CN108620038A - A kind of automobile-used purifying filter element and preparation method thereof - Google Patents
A kind of automobile-used purifying filter element and preparation method thereof Download PDFInfo
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- CN108620038A CN108620038A CN201810423138.0A CN201810423138A CN108620038A CN 108620038 A CN108620038 A CN 108620038A CN 201810423138 A CN201810423138 A CN 201810423138A CN 108620038 A CN108620038 A CN 108620038A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The present invention relates to automobile-used purifying filter element technical fields, and in particular to a kind of automobile-used purifying filter element and preparation method thereof, the preparation method of the automobile-used purifying filter element includes the following steps：(1) foaming agent is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains polypropylene fibre, and calcining obtains porous carbon fiber；(2) porous carbon fiber, kaolin, soluble metallic salt, silane coupling agent and organic titanate are subjected to thermal response in a solvent, obtain modified porous carbon fiber；(3) diallyl dimethyl ammoniumchloride is added after disperseing modified porous carbon fiber in a solvent, is subsequently added into graphene oxide, after stirring evenly, obtains automobile-used cleanser；(4) by automobile-used cleanser and attapulgite, pressing mold is molded after mixing, and automobile-used purifying filter element is obtained after sintering.The automobile-used purifying filter element of the present invention can adsorb interior VOCs, and carry out situ catalytic degradation in adsorption site, have catalytic degradation efficiency height, thorough feature of degrading.
Description
Technical field
The present invention relates to automobile-used purifying filter element technical fields, and in particular to a kind of automobile-used purifying filter element and preparation method thereof.
Background technology
It is easy to cause acute poisoning, less serious case that can go out when VOCs (volatile organic compounds) excessive concentration in room air
Now headache, dizzy, cough, Nausea and vomiting are in dead drunk liquor-saturated shape；Severe one will appear hepatotoxicity or even go into a coma quickly, and some can also energy
It is in peril of one's life.It hangs up one's hat in the interior that VOCs pollutes, slow poisoning, damage liver and nervous system can be caused to cause entirely
Body inability, drowsiness, pruitus etc..Some can also can cause endocrine disorder, influence sexual function；Benzene and dimethylbenzene can also damage
System, so that cause leukaemia.Oneself is caused through being determined as carcinogenic by the World Health Organization and causing deformed material by VOCs at present
The health problem that indoor environmental pollution is brought has become the new hot spot that the public attractes attention.
With the development of the social economy, automobile has become common walking-replacing tool, but containing big in automobile indoor air
The reason of VOCs of amount, generation VOCs is mainly in interior plastic parts containing a large amount of volatilizable pollutant.At present frequently with
The method of car room irritative gas of going out is to open the window, and by noxious gas emission to air, and works as environment temperature mistake
When high or too low, this discharging modes are just restricted, or substance of the purchase with adsorptivity adsorbs pernicious gas, but this
The substance of class adsorptivity mostly can only adsorb indoor pollutant, not carry out degradation treatment to it, to will produce
Secondary pollution still has larger harm to human body.
Invention content
It is of the existing technology the purpose of the invention is to overcome the problems, such as, a kind of preparation side of automobile-used purifying filter element is provided
Method, it can adsorb indoor VOCs, and can carry out ira situ degradation to VOCs in absorption point, have high catalytic efficiency, degradation
Thorough advantage.
To achieve the goals above, the present invention provides a kind of preparation method of automobile-used purifying filter element, includes the following steps：
(1) foaming agent is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains polypropylene fibre, by poly- third
Alkene fiber calcines 2~4h at 300~450 DEG C, obtains porous carbon fiber；
(2) porous carbon fiber, kaolin, soluble metallic salt, silane coupling agent and organic titanate are mixed in a solvent
Close uniformly after, obtain mixed system, then be added inorganic acid adjust mixed system pH value be acidity, then ultrasound 15~
30min, then 3~6h of sealing reaction at 80~120 DEG C, obtains modified porous carbon fiber；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in a solvent, diallyl dimethyl is then added
Ammonium chloride continues 30~45min of ultrasound, is subsequently added into graphene oxide, is dried after stirring 30~45min, obtains automobile-used purification
Agent；
(4) it is 1 by weight by above-mentioned automobile-used cleanser and attapulgite:The ratio of (30~100) is uniformly mixed, then
Pressing mold is molded, and is sintered in atmosphere of inert gases, and the automobile-used purifying filter element of ira situ degradation VOCs is obtained.
The present invention also provides a kind of automobile-used purifying filter elements being prepared according to the above method.
Through the above technical solutions, foaming agent is added in the present invention in acrylic resin first, and carry out electrostatic spinning and
Calcining, obtains porous carbon fiber, ultrasonic after then mixing porous carbon fiber with kaolin, metal ion and organic titanate,
Kaolin and organic titanate can be made to enter in the hole of porous carbon fiber, then carry out closing thermal response, obtain metal from
Titania-doped (the M-TiO of son2), it can have efficient catalytic performance in wider wave-length coverage, pass through M-TiO2To height
Ridge soil is further modified, and the modified kaolin with catalytic performance is generated in the hole of porous carbon fiber, i.e., modified porous
Carbon fiber finally reacts modified porous carbon fiber with diallyl dimethyl ammoniumchloride, and modified porous carbon fiber is made to carry
Positive charge, then the modified porous carbon fiber for waiting for positive charge is stirred to react with negatively charged graphite oxide, using graphite oxide
Alkene is further modified modified porous carbon fiber, improves the performance of its catalytic degradation VOCs.The automobile-used purification filter of the present invention
Core contains abundant pore structure, and specific surface area is high, can adsorb indoor VOCs；And the modified kaolin in hole can be
VOCs is catalytically decomposed in adsorption site, has the characteristics that high catalytic efficiency, degradation are thorough.
Specific implementation mode
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of automobile-used purifying filter element, is made of the substance of following parts by weight：5~15 parts by weight of kaolin,
3~12 parts by weight of organic titanate, 0.1~1 parts by weight of soluble metallic salt, 1~3 parts by weight of silane coupling agent, graphite oxide
5~8 parts by weight of alkene, 3~8 parts by weight of diallyl dimethyl ammoniumchloride, 1~5 parts by weight of foaming agent, acrylic resin 80~
150 parts by weight, 2~10 parts by weight of inorganic acid, 10~50 parts by weight of solvent, 1000~5000 parts by weight of attapulgite.Preferred stripe
Under part, the automobile-used purifying filter element is made of the substance of following parts by weight：6~12 parts by weight of kaolin, organic titanate 5~
10 parts by weight, 0.3~0.8 parts by weight of soluble metallic salt, 1.2~1.8 parts by weight of silane coupling agent, 5~8 weight of graphene oxide
Measure part, 3~8 parts by weight of diallyl dimethyl ammoniumchloride, 1~5 parts by weight of foaming agent, 100~120 weight of acrylic resin
Part, 3~6 parts by weight of inorganic acid, 10~50 parts by weight of solvent, 1000~5000 parts by weight of attapulgite.
The present invention also provides a kind of preparation methods of the automobile-used purifying filter element, include the following steps：
(1) foaming agent is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains polypropylene fibre, by poly- third
Alkene fiber calcines 2~4h at 300~450 DEG C, obtains porous carbon fiber；
(2) porous carbon fiber, kaolin, soluble metallic salt, silane coupling agent and organic titanate are mixed in a solvent
Close uniformly after, obtain mixed system, then be added inorganic acid adjust mixed system pH value be acidity, then ultrasound 15~
30min, then 3~6h of sealing reaction at 80~120 DEG C, obtains modified porous carbon fiber；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in a solvent, diallyl dimethyl is then added
Ammonium chloride continues 30~45min of ultrasound, is subsequently added into graphene oxide, is dried after stirring 30~45min, obtains automobile-used purification
Agent；
(4) it is 1 by weight by above-mentioned automobile-used cleanser and attapulgite:The ratio of (10~50) is uniformly mixed, then
Pressing mold is molded, and is sintered in atmosphere of inert gases, and the automobile-used purifying filter element of ira situ degradation VOCs is obtained.
Foaming agent is added in the present invention in acrylic resin first, and carries out electrostatic spinning and calcining, obtains porous carbon fiber
It ties up, under optimum condition, the electrostatic spinning process is：30~50kV of supply voltage, spinning temperature are 25~35 DEG C, relative humidity
60~75%；Multi needle spinneret unit syringe needle 25~35cm of spacing, spinneret unit syringe needle quantity are 60~90；The foaming agent
Selected from least one of azo-compound, sulfonyl hydrazines compound, nitroso compound and carbonate.
