CN105642333B - A kind of Multifunctional environment purification composite material and preparation method and application - Google Patents
A kind of Multifunctional environment purification composite material and preparation method and application Download PDFInfo
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- 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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- 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
- B01D53/90—Injecting reactants
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J23/34—Manganese
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- B01D2251/00—Reactants
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- B01D2251/104—Ozone
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Abstract
The invention discloses a kind of Multifunctional environments to purify composite material, and it includes molecular sieve carrier, TiO which, which is a kind of,2And the catalyst of a small amount of transition metal oxide, the TiO2It is supported on the molecular sieve carrier with transition metal oxide.The invention also discloses the preparation method of above-mentioned Multifunctional environment purification composite material, the catalyst prepared has many characteristics, such as high-specific surface area, high catalytic oxidation activity, active component high degree of dispersion and purification stability and high efficiency；The present invention further discloses application of the above-mentioned Multifunctional environment purification composite material in photochemical catalytic oxidation and catalytic ozonation synergistic purification pollutant, multifunctional composite not only absorbs ultraviolet light and generates good Photocatalytic oxidation activity, simultaneously can also efficient-decomposition ozone and using ozone decompose generate highly reactive form of oxygen oxidation stain object, and realize photochemical catalytic oxidation and catalytic ozonation synergistic purification pollutant, degradation is thorough, purification efficiency is high.
Description
Technical field
The invention belongs to waste gas purification Material Fields, and in particular to a kind of Multifunctional environment purification composite catalyst and its system
Preparation Method and application.
Background technique
Currently, China's atmospheric environment situation very severe, with fine particle (PM2.5), ozone (O3) etc. the area that is characterized
Property compound pollution in domain becomes increasingly conspicuous, and the frequency that air heavily contaminated phenomenon occurs simultaneously on a large scale in region is increasing, becomes
Outstanding problem in Sustainable Socioeconomic Development.It is organic as the main producers object volatility for promoting ozone and PM2.5 to be formed
Object (VOCs) is also increasingly subject to the concern of society.Therefore, the discharge for controlling VOCs is that PM2.5 and low latitude ozone are dirty in control atmosphere
One of the important means of dye.Especially in recent years, the developed areas atmosphere pollution such as Pearl River Delta, the Yangtze River Delta, Jing-jin-ji region is increasingly tight
Weight, gray haze day becomes more and more, this makes fine particles pollution representated by ozone and PM 2.5, gradually development be big city and
The primary formidable enemy of regional air pollution.
VOCs is related to that industry is numerous, type is more various, ingredient is more complicated, toxicity is stronger, and existing life source from a wealth of sources is again
There is industrial source, be the difficult point and key of China's air contaminant treatment, the end-of-pipe control technology of VOCs can be divided into two major classes: return
Receipts technology and destruction technology lack innovation since the developmental research of scavenging material, technology and technique etc. is weak especially on material
And breakthrough, and catalyst wherein play the role of it is very important, cause to lack at present efficiently, economic and stable VOCs and
Indoor combined pollutant administering method.Control technology is mainly heat-accumulation combustion (RTO), catalysis oxidation, directly combustion both at home and abroad at present
Burning, absorption, bioanalysis, absