CN109603532A - A kind of composite spraying agent and preparation method thereof of decomposing formaldehyde benzene homologues TVOC - Google Patents
A kind of composite spraying agent and preparation method thereof of decomposing formaldehyde benzene homologues TVOC Download PDFInfo
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- CN109603532A CN109603532A CN201910023326.9A CN201910023326A CN109603532A CN 109603532 A CN109603532 A CN 109603532A CN 201910023326 A CN201910023326 A CN 201910023326A CN 109603532 A CN109603532 A CN 109603532A
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- tvoc
- benzene homologues
- carbon aerogels
- decomposing formaldehyde
- spraying agent
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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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7027—Aromatic hydrocarbons
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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 invention discloses the composite spraying agent and preparation method thereof of decomposing formaldehyde benzene homologues TVOC a kind of, the main points of technical solution are that absorption carrier is the carbon aerogels for adulterating tourmaline, nano photo-catalytic Cu2O‑TiO2Compound, stable dispersant are naturally occurring emulsifying agent, obtain absorption carrier using aeroge method, using the recombination process of micro-emulsion method for preparing nano photocatalyst and processing absorption carrier and photocatalyst.The beneficial effects of the invention are as follows can guarantee photocatalyst photocatalysis Decomposition reaction occurs under the conditions of natural lighting, core component depth is compound, reinforces the synergistic effect of adsorption-decomposition function, core group gradation diameter is down to 5nm or so, using high-pressure fog, pollution sources, fast degradation harmful substance can be goed deep into.
Description
Technical field
The present invention relates to environment protection field more particularly to a kind of the composite spraying agent and its preparation of decomposing formaldehyde benzene homologues TVOC
Method.
Background technique
The TVOC such as formaldehyde caused by household building materials, benzene homologues, which have human health, to be seriously endangered, therefore is gone out on the market
Many products and technology are showed to solve this problem.
Absorption-decomposition method that the normal method of removal formaldehyde benzene homologues TVOC has absorption method, decomposition method and the two to combine,
Absorption-decomposition method is more efficient compared to single processing method, and removal harmful substance is more thorough.Absorption-decomposition method is big at present
Mostly use active carbon and photocatalyst compound, on this basis, people have also carried out compounding ingredients material and preparation method thereof greatly
Amount is explored, and in the hope of improving product to degradation effect of harmful substance, enriches the function of product.
Such as application No. is the Chinese invention patents of CN200910013325.2 to disclose a kind of liquid active carbon colloid cream
Liquid and preparation method thereof by supermolecule poly cage type siloxanes, nano level active charcoal, nano diatomite, is received according to parts by weight
Rice titanium dioxide, nano-tourmaline, nano silica, rare earth activators, polyethylene glycol, sodium benzoate, calgon, ammonia
Base acid, vitamin C, surfactant are added in blender under the low speed of 40-50r/min and stir 0.5-1 hours, are put into ball milling
Machine carries out ball milling, ball milling speed 40-50r/min；Place into the moderate-speed mixer mixing 30- in blender with 300-500r/min
50 minutes；It places into 1-1.5 hours dry in 100-150 degrees Celsius of dryer；Place into high-speed mixer high speed 1500-
3000r/min is stirred 20-40 minutes；Impurity removing is removed with 100-150 mesh screen, both obtains pulvis；By carboxymethyl cellulose plus
Enter into distilled water, impregnates 2-3 days, spare solvent is made；Above-mentioned pulvis and spare solvent are put into low speed 40- in blender
50r/min is stirred 1.5-2 hours, then moderate-speed mixer mixing 300-500r/min is stirred 30-50 minutes；It is stirred above-mentioned
Mixed material is mixed to carry out decentralized processing 20-40 minutes using high-shear emulsion machine；It is carried out at dispersion with ultrasonic dispersing machine
Reason 5-15 minutes, obtains liquid active carbon colloid emulsion.
