CN108816217A - A kind of preparation method of the automobile-used cleanser of ira situ degradation VOCs - Google Patents
A kind of preparation method of the automobile-used cleanser of ira situ degradation VOCs Download PDFInfo
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- CN108816217A CN108816217A CN201810423132.3A CN201810423132A CN108816217A CN 108816217 A CN108816217 A CN 108816217A CN 201810423132 A CN201810423132 A CN 201810423132A CN 108816217 A CN108816217 A CN 108816217A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- 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
- 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 cleanser technical fields, and in particular to a kind of preparation method of the automobile-used cleanser of ira situ degradation VOCs, the preparation method of the automobile-used cleanser of the ira situ degradation VOCs include 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 dispersing modified porous carbon fiber in a solvent, is subsequently added into graphene oxide, after mixing evenly, obtains the automobile-used cleanser of ira situ degradation VOCs.The automobile-used cleanser of ira situ degradation VOCs of the 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 cleanser technical fields, and in particular to a kind of system of the automobile-used cleanser of ira situ degradation VOCs
Preparation Method.
Background technique
It is easy to cause acute poisoning when VOCs (volatile organic compounds) excessive concentration in room air, less serious case can go out
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 of VOCs pollution, slow poisoning can be caused, damage liver and nervous system 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 determined as carcinogenic and causes deformed material by the World Health Organization at present, is caused by VOCs
Indoor environmental pollution bring health problem 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 into air, and works as environment temperature mistake
When high or too low, this discharging modes are just restricted, or there is the substance of adsorptivity to adsorb pernicious gas, but this for purchase
The substance of class adsorptivity mostly can only adsorb indoor pollutant, not carry out degradation treatment to it, to can generate
Secondary pollution still has biggish harm to human body.
Summary of the invention
It is of the existing technology the purpose of the invention is to overcome the problems, such as, a kind of the automobile-used net of ira situ degradation VOCs is provided
The preparation method of agent, it can adsorb indoor VOCs, and can carry out ira situ degradation to VOCs in absorption point, have catalysis
It is high-efficient, thorough advantage of degrading.
To achieve the goals above, the present invention provides a kind of preparation method of the automobile-used cleanser of ira situ degradation VOCs, packet
Include 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, dries after stirring 30~45min, obtains ira situ degradation
The automobile-used cleanser of VOCs.
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,
Can make kaolin and organic titanate enters 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
Modified porous carbon fiber is finally reacted with diallyl dimethyl ammoniumchloride, has modified porous carbon fiber by carbon fiber
Positive charge, then will be stirred to react to the modified porous carbon fiber of positive charge with negatively charged graphite oxide, using graphite oxide
Alkene is further modified modified porous carbon fiber, improves the performance of its catalytic degradation VOCs.Ira situ degradation of the invention
The automobile-used cleanser pore structure rich in of VOCs, specific surface area is high, can adsorb indoor VOCs；And changing in hole
Property kaolin VOCs can be catalytically decomposed in adsorption site, have the characteristics that high catalytic efficiency, degradation it is thorough.
Specific embodiment
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 the automobile-used cleanser of ira situ degradation VOCs a kind of, is made of the substance of following parts by weight：Kaolin 5
~15 parts by weight, 3~12 parts by weight of organic titanate, 0.1~1 parts by weight of soluble metallic salt, 1~3 weight of silane coupling agent
Part, is gathered at 5~8 parts by weight of graphene oxide, 3~8 parts by weight of diallyl dimethyl ammoniumchloride, 1~5 parts by weight of foaming agent
80~150 parts by weight of allyl resin, 2~10 parts by weight of inorganic acid, 10~50 parts by weight of solvent.Under optimum condition, the original position
The automobile-used cleanser of degradation VOCs, 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
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.
The present invention also provides a kind of preparation methods of the automobile-used cleanser of ira situ degradation VOCs, 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, dries after stirring 30~45min, obtains ira situ degradation
The automobile-used cleanser of VOCs.
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.
Pore structure rich in kaolin, can adsorb the VOCs of air, in order to improve kaolinic specific surface
It is long-pending, it further include modifying kaolin processing under optimum condition, in the present invention, the modifying kaolin treatment process is：It will be high
After the grinding uniformly of ridge soil, 3~6h is then calcined at 300~500 DEG C.It is further preferred that the kaolinic partial 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, the positive fourth of metatitanic acid four
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 to titanium dioxide using metal ion, to widen titanium dioxide to visible light
Sensibility allows it to have 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 for 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 has positive charge, then will be stirred to react to the modified porous carbon fiber of positive charge 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- diethylformamide, ethyl alcohol, acetic acid, ethyl acetate, chloroform, tetrahydrofuran, petroleum ether, dimethyl are sub-
At least one of sulfone and water.
