon atom thickness.Graphene has perfect hybrid structure, and large conjugated system makes its electron transport ability very strong, and the raw material of synthesizing graphite alkene is graphite, cheap; Graphene has outstanding physics and electrical properties, as high in high-specific surface area, high conductivity, mechanical strength, be easy to modify and large-scale production etc.The appearance of Graphene causes the interest that researchers are huge, it has unusual electric conductivity, higher intensity and fabulous light transmission, in a lot of fields, Graphene all has larger application prospect, as can be substituted for silicon prepared the excellent material of electronic product, nanometer circuit, good solar cell material etc.Graphene also rarely has report for the research of modification deduster filtrate, and the present invention wishes to develop a kind of Graphene modified filter material, overcomes the physical imperfection of traditional filtrate, extends filtrate service time, and can the novel filtrate of associated treatment multiple pollutant.
For the problems referred to above, we explore by experiment, have proposed a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber.
Summary of the invention
Object of the present invention is exactly to provide a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions: a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber, it is characterized in that, and comprise the following steps:
1) preparation of graphene dispersing solution: take graphite as raw material, make required Graphene by oxidation-reduction process, and be dispersed in the organic solvents such as water or ethanol;
2) preliminary treatment of filter fiber filter material surface: adopt 3-aminopropyl triethoxysilane etc. to mix by the volume ratio of 1:3 with ethanol as coupling agent filter fiber filtrate, be sprayed on uniformly filter fiber filter material surface;
3) coating to filter media fibre by the Graphene colloidal sol of making: the Graphene colloidal sol that the mode that employing is dipped or sprayed is made step (1) is coated in step (2) gained filter fiber filter material surface;
4) the dry processing of filter media fibre: after the stabilisation of placement naturally of 24 hours, recycling water or light naphtha clean, and filter fiber filtrate is dried 10 hours in 110 ℃ in vacuum drying chamber by step (3) gained filter media fibre.
Its concrete preparation process of described graphene dispersing solution is: Graphene and be scattered in water or organic solvent in form graphene suspension, by the water to graphene suspension, add polarity dispersant, after stirring, after ultrasonic dispersion, be mixed and made into graphene dispersing solution, the concentration of Graphene is 0.5-20g/L; Described polarity dispersant is polyacrylamide or polyvinyl alcohol, and graphene uniform is scattered in these dispersant nonpolar liquids.
Or, described graphene dispersing solution is to make by the following method: the step of the method by graphite powder by oxidation-reduction by graphite-graphene oxide-Graphene makes graphene oxide or reduction state graphene, make its ultrasonic being scattered in the organic solvents such as water or ethanol, can obtain stable graphene dispersing solution.
Described Graphene is graphene oxide, reduction state graphene or the compound of the two; Its raw material sources are that graphene oxide or graphite oxide make through disperseing, reducing.
Described filter fiber filtrate refers to that one or more in polyurethane, polyamide fiber, poly-propionitrile fiber, polyphenylene sulfide or polytetrafluoroethylene fibre are compound, and its state is fibre bundle before knitting or the filter cloth of forming.
Described painting method refers to filter media fibre to be immersed in graphene dispersing solution to infiltrate and applies, or utilizes spray gun that graphene dispersing solution is sprayed on fibre bundle or form the fiber surface of filter cloth.
Filter media fibre after coating is after the stabilisation of placement naturally of 24 hours, and recycling water or light naphtha clean, and pass through afterwards normal pressure or vacuumize, make required Graphene modified filter material fiber.Described light naphtha comprises ethanol, propyl alcohol.
The chemical method of described oxidation-reduction is: native graphite is made to graphene oxide (GO) or reduction state graphene through Hummers method by oxidation-reduction process and through ultrasonic dispersion, and the oxidant adopting in oxidizing process is dense H
2sO
4and KMnO
4, adding reductant is hydrazine hydrate, sodium borohydride etc.
Described filter fiber filtrate refers to that one or more in polyurethane, polyamide fiber, poly-propionitrile fiber, polyphenylene sulfide or polytetrafluoroethylene fibre are compound, and its state is fibre bundle before knitting or the filter cloth of forming.
Described painting method refers to filter media fibre to be immersed in Graphene colloidal sol to infiltrate and applies, or utilizes spray gun that Graphene colloidal sol is sprayed on fibre bundle or form the fiber surface of filter cloth.
Filter media fibre after coating is after the stabilisation of placement naturally of 24 hours, and recycling water or light naphtha clean, and pass through afterwards normal pressure or vacuumize, make required Graphene modified filter material fiber.
The filter fabric of bag filter precipitator fiber of the Graphene modification that the present invention adopts, has strengthened the fibre strength of filtrate, has greatly reduced broken bag rate, has extended the service life of filter bag.Meanwhile, Graphene coating is by the NO in filter media fibre and flue gas
2, SO
2and the oxidisability such as oxygen or corrosive gas effectively isolate, thereby alleviated the fibrous fracture phenomenon of filtrate because being corroded or being oxidized.In addition, by means of the great adsorption capacity in Graphene surface, can be to the mercury in flue gas or NO
2etc. component, carry out effective adsorbing and trapping.
Graphene modified filter material fiber provided by the invention is applicable to coal-fired and non-ferrous metal metallurgy fume dust remover.Compare with conventional pocket type filter media fibre, graphene coated fiber is expected to have following advantage:
1) fiber surface graphene coated after, due to the intermolecular force between graphene film or between graphene film and fiber surface, be equivalent to make fibrillation surface to form a kind of nano level accumulating film, and the pliability of this film and mechanical strength are very good, can obviously strengthen the mechanical strength of filter media fibre, reduce the mechanical damage effects of external force to filter bag such as pulse dust cleaning, thereby obviously extend the service life of filtrate;
2) because Graphene has extraordinary electric conductivity, can be rapidly the electric charge of its surperficial grieshoch institute carrier band be shifted and discharged, this characteristic is particularly important to the pocket type selection of filtering material in electricity bag compound dust-collection device.Meanwhile, this class filtrate is also particularly suitable for having the filtration treatment of antistatic dust;
3), due to the protective effect of Graphene coating, can avoid micro-harmful constituent in institute's flow of process air to the corrosion of filter media fibre and oxidation, especially for preventing and treating O in electricity bag compound dust-collection device
3, NO
2and SO
3direct disoperation etc. component to filtrate, the service life of prolongation filtrate;
4) because Graphene class material has compared with bigger serface, to the part pollutant in flue gas, as mercury, NO
2agent HCl etc. has fine adsorbing and trapping effect, can promote nonvalent mercury to transform to its oxidation state.Strengthened the trapping effect of mercury.
5) Graphene has good hydrophobicity, can suppress the dewfall phenomenon of filtrate in high temperature wet flue gas.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
With graphene oxide to filter media fibre modification: the graphite powder graphite oxide that oxidation is made through Hummers method, is dissolved in the graphite oxide solution of making 2mg/mL in deionized water water after dry; Add afterwards 0.1% polyacrylamide and ultrasonic processing 30 minutes under 50w power, the stable graphene oxide dispersion liquid that obtains concentration and be 2mg/mL is standby;
Getting area is 100cm
2pPS (polyphenylene sulfide) filtrate (fiber that is 2-5 μ m by diameter is made into), with 3-aminopropyl triethoxysilane, as coupling agent and ethanol, by 1:3 mass ratio, be mixed and made into pretreatment liquid 2-3mL, be sprayed on uniformly filter fiber filter material surface;
The graphene suspension of making is coated in to filter media fibre surface uniformly by the mode of dipping, through 5 hours naturally place after stabilisation, the ethanolic solution that recycles deionized water or 70% cleans, filter fiber filtrate is dried 10 hours in 110 ℃ in vacuum drying chamber, can make the PPS filter media fibre with graphene oxide modification.
Embodiment 2
With graphene oxide to filter media fibre modification: the graphite powder graphite oxide that oxidation is made through Hummers method, is dissolved in the graphite oxide solution of making 2mg/mL in deionized water water after dry; The acetic acid that adds 2mL concentration 10% as reductant and emulsifying agent, adds 0.1% polyacrylamide and ultrasonic processing 60 minutes under 50w power with polyvinyl alcohol mixing liquid afterwards, and the stable graphene oxide dispersion liquid that obtains concentration and be 2mg/mL is standby;
By the polyurethane fiber silk group of 10g diameter 5-10 μ m; With 3-aminopropyl triethoxysilane, as coupling agent, mix by the volume ratio of 1:3 with ethanol, then cellosilk mass is immersed, soak and pull out and dry after 4-5 hour;
Afterwards, again silk group is immersed in above-mentioned prepared graphene suspension and soaks 2-3, after pulling out through 5 hours naturally place, graphene film is deposited on after fiber surface stabilisation gradually, recycling water or light naphtha ethanol clean, filter fiber filtrate is dried 10 hours in 110 ℃ in vacuum drying chamber, can make the PPS filter media fibre with graphene oxide modification.
Embodiment 3
The graphite powder graphite oxide that oxidation is made through Hummers method, is dissolved in the graphite oxide solution of making 2mg/mL in deionized water water after being dried; The acetic acid that adds 2mL concentration 10% as reductant and emulsifying agent, adds 0.1% polyacrylamide and ultrasonic processing 60 minutes under 50w power with polyvinyl alcohol mixing liquid afterwards, and the stable graphene oxide dispersion liquid that obtains concentration and be 2mg/mL is standby
By 0.3m
2pPS filtrate in vacuum drying chamber, dry 10 hours in 110 ℃, with 3-aminopropyl triethoxysilane, as coupling agent, mix with ethanol 1:3, be sprayed on uniformly filter fiber filter material surface, and dry;
The graphene suspension of making is coated in to filter media fibre surface uniformly by the mode of dipping, through 5 hours naturally place after stabilisation, recycling water or light naphtha clean, filter fiber filtrate is dried 10 hours in 90 ℃ in vacuum drying chamber, can make the PPS filter media fibre with graphene oxide modification.