Contain abundant pore structure in kaolin, the VOCs of air can be adsorbed, in order to improve kaolinic specific surface
It is long-pending, further include modifying kaolin processing under optimum condition, in the present invention, the modifying kaolin treatment process is：It will be high
After the soil grinding uniformly of ridge, 3~6h is then calcined at 300~500 DEG C.It is further preferred that the kaolinic grain size is 200
~300 mesh.
It is ultrasonic after porous carbon fiber is mixed with kaolin, metal ion and organic titanate, kaolin can be made and had
Organic titanate enters in the hole of porous carbon fiber, then carries out closing thermal response, obtains metal ion doped titanium dioxide (M-
TiO2), it can have efficient catalytic performance in wider wave-length coverage, pass through M-TiO2Kaolin is further modified,
The modified kaolin with catalytic performance is generated in the hole of porous carbon fiber, i.e., modified porous carbon fiber.Under optimum condition,
The organic titanate is selected from tetraethyl titanate, tetramethoxy titanate ester, tetraisopropyl titanate, tetrabutyl titanate, four positive fourth of metatitanic acid
At least one of ester.
Under optimum condition, the silane coupling agent is selected from Silane coupling agent KH550, silane coupling agent KH560, silane coupled
Agent KH570, silane coupling agent KH580, silane coupling agent KH590, silane coupling agent KH792, silane coupling agent KBM602, silane
At least one of coupling agent A151 and silane coupling A 171.
The present invention is doped modification using metal ion to titanium dioxide, to widen titanium dioxide to visible light
Sensibility so that it can have an efficient catalytic performance in wider wave-length coverage, under optimum condition, the soluble metal
Salt is selected from soluble transition metal salt, for example, can be soluble manganese salt, soluble tungsten salt, soluble ferric iron salt, soluble copper salt,
At least one of soluble gold salt, soluble silver salt, soluble platinum salt, soluble rhodium salt or soluble palladium salt.
In the present invention, modified porous carbon fiber is reacted with diallyl dimethyl ammoniumchloride, makes modified porous carbon fiber
Dimension carries positive charge, then the modified porous carbon fiber for waiting for positive charge is stirred to react with negatively charged graphite oxide, using oxygen
Graphite alkene is further modified modified porous carbon fiber, improves the performance of its catalytic degradation VOCs.
It is further preferred that the solvent is selected from acetone, n,N-Dimethylformamide, N-Methyl pyrrolidone, N, N- bis-
Methylacetamide, N, N- diethylformamides, ethyl alcohol, acetic acid, ethyl acetate, chloroform, tetrahydrofuran, petroleum ether, dimethyl are sub-
At least one of sulfone and water.
It is concave-convex the filter core with purification function is made by automobile-used cleanser and attapulgite mixed sintering in the present invention
Containing abundant part pore structure in stick soil, the pernicious gas in air can be adsorbed, then by automobile-used cleanser to being harmful to gas
Body carries out catalytic degradation, has the function that purify air.
The present invention also provides a kind of automobile-used purifying filter elements being prepared according to the above method.
The automobile-used purifying filter element of the present invention contains abundant pore structure, and specific surface area is high, can adsorb indoor VOCs；
And the modified kaolin in hole can be catalytically decomposed VOCs in adsorption site, have high catalytic efficiency, degradation thorough
The characteristics of.
The present invention will be described in detail by way of examples below.
Embodiment 1
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：8 parts by weight of kaolin, 8 weight of tetraethyl titanate
Part, 0.5 parts by weight of nickel acetate, silane coupling agent KH7921.5 parts by weight, 4 parts by weight of graphene oxide, polydiene dimethylamine
4 parts by weight of ammonium chloride, N, 3 parts by weight of N '-dinitrosopentamethlyene tetramines, 105 parts by weight of acrylic resin, hydrochloric acid (2M)
4 parts by weight, 50 parts by weight of ethyl alcohol, 2000 parts by weight of attapulgite.