In above-mentioned technical proposal, inventor widens titanium dioxide using rare earth activators to the absorption bands of light, allows light
Light-catalyzed reaction can occur under conditions of natural lighting for catalyst, but during the preparation process, simultaneously by all important components
The exposure level of progress mechanical stirring, rare earth activators and titanium dioxide is difficult to ensure, it is difficult to which interaction generates expected skill
Art effect.Latex liquid water content is higher, is coated in body surface, slow drying speed, photocatalyst can not quickly with the oxygen in air
Gas contact, also just can not quickly generate light-catalyzed reaction.
Summary of the invention
In view of the above technical problems, the present invention provide it is a kind of can under the conditions of natural lighting decomposing formaldehyde benzene homologues TVOC
Composite spraying agent and preparation method thereof, the spray liniment are sprayed by high-pressure atomization bottle, and the partial size of effective component is low can be to 5nm, energy
The deep enough fast and effective decomposing harmful substances of pollution sources.
The invention is realized by the following technical scheme:
A kind of composite spraying agent of decomposing formaldehyde benzene homologues TVOC, by absorption carrier, nano photo-catalytic, stable dispersant group
At；According to mass percent, absorption carrier, nano photo-catalytic, stable dispersant content be respectively 15~30%, 5%~
15%, 55%~80%, the absorption carrier is the carbon aerogels for adulterating tourmaline；The nano photo-catalytic is Cu2O-TiO2It is multiple
Close object；The stable dispersant is naturally occurring emulsifying agent.
Preferably, in the carbon aerogels of the doping tourmaline, the mass percent of tourmaline is 1~10%.
Preferably, the Cu2O-TiO2In compound, Cu2The mass percent of O is 30~70%.
Preferably, the naturally occurring emulsifying agent is olive source emulsifier.
Above-mentioned composite spraying agent the preparation method is as follows:
S1, the carbon aerogels of doping tourmaline are obtained using aeroge method；
S2, Cu is prepared using microemulsion method2O-TiO2The co-precipitation presoma of compound；
S3, the product of S1, S2 carried out using microemulsion method it is compound.
S4, after mixing the product of S3 with naturally occurring emulsifying agent, it is packed into high-pressure fog bottle, obtains final products.
Wherein S1 the following steps are included:
S11, under atmosphere of inert gases, by the presoma of high temperature cabonization carbon aerogels, carbon steam is generated, after condensation
To pure carbon aerogels；
S12, after activating the carbon aerogels that S11 is obtained with KOH, the operating process of S11, the carbon airsetting after being activated are repeated
Glue；
S13, by nano-tourmaline and S12 to product be sufficiently mixed after, repeat the operating process in S11, mixed
The carbon aerogels of miscellaneous tourmaline.
Wherein S2 the following steps are included:
The microemulsion system that S21, configuration are made of surfactant, cosurfactant, water, oil；
S22, Cu is respectively configured2O presoma microemulsion, TiO2Presoma microemulsion, ammonia microemulsion, then mix three
Stirring is closed, until starting to precipitate；
Wherein S3 the following steps are included:
The carbon aerogels microemulsion of S31, configuration doping tourmaline；
S32, when S22 starts to precipitate, immediately be added S31 product, it is static after stirring；
S33, the product for being filtered, washed S32, and the standing and drying under constant-temperature vacuum environment obtain absorption carrier and light touching
The combination product of matchmaker.
Preferably, the presoma of carbon aerogels described in S11 is chitosan, bagasse, coconut husk.
Preferably, atmosphere of inert gases described in S11 is nitrogen, argon gas, xenon.
Preferably, high temperature described in S11 is 600~800 DEG C.
Preferably, surfactant described in S21 is bis- (2- ethylhexyl) Disodium sulfosuccinates (AOT), 16
Alkyl trimethyl ammonium bromide (CATB)；It is described to help surface agent and oil is n-hexyl alcohol；Normal heptane, the water are deionized water.
Preferably, in microemulsion system described in S21, oil, cosurfactant, surfactant, water ratio be
7:1:4:1。
Preferably, the temperature in constant-temperature vacuum environment described in S33 is 30~40 DEG C, and pressure is negative 1~3 atmosphere
Pressure.
After adopting the above technical scheme, the method have the advantages that:
1, it can guarantee that photocatalysis Decomposition reaction occurs under the conditions of natural lighting for photocatalyst.Cu2O is p-type semiconductor, band gap
It is relatively narrow, Cu2O and TiO2Band structure matching, under visible light conditions, light induced electron is from Cu2The conduction band of O is transferred to TiO2's
In conduction band, promote TiO2Light-catalyzed reaction.
2, high absorption property can be obtained.Carbon aerogels have more high-specific surface area, higher hole compared to general active carbon
Rate, less dense and stability are preferable, are one of optimal materials of catalyst carrier.
3, core component depth is compound, reinforces the synergistic effect of adsorption-decomposition function.The nano material prepared using microemulsion method
Particle diameter distribution is relatively narrow, size tunable, not easy to reunite between particle, and stability is good.
4, core group gradation diameter can go deep into pollution sources, fast degradation harmful substance using high-pressure fog down to 5nm or so.
5, tourmaline can issue far infrared, generate anion, have healthcare function to human health.
6, safe and reliable using naturally occurring emulsifying agent.If the emulsifier in olive source is a kind of safety, PEG is free of, mildly,
100% from renewable raw materials natural O/W emulsifier.It is very easy to prepare stable crystalline emulsion, high temperature and low temperature
Under have significant stability；More, such as the Taobao of purchasing channel.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done below with reference to preferred embodiment and is preferably illustrated.This field
It is to be understood by the skilled artisans that specifically described content is illustrative and be not restrictive below, this hair should not be limited with this
Bright protection scope.
Embodiment 1
A kind of composite spraying agent of decomposing formaldehyde benzene homologues TVOC, according to mass percent, when electrical by 20% doping
Carbon aerogels, 10% Cu2O-TiO2Compound photocatalyst, 70% olive source naturally occurring emulsifying agent, wherein adulterating tourmaline
In carbon aerogels, tourmaline mass percent is 3%, Cu2O-TiO2In compound photocatalyst, Cu2The mass percent of O is
30%.
In detail the preparation method is as follows:
S1, the carbon aerogels that tourmaline must be adulterated using aeroge method
S11,25g chitosan is dispersed in 500mL deionized water, the ice vinegar that volume fraction is 2% is then added dropwise
Solution is placed on stirring 30min on magnetic stirring apparatus and obtains clear solution by acid.3h is stood, chitosan solution is put into -75 DEG C
In the environment of freeze 12h after freeze-drying to whole moisture are removed, the chitosan after freeze-drying is put into tube furnace, lazy
Property atmosphere under, be to slowly warm up to 600 DEG C, then keep 5h at this temperature, required carbon aerogels can be obtained after cooling.
S12, carbon aerogels obtained in S11 step and KOH solution are mixed according to the ratio of mass ratio 1:3, will be mixed
Drying is completely disappeared to moisture in the environment of object is put into 100 DEG C, then mixture is put into tube furnace, in atmosphere of inert gases
Under be to slowly warm up to 600 DEG C, then keep 5h at this temperature.Product is washed with dilute hydrochloric acid to neutrality after cooling, is then existed
Dry 12h, completes activation process in the environment of 70 DEG C.
S13, claim nanometer to take elbaite powder 8g, mixed with the product in S12 step, appropriate amount of deionized water is added, puts
Enter and stir 30min in ultrasonic stirring pool, 2h is stood after stirring, filter, obtained solid product repeats the aeroge in S11
Operation, obtains tourmaline/carbon aerogels combination product.