The automobile-used cleanser pore structure rich in of ira situ degradation VOCs of the invention, specific surface area is high, can inhale
Attached indoor VOCs；And the modified kaolin in hole can be catalytically decomposed VOCs in adsorption site, have catalysis effect
The feature that rate is high, degradation is thorough.
The present invention will be described in detail by way of examples below.
Embodiment 1
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：8 parts by weight of kaolin, titanium
Sour 8 parts by weight of tetra-ethyl ester, silane coupling agent KH7921.5 parts by weight, 4 parts by weight of graphene oxide, are gathered at 0.5 parts by weight of nickel acetate
4 parts by weight of diallyldimethylammonium chloride, N, 3 parts by weight of N '-dinitrosopentamethlyene tetramine, 105 weight of acrylic resin
Measure part, 4 parts by weight of hydrochloric acid (2M), 50 parts by weight of ethyl alcohol.
The preparation method of the automobile-used cleanser of the ira situ degradation VOCs, includes the following steps：
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramine is 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 meshes is crossed, then calcine 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 ira situ degradation VOCs
Automobile-used cleanser.
Embodiment 2
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：12 parts by weight of kaolin, titanium
Sour 5 parts by weight of tetra-isopropyl, 0.8 parts by weight of iron chloride, silane coupling agent KH5801.8 parts by weight, 6 parts by weight of graphene oxide,
5 parts by weight of diallyl dimethyl ammoniumchloride, N, 2 parts by weight of N '-dinitrosopentamethlyene tetramine, acrylic resin 100
Parts by weight, 3 parts by weight of hydrochloric acid (3M), 45 parts by weight of water.
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramine is 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 meshes is crossed, then calcine 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 ira situ degradation VOCs's
Automobile-used cleanser.
Embodiment 3
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：6 parts by weight of kaolin, titanium
Sour four methyl esters, 10 parts by weight, 0.3 parts by weight of nitrate, 1.2 parts by weight of Silane coupling agent KH550,6 parts by weight of graphene oxide,
7 parts by weight of diallyl dimethyl ammoniumchloride, 3 parts by weight of 4,4- oxobenzenesulfonyl hydrazide, 120 parts by weight of acrylic resin,
6 parts by weight of sulfuric acid (2M), 40 parts by weight of ethyl alcohol.
(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 meshes is crossed, then calcine 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 ira situ degradation VOCs
Automobile-used cleanser.
Embodiment 4
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：15 parts by weight of kaolin, titanium
3 parts by weight of sour four methyl esters, 1 parts by weight of silver nitrate, silane coupling agent KH5903 parts by weight, 5 parts by weight of graphene oxide, polydiene
8 parts by weight of diallyidimethylammonium chloride, 5 parts by weight of sodium carbonate, 80 parts by weight of acrylic resin, 10 parts by weight of inorganic acid, hydrochloric acid
(2M) 10 parts by weight, 10 parts by weight of water.
(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 meshes is crossed, then calcine 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 ira situ degradation VOCs's
Automobile-used cleanser.
Embodiment 5
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：5 parts by weight of kaolin, titanium
Sour four N-butyls, 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,
3 parts by weight of diallyl dimethyl ammoniumchloride, 1 parts by weight of sodium carbonate, 150 parts by weight of acrylic resin, 2 weight of hydrochloric acid (2M)
Part, 30 parts by weight of acetone.
(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 meshes is crossed, then calcine 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 ira situ degradation VOCs
Automobile-used cleanser.
Comparative example 1
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：8 parts by weight of kaolin, titanium
Sour 8 parts by weight of tetra-ethyl ester, silane coupling agent KH7921.5 parts by weight, 4 parts by weight of graphene oxide, diallyl dimethyl chlorine
Change 4 parts by weight of ammonium, N, 3 parts by weight of N '-dinitrosopentamethlyene tetramine, 105 parts by weight of acrylic resin, 50 weight of ethyl alcohol
Part.
The preparation method of the automobile-used cleanser of the ira situ degradation VOCs, includes the following steps：
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramine is 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 meshes is crossed, then calcine 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；
(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 ira situ degradation VOCs
Automobile-used cleanser.
Comparative example 2
A kind of automobile-used cleanser of ira situ degradation VOCs, is made of the substance of following parts by weight：8 parts by weight of kaolin, titanium
Sour 8 parts by weight of tetra-ethyl ester, 0.5 parts by weight of nickel acetate, 1.5 parts by weight of silane coupling agent KH792, diallyl dimethyl chlorine
Change 4 parts by weight of ammonium, N, 3 parts by weight of N '-dinitrosopentamethlyene tetramine, 105 parts by weight of acrylic resin, 4 weight of hydrochloric acid (2M)
Measure part, 50 parts by weight of ethyl alcohol.