The preparation method of the automobile-used purifying filter element, includes the following steps：
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramines are uniformly mixed, and then electrostatic spinning obtains
To polypropylene fibre, the electrostatic spinning process is：Supply voltage 50kV, spinning temperature are 35 DEG C, relative humidity 75%；Spininess
Head spinneret unit syringe needle spacing 35cm, spinneret unit syringe needle quantity are 90；
Polypropylene fibre is calcined into 3h at 350 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 5h at 400 DEG C；
Porous carbon fiber, kaolin, nickel acetate, silane coupling agent KH792 and tetraethyl titanate are mixed in ethanol
After even, mixed system is obtained, hydrochloric acid (2M) is then added and adjusts the pH value of mixed system for 5.8,15~30min of ultrasound, then
3~6h of sealing reaction, obtains modified porous carbon fiber at 80~120 DEG C；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in ethanol, diallyl dimethyl is then added
Ammonium chloride continues 30~45min of ultrasound, is subsequently added into graphene oxide, after stirring 30~45min, obtains automobile-used cleanser；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Embodiment 2
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：12 parts by weight of kaolin, tetraisopropyl titanate 5
Parts by weight, 0.8 parts by weight of iron chloride, silane coupling agent KH5801.8 parts by weight, 6 parts by weight of graphene oxide, polydiene propyl
5 parts by weight of alkyl dimethyl ammonium chloride, N, 2 parts by weight of N '-dinitrosopentamethlyene tetramines, 100 parts by weight of acrylic resin, hydrochloric acid
(3M) 3 parts by weight, 45 parts by weight of water, 3000 parts by weight of attapulgite.
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramines are uniformly mixed, and then electrostatic spinning obtains
To polypropylene fibre, the electrostatic spinning process is：Supply voltage 50kV, spinning temperature are 35 DEG C, relative humidity 75%；Spininess
Head spinneret unit syringe needle spacing 35cm, spinneret unit syringe needle quantity are 90；
Polypropylene fibre is calcined into 2.5h at 400 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 5h at 350 DEG C；
Porous carbon fiber, kaolin, iron chloride, silane coupling agent KH580 and tetraisopropyl titanate are mixed in water
After even, mixed system is obtained, hydrochloric acid (3M) is then added and adjusts the pH value of mixed system for 5.3,15~30min of ultrasound, then
Sealing reaction 4h, obtains modified porous carbon fiber at 100 DEG C；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in water, diallyl dimethyl chlorine is then added
Change ammonium, continue 30~45min of ultrasound, be subsequently added into graphene oxide, after stirring 30~45min, obtains automobile-used cleanser；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Embodiment 3
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：6 parts by weight of kaolin, 10 weight of tetramethoxy titanate ester
Measure part, 0.3 parts by weight of nitrate, 1.2 parts by weight of Silane coupling agent KH550,6 parts by weight of graphene oxide, polydiene propyl two
7 parts by weight of ammonio methacrylate, 3 parts by weight of 4,4- oxobenzenesulfonyl hydrazide, 120 parts by weight of acrylic resin, 6 weight of sulfuric acid (2M)
Part, 40 parts by weight of ethyl alcohol, 2500 parts by weight of attapulgite.
(1) 4,4- oxobenzenesulfonyl hydrazide is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains poly- third
Alkene fiber, the electrostatic spinning process are：Supply voltage 50kV, spinning temperature are 35 DEG C, relative humidity 75%；Multi needle spinneret
Unit syringe needle spacing 35cm, spinneret unit syringe needle quantity are 90；
Polypropylene fibre is calcined into 2.5h at 350 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 4h at 400 DEG C；
Porous carbon fiber, kaolin, silver nitrate, Silane coupling agent KH550 and tetramethoxy titanate ester are mixed in ethanol
After even, mixed system is obtained, it is 6 that sulfuric acid (2M), which is then added, and adjusts the pH value of mixed system, then 15~30min of ultrasound exists
Sealing reaction 3h, obtains modified porous carbon fiber at 120 DEG C；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in ethanol, diallyl dimethyl is then added
Ammonium chloride continues 30~45min of ultrasound, is subsequently added into graphene oxide, after stirring 30~45min, obtains automobile-used cleanser；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Embodiment 4
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：15 parts by weight of kaolin, 3 weight of tetramethoxy titanate ester
Measure part, 1 parts by weight of silver nitrate, silane coupling agent KH5903 parts by weight, 5 parts by weight of graphene oxide, diallyl dimethyl
8 parts by weight of ammonium chloride, 5 parts by weight of sodium carbonate, 80 parts by weight of acrylic resin, 10 parts by weight of inorganic acid, 10 weight of hydrochloric acid (2M)
Part, 10 parts by weight of water, 1000 parts by weight of attapulgite.