S2, Cu is prepared using microemulsion method2O-TiO2The co-precipitation presoma of compound
S21, configuration microemulsion system.Using cetyl trimethylammonium bromide (CATB) be used as surfactant, just oneself
Alcohol is as oil phase and cosurfactant, and deionized water is as water phase.By n-hexyl alcohol, CATB, deionized water according to mass ratio 8:
Mixture, is stirred 30min strongly at room temperature, obtains the microemulsion of clear by 4:1 mixing.
S22, preparation TiO2Presoma microemulsion.3g metatitanic acid is taken, the 15mL concentrated sulfuric acid is added, is stirred completely molten to metatitanic acid
Solution, takes microemulsion obtained by a part of S21, meta-titanium acid solution is slowly added thereto, and stirs to solution clear, obtains
Metatitanic acid microemulsion.Microemulsion obtained by a part of S21 is separately taken, ammonium hydroxide is slowly added thereto, stirring is saturating to solution clarification
It is bright, obtain ammonia microemulsion.
S23, preparation Cu2O presoma microemulsion.1g copper chloride is taken, deionized water is added dropwise until being just completely dissolved, takes one
Microemulsion obtained by the S21 of part, copper chloride solution is slowly added thereto, and is stirred to solution clear, is obtained copper chloride
Microemulsion.
S24, preparation Cu2O-TiO2Composite micro-emulsion liquid.First metatitanic acid microemulsion and copper chloride microemulsion are mixed
30min is slow added into ammonia microemulsion, after enough ammonia microemulsions are added, persistently stirs 2h, heavy until starting to be precipitated
It forms sediment.
S3, the product of S1, S2 carried out using microemulsion method it is compound
S31, the A for obtaining S13 are ground to powder, are slowly added to the microemulsion that S21 is obtained, and stirring forms stable suspension
Liquid.
S32, absorption carrier A and photocatalyst B are compound.When the solution of S24 starts that precipitating is precipitated, S31 is obtained immediately
Suspension is slowly added thereto, and stirs 2h, stands 5h.
S33, the final combination product to AB separated.By S32 to product filter, solid portion first uses ethyl alcohol
Surfactant is washed away, then is washed with deionized.Product after washing, which is placed in constant-temperature vacuum case, is aged 5h, and environment temperature is set
35 DEG C are set to, 1.5 atmospheric pressure that are negative are arranged in pressure.
S4, the product of S33 is added in the naturally occurring emulsifying agent in olive source, stirs evenly, is packed into the high pressure of 5 atmospheric pressure
In spray bottle, the composite spraying agent of decomposing formaldehyde benzene homologues TVOC a kind of is obtained.
Embodiment 2
By Cu in embodiment 12O-TiO2Cu in compound2The mass percent of O is adjusted to 40%, keeps other conditions not
Become.
Embodiment 3
By Cu in embodiment 12O-TiO2Cu in compound2The mass percent of O is adjusted to 50%, keeps other conditions not
Become.
Embodiment 4
By Cu in embodiment 12O-TiO2Cu in compound2The mass percent of O is adjusted to 60%, keeps other conditions not
Become.
Embodiment 5
By Cu in embodiment 12O-TiO2Cu in compound2The mass percent of O is adjusted to 70%, keeps other conditions not
Become.
Degradation Formaldehyde efficacy test is carried out to the product of embodiment 1,2,3,4,5, test method is as follows:
(1) preparing 5 volumes is the identical colourless transparent glass bottle of 1L, respectively number 1,2,3,4,5, while to 5 glass
3 drop formalins are instilled in glass bottle, after 30min, check initial concentration of formaldehyde, and being denoted as initial concentration is C0。
(2) spray nozzle of the product in embodiment 1,2,3,4,5 respectively opens the activity of firmly 1,2,3,4,5 flint glass F bottles
Mouth is pressed 1 time with identical dynamics and time, seals vial active open immediately after.