Above-mentioned modified filter material and unmodified filtrate are contrasted, found that, the filtrate electric conductivity after modification improves 10 times of left and right, and drawing mechanical performance improves more than 50%; Again above-mentioned modified filter material is made to filter bag, and compare with the made filter bag of unmodified filtrate, after found that modification, to the efficiency of dust collection of PM2.5 fine particle, can improve 5-10%, best removal efficiency to heavy metal Hg can reach more than 70%, and the NO2 in flue gas is also had to obvious Adsorption effect.
Embodiment 4
A method of utilizing Graphene modification filter fabric of bag filter precipitator fiber, comprises the following steps:
1) preparation of graphene dispersing solution:
A. Graphene makes by oxidation-reduction process via Hummers method: the graphite powder graphite oxide that oxidation is made through Hummers method through 90 degree condensing reflux 12h, and makes the graphene solution of 2mg/mL under the effect of hydrazine hydrate after ultrasonic dispersion.
B. by add polarity dispersant in graphene solution, after high-speed stirred and ultrasonic dispersion, make stable graphene dispersing solution, described polarity dispersant is polyacrylamide or polyvinyl alcohol.
2) preliminary treatment of filter fiber filter material surface: filter fiber filtrate is mixed by the volume ratio of 1:3 with ethanol as coupling agent with 3-aminopropyl triethoxysilane, be sprayed on uniformly filter fiber filter material surface; Described filter fiber filtrate refers to that one or more in polyurethane, polyamide fiber, poly-propionitrile fiber, polyphenylene sulfide or polytetrafluoroethylene fibre are compound, and its state is fibre bundle before knitting or the filter cloth of forming.
3) coating to filter media fibre by the Graphene colloidal sol of making: the Graphene colloidal sol that the mode that employing is dipped or sprayed is made step (1) is coated in step (2) gained filter fiber filter material surface; Described painting method refers to filter media fibre to be immersed in graphene dispersing solution to infiltrate and applies, or utilizes spray gun that graphene dispersing solution is sprayed on fibre bundle or form the fiber surface of filter cloth.
4) the dry processing of filter media fibre: after the stabilisation of placement naturally of 2 hours, recycling water or light naphtha propyl alcohol clean, and filter fiber filtrate is dried 10 hours in 110 ℃ in vacuum drying chamber by step (3) gained filter media fibre.
Claims (7)
1. a method of utilizing Graphene modification filter fabric of bag filter precipitator fiber, is characterized in that, comprises the following steps:
1) preparation of graphene dispersing solution: take graphite as raw material, by oxidation-reduction method make Graphene and be scattered in water or organic solvent in;
2) preliminary treatment of filter fiber filter material surface: adopt 3-aminopropyl triethoxysilane to mix by the volume ratio of 1: 3 with ethanol as coupling agent filter fiber filtrate, be sprayed on uniformly filter fiber filter material surface;
3) coating to filter media fibre by the graphene dispersing solution of making: the graphene dispersing solution that the mode that employing is dipped or sprayed is made step (1) is coated in step (2) gained filter fiber filter material surface;
4) the dry processing of filter media fibre: after the stabilisation of placement naturally of 24 hours, recycling water or light naphtha clean, and filter fiber filtrate is dried 10 hours in 110 ℃ in vacuum drying chamber by step (3) gained filter media fibre.
2. a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber according to claim 1, it is characterized in that, concrete steps prepared by described graphene dispersing solution are: Graphene and be scattered in water or organic solvent in form graphene suspension, by the water to graphene suspension, add polarity dispersant, after stirring, after ultrasonic dispersion, be mixed and made into graphene dispersing solution, the concentration of Graphene is 0.5-20g/L; Described polarity dispersant is polyacrylamide or polyvinyl alcohol, and graphene uniform is scattered in these dispersant nonpolar liquids.
3. a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber according to claim 1, it is characterized in that, described graphene dispersing solution is to make by the following method: the step of the method by graphite powder by oxidation-reduction by graphite-graphene oxide-Graphene makes graphene oxide or reduction state graphene, make its ultrasonic being scattered in water or organic solvent, can obtain stable graphene dispersing solution, described organic solvent comprises ethanol.
4. according to a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber described in claim 1 or 2 or 3, it is characterized in that, described Graphene is graphene oxide, reduction state graphene or the compound of the two; Its raw material sources are that graphene oxide or graphite oxide make through disperseing, reducing.
5. a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber according to claim 1, it is characterized in that, described filter fiber filtrate refers to that one or more in polyurethane, polyamide fiber, poly-propionitrile fiber, polyphenylene sulfide or polytetrafluoroethylene fibre are compound, and its state is fibre bundle before knitting or the filter cloth of forming.
6. a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber according to claim 1, it is characterized in that, described painting method refers to filter media fibre to be immersed in graphene dispersing solution to infiltrate and applies, or utilizes spray gun that graphene dispersing solution is sprayed on fibre bundle or form the fiber surface of filter cloth.
7. a kind of method of utilizing Graphene modification filter fabric of bag filter precipitator fiber according to claim 1, it is characterized in that, filter media fibre after coating is after the stabilisation of placement naturally of 2-20 hour, recycling water or light naphtha clean, pass through afterwards normal pressure or vacuumize, make required Graphene modified filter material fiber.
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