(1) sodium carbonate is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains polypropylene fibre, described quiet
Electrospinning process is：Supply voltage 30kV, spinning temperature are 25 DEG C, relative humidity 60%；Multi needle spinneret unit syringe needle spacing
25cm, spinneret unit syringe needle quantity are 60；
Polypropylene fibre is calcined into 4h at 450 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 3h at 500 DEG C；
Porous carbon fiber, kaolin, silver nitrate, silane coupling agent KH590 and tetramethoxy titanate ester are uniformly mixed in water
Afterwards, mixed system is obtained, it is 4.5 that hydrochloric acid (2M), which is then added, and adjusts the pH value of mixed system, and reaction is then sealed at 80 DEG C
6h obtains modified porous carbon fiber；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in water, diallyl dimethyl chlorine is then added
Change ammonium, continue 30~45min of ultrasound, be subsequently added into graphene oxide, after stirring 30~45min, obtains automobile-used cleanser；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Embodiment 5
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：5 parts by weight of kaolin, tetra-n-butyl titanate 12
Parts by weight, 0.1 parts by weight of manganese chloride, silane coupling agent KH5901 parts by weight, 8 parts by weight of graphene oxide, polydiene propyl two
3 parts by weight of ammonio methacrylate, 1 parts by weight of sodium carbonate, 150 parts by weight of acrylic resin, 2 parts by weight of hydrochloric acid (2M), 30 weight of acetone
Measure part, 5000 parts by weight of attapulgite.
(1) sodium carbonate is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains polypropylene fibre, described quiet
Electrospinning process is：Supply voltage 30kV, spinning temperature are 25 DEG C, relative humidity 60%；Multi needle spinneret unit syringe needle spacing
25cm, spinneret unit syringe needle quantity are 60；
Polypropylene fibre is calcined into 2h at 300 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 6h at 300 DEG C；
Porous carbon fiber, kaolin, manganese chloride, silane coupling agent KH590 and tetra-n-butyl titanate are mixed in acetone
After uniformly, mixed system is obtained, hydrochloric acid (2M) is then added and adjusts the pH value of mixed system for 6.3,15~30min of ultrasound, so
The sealing reaction 3h at 100 DEG C afterwards, obtains modified porous carbon fiber；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in acetone, diallyl dimethyl is then added
Ammonium chloride continues 30~45min of ultrasound, is subsequently added into graphene oxide, after stirring 30~45min, obtains automobile-used cleanser；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Comparative example 1
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：8 parts by weight of kaolin, 8 weight of tetraethyl titanate
Part, silane coupling agent KH7921.5 parts by weight, 4 parts by weight of graphene oxide, 4 parts by weight of diallyl dimethyl ammoniumchloride,
3 parts by weight of N, N '-dinitrosopentamethlyene tetramine, 105 parts by weight of acrylic resin, 50 parts by weight of ethyl alcohol.
The preparation method of the automobile-used purifying filter element, includes the following steps：
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramines are uniformly mixed, and then electrostatic spinning obtains
To polypropylene fibre, the electrostatic spinning process is：Supply voltage 50kV, spinning temperature are 35 DEG C, relative humidity 75%；Spininess
Head spinneret unit syringe needle spacing 35cm, spinneret unit syringe needle quantity are 90；
Polypropylene fibre is calcined into 3h at 350 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 5h at 400 DEG C；
In ethanol after mixing by porous carbon fiber, kaolin, silane coupling agent KH792 and tetraethyl titanate, it obtains
To mixed system, 15~30min of ultrasound, then 3~6h of sealing reaction at 80~120 DEG C, obtains modified porous carbon fiber；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Comparative example 2
A kind of automobile-used purifying filter element, is made of the substance of following parts by weight：8 parts by weight of kaolin, 8 weight of tetraethyl titanate
Part, 0.5 parts by weight of nickel acetate, silane coupling agent KH7921.5 parts by weight, 4 parts by weight of diallyl dimethyl ammoniumchloride, N,
3 parts by weight of N '-dinitrosopentamethlyene tetramines, 105 parts by weight of acrylic resin, 4 parts by weight of hydrochloric acid (2M), 50 weight of ethyl alcohol
Part.