(3) under the conditions of natural lighting, it is respectively C that concentration of formaldehyde inside each bottle is tested after a hour1、C2、C3、C4、
C5。
Test result is as follows:
| Embodiment number | Cu2O mass percent | Initial concentration (mg/L) | Concentration (mg/L) after degradation | Absorptivity |
| 1 | 30% | 255 | 131 | 48.63% |
| 2 | 40% | 256 | 97 | 62.11% |
| 3 | 50% | 254 | 56 | 77.95% |
| 4 | 60% | 254 | 18 | 92.91% |
| 5 | 70% | 253 | 61 | 75.89% |
In conclusion working as Cu2O-TiO2Cu in compound2When the mass percent of O is 60%, final products PARA FORMALDEHYDE PRILLS(91,95)
Assimilation effect is best.
Claims (10)
1. a kind of composite spraying agent of decomposing formaldehyde benzene homologues TVOC, which is characterized in that its each component and its shared quality
Percentage are as follows:
The carbon aerogels of doping tourmaline: 15~30%；
Cu2O-TiO2Composite photo catalyst: 5%~15%；
Naturally occurring emulsifying agent: 55%~80%.
2. the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as described in claim 1, which is characterized in that the doping is electrical
In the carbon aerogels of stone, the mass percent of tourmaline is 1~10%.
3. the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as described in claim 1, which is characterized in that the Cu2O-TiO2
In compound, Cu2The mass percent of O is 30~70%.
4. the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as claimed in claim 3, which is characterized in that the Cu2O-TiO2
In compound, Cu2The mass percent of O is 60%.
5. the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as described in claim 1, which is characterized in that described natural emulsified
Agent is the naturally occurring emulsifying agent in olive source.
6. a kind of preparation method of the composite spraying agent of decomposing formaldehyde benzene homologues TVOC, which comprises the following steps:
S1, the carbon aerogels of doping tourmaline are obtained using aeroge method；
S2, Cu is prepared using microemulsion method2O-TiO2The co-precipitation presoma of compound；
S3, the product of S1, S2 carried out using microemulsion method it is compound；
S4, after mixing the product of S3 with naturally occurring emulsifying agent, it is packed into high-pressure fog bottle, obtains final products.
Wherein S1 the following steps are included:
S11, under atmosphere of inert gases, by the presoma of high temperature cabonization carbon aerogels, generate carbon steam, obtained after condensation pure
Net carbon aerogels；
S12, after activating the carbon aerogels that S11 is obtained with KOH, the operating process of S11, the carbon aerogels after being activated are repeated；
S13, by nano-tourmaline and S12 to product be sufficiently mixed after, repeat the operating process in S11, obtain doping electricity
The carbon aerogels of gas stone.
Wherein S2 the following steps are included:
The microemulsion system that S21, configuration are made of surfactant, cosurfactant, water, oil；
S22, Cu is respectively configured2O presoma microemulsion, TiO2Then three is mixed and is stirred by presoma microemulsion, ammonia microemulsion
It mixes, until starting to precipitate；
Wherein S3 the following steps are included:
The carbon aerogels microemulsion of S31, configuration doping tourmaline；
S32, when S22 starts to precipitate, immediately be added S31 product, stood after stirring；
S33, the product for being filtered, washed S32, and the standing and drying under constant-temperature vacuum environment obtain absorption carrier and photocatalyst
Combination product.
7. the preparation method of the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as claimed in claim 6, which is characterized in that
The presoma of carbon aerogels described in S11 is chitosan solution, bagasse, coconut husk.
8. the preparation method of the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as claimed in claim 6, which is characterized in that
Surfactant described in S21 is cetyl trimethylammonium bromide (CATB), and the cosurfactant and oil are positive
Hexanol, water are deionized water.
9. the preparation method of the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as claimed in claim 6, which is characterized in that institute
State n-hexyl alcohol, CATB, deionized water mass ratio be 8:4:1.
10. the preparation method of the composite spraying agent of decomposing formaldehyde benzene homologues TVOC as claimed in claim 6, which is characterized in that
Temperature in constant-temperature vacuum environment described in S33 is 30~40 DEG C, and pressure is negative 1~3 atmospheric pressure.
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Application publication date: 20190412 |
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