The preparation method of the automobile-used cleanser of the ira situ degradation VOCs, includes the following steps：
(1) N is added in acrylic resin, N '-dinitrosopentamethlyene tetramine is 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 meshes is crossed, then calcine 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.
Experiment test：
Purification of the automobile-used cleanser of ira situ degradation VOCs in 1-5 of the embodiment of the present invention and comparative example 1-2 to VOCs
It can evaluate and be carried out in the straight type polytetrafluoroethylene (PTFE) pipe reactor of Φ 20mm, long 200mm, by the automobile-used cleanser of ira situ degradation VOCs
Be added polytetrafluoroethylene (PTFE) pipe reactor in, then by polytetrafluoroethylene (PTFE) pipe reactor be evacuated to pressure be -1.0KPa, then to
Unstripped gas is injected in polytetrafluoroethylene (PTFE) pipe reactor to normal pressure, tests purification of the VOCs catalytic purification agent to VOCs under different time
Rate, unstripped gas group become：VOCs concentration 21ppm (is 3 by formaldehyde, benzene,toluene,xylene 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 VOCs catalytic purification agent PARA FORMALDEHYDE PRILLS(91,95) in embodiment and comparative example
| 2h | 24h | 15 days | |
| Embodiment 1 | 41.6 | 79.2 | 98.5 |
| Embodiment 2 | 40.3 | 76.1 | 98.0 |
| Embodiment 3 | 36.0 | 74.6 | 94.2 |
| Embodiment 4 | 34.8 | 69.2 | 93.12 |
| Embodiment 5 | 29.1 | 72.5 | 96.2 |
| Comparative example 1 | 13.2 | 51.8 | 91.3 |
| Comparative example 2 | 23.6 | 60.8 | 88.8 |
Table 2：The purifying property of VOCs catalytic purification agent in embodiment and comparative example to benzene
Table 3：The purifying property of VOCs catalytic purification agent in embodiment and comparative example to toluene
| 2h | 24h | 15 days | |
| Embodiment 1 | 44.2 | 75.2 | 90.8 |
| Embodiment 2 | 42.3 | 72.2 | 96.9 |
| Embodiment 3 | 39.9 | 73.5 | 97.6 |
| Embodiment 4 | 40.8 | 72.1 | 93.1 |
| Embodiment 5 | 39.2 | 69.0 | 91.8 |
| Comparative example 1 | 31.5 | 61.4 | 87.2 |
| Comparative example 2 | 22.2 | 57.2 | 80.5 |
Table 4：The purifying property of VOCs catalytic purification agent paraxylene in embodiment and comparative example
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, 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, is belonged to
Protection scope of the present invention.
Claims (8)
1. the automobile-used cleanser preparation method of ira situ degradation VOCs a kind of, 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, dries after stirring 30~45min, obtains ira situ degradation VOCs
Automobile-used cleanser.
2. the preparation method of the automobile-used cleanser of ira situ degradation VOCs 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 meshes are crossed, then
3~6h is calcined at 300~500 DEG C.
3. the preparation method of the automobile-used cleanser of ira situ degradation VOCs according to claim 2, which is characterized in that the height
The partial size of ridge soil is 200~300 mesh.
4. the preparation method of the automobile-used cleanser of ira situ degradation VOCs according to claim 1, which is characterized in that the hair
Infusion is selected from least one of azo-compound, sulfonyl hydrazines compound, nitroso compound and carbonate.
5. the preparation method of the automobile-used cleanser of ira situ degradation VOCs according to claim 1, which is characterized in that described to have
Organic titanate is in tetraethyl titanate, tetramethoxy titanate ester, tetraisopropyl titanate, tetrabutyl titanate, tetra-n-butyl titanate
It is at least one.
6. the preparation method of the automobile-used cleanser of ira situ degradation VOCs according to claim 1, which is characterized in that it is described can
Soluble metal salts is selected from soluble manganese salt, soluble tungsten salt, soluble ferric iron salt, soluble copper salt, soluble gold salt, silver soluble
At least one of salt, soluble platinum salt, soluble rhodium salt or soluble palladium salt.
7. the preparation method of the automobile-used cleanser of ira situ degradation VOCs according to claim 1, which is characterized in that the silicon
Alkane coupling agent be selected from Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570, silane coupling agent KH580,
Silane coupling agent KH590, silane coupling agent KH792, silane coupling agent KBM602, silane coupling A 151 and silane coupling agent
At least one of A171.
8. the preparation method of the automobile-used cleanser of ira situ degradation VOCs according to claim 1, which is characterized in that described molten
Agent be selected from acetone, N,N-dimethylformamide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide, N, N- diethylformamide,
At least one of ethyl alcohol, acetic acid, ethyl acetate, chloroform, tetrahydrofuran, petroleum ether, dimethyl sulfoxide and water.
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