The preparation method of the automobile-used purifying filter element, includes the following steps：
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramines are uniformly mixed, and then electrostatic spinning obtains
To polypropylene fibre, the electrostatic spinning process is：Supply voltage 50kV, spinning temperature are 35 DEG C, relative humidity 75%；Spininess
Head spinneret unit syringe needle spacing 35cm, spinneret unit syringe needle quantity are 90；
Polypropylene fibre is calcined into 3h at 350 DEG C, obtains porous carbon fiber；
(2) by after kaolin grinding uniformly, 200 mesh sieve is crossed, then calcines 5h at 400 DEG C；
Porous carbon fiber, kaolin, nickel acetate, silane coupling agent KH792 and tetraethyl titanate are mixed in ethanol
After even, mixed system is obtained, hydrochloric acid (2M) is then added and adjusts the pH value of mixed system for 5.8,15~30min of ultrasound, then
3~6h of sealing reaction, obtains modified porous carbon fiber at 80~120 DEG C；
(4) the above-mentioned automobile-used purifying filter element of 100 parts by weight is taken to be uniformly mixed with attapulgite, then pressing mold is molded, and in argon
Atmosphere encloses middle sintering, obtains automobile-used purifying filter element.
Experiment test：
Automobile-used purifying filter element in 1-5 of the embodiment of the present invention and comparative example 1-2 evaluates in Φ the purifying property of VOCs
It is carried out in the straight type polytetrafluoroethylene (PTFE) pipe reactor of 20mm, long 200mm, polytetrafluoroethylene (PTFE) pipe reactor is added in automobile-used purifying filter element
In (diameter of automobile-used purifying filter element is slightly less than the internal diameter of polytetrafluoroethylene (PTFE) pipe reactor), then by polytetrafluoroethylene (PTFE) pipe reactor
It is -1.0KPa to be evacuated to pressure, and unstripped gas is then injected into polytetrafluoroethylene (PTFE) pipe reactor to normal pressure, tests different time
Under automobile-used purifying filter element the purifying rate of VOCs, unstripped gas group are become：VOCs concentration 21ppm is (by formaldehyde, benzene,toluene,xylene
It is 3 in molar ratio:2:1:1), remaining is air.Reaction carries out under 25 DEG C of atmospheric pressure environments, and experimental result is as shown in table 1~4.
Table 1：The purifying property of automobile-used purifying filter element PARA FORMALDEHYDE PRILLS(91,95) in embodiment and comparative example
| 2h | 24h | 15 days | |
| Embodiment 1 | 40.8 | 77.6 | 96.5 |
| Embodiment 2 | 39.5 | 74.6 | 96.0 |
| Embodiment 3 | 35.3 | 73.1 | 92.3 |
| Embodiment 4 | 34.1 | 67.8 | 91.3 |
| Embodiment 5 | 28.5 | 71.1 | 94.3 |
| Comparative example 1 | 12.9 | 50.8 | 89.5 |
| Comparative example 2 | 23.1 | 59.6 | 87.0 |
Table 2：The purifying property of automobile-used purifying filter element in embodiment and comparative example to benzene
| 2h | 24h | 15 days | |
| Embodiment 1 | 41.5 | 75.1 | 91.2 |
| Embodiment 2 | 40.3 | 72.4 | 91.8 |
| Embodiment 3 | 36.4 | 71.3 | 87.9 |
| Embodiment 4 | 35.3 | 66.2 | 86.8 |
| Embodiment 5 | 30.2 | 69.2 | 89.4 |
| Comparative example 1 | 16.3 | 50.6 | 79.5 |
| Comparative example 2 | 18.0 | 58.1 | 83.1 |
Table 3：The purifying property of automobile-used purifying filter element in embodiment and comparative example to toluene
| 2h | 24h | 15 days | |
| Embodiment 1 | 43.8 | 74.4 | 89.9 |
| Embodiment 2 | 41.9 | 71.5 | 95.9 |
| Embodiment 3 | 39.5 | 72.8 | 96.6 |
| Embodiment 4 | 40.4 | 71.4 | 92.2 |
| Embodiment 5 | 38.8 | 68.3 | 90.9 |
| Comparative example 1 | 31.2 | 60.8 | 86.3 |
| Comparative example 2 | 22.0 | 56.6 | 79.7 |
Table 4：The purifying property of automobile-used purifying filter element paraxylene in embodiment and comparative example
| 2h | 24h | 15 days | |
| Embodiment 1 | 42.3 | 73.4 | 86.0 |
| Embodiment 2 | 40.3 | 70.4 | 92.2 |
| Embodiment 3 | 37.9 | 71.7 | 92.8 |
| Embodiment 4 | 38.8 | 70.3 | 88.3 |
| Embodiment 5 | 37.2 | 67.1 | 87.0 |
| Comparative example 1 | 29.5 | 59.6 | 82.4 |
| Comparative example 2 | 20.2 | 55.3 | 75.7 |
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In the skill of the present invention
In art conception range, technical scheme of the present invention can be carried out a variety of simple variants, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, belongs to
Protection scope of the present invention.
Claims (9)
1. a kind of automobile-used purifying filter element preparation method, which is characterized in that include the following steps：
(1) foaming agent is added in acrylic resin to be uniformly mixed, then electrostatic spinning obtains polypropylene fibre, by polypropylene fibre
Dimension calcines 2~4h at 300~450 DEG C, obtains porous carbon fiber；
(2) porous carbon fiber, kaolin, soluble metallic salt, silane coupling agent and organic titanate are mixed in a solvent
After even, mixed system is obtained, it is acidity that inorganic acid, which is then added, and adjusts the pH value of mixed system, then 15~30min of ultrasound, so
3~6h of sealing reaction at 80~120 DEG C afterwards, obtains modified porous carbon fiber；
(3) by modified porous carbon fiber 15~30min of ultrasonic disperse in a solvent, diallyl dimethyl chlorination is then added
Ammonium continues 30~45min of ultrasound, is subsequently added into graphene oxide, is dried after stirring 30~45min, obtains automobile-used cleanser；
(4) it is 1 by weight by above-mentioned automobile-used cleanser and attapulgite:The ratio of (10~50) is uniformly mixed, then pressing mold
Molding, and be sintered in atmosphere of inert gases, obtain automobile-used purifying filter element.
2. the preparation method of automobile-used purifying filter element according to claim 1, which is characterized in that further include modifying kaolin
Processing, the modifying kaolin treatment process are：After kaolin grinding uniformly, 200 mesh sieve is crossed, then at 300~500 DEG C
3~6h of lower calcining.
3. the preparation method of automobile-used purifying filter element according to claim 2, which is characterized in that the kaolinic grain size is
200~300 mesh.
4. the preparation method of automobile-used purifying filter element according to claim 1, which is characterized in that the foaming agent is selected from azo
At least one of compound, sulfonyl hydrazines compound, nitroso compound and carbonate.
5. the preparation method of automobile-used purifying filter element according to claim 1, which is characterized in that the organic titanate is selected from
At least one of tetraethyl titanate, tetramethoxy titanate ester, tetraisopropyl titanate, tetrabutyl titanate, tetra-n-butyl titanate.
6. the preparation method of automobile-used purifying filter element according to claim 1, which is characterized in that the soluble metallic salt choosing
From soluble manganese salt, soluble tungsten salt, soluble ferric iron salt, soluble copper salt, soluble gold salt, soluble silver salt, soluble platinum
At least one of salt, soluble rhodium salt or soluble palladium salt.
7. the preparation method of automobile-used purifying filter element according to claim 1, which is characterized in that the silane coupling agent is selected from
Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH580, silane coupling agent
In KH590, silane coupling agent KH792, silane coupling agent KBM602, silane coupling A 151 and silane coupling A 171 at least
It is a kind of.
8. the preparation method of automobile-used purifying filter element according to claim 1, which is characterized in that the solvent be selected from acetone,
N,N-dimethylformamide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, N, N- diethylformamides, ethyl alcohol, acetic acid,
At least one of ethyl acetate, chloroform, tetrahydrofuran, petroleum ether, dimethyl sulfoxide (DMSO) and water.
9. a kind of automobile-used purifying filter element, which is characterized in that according to the preparation method system described in any one of claim 1~8
It is standby to obtain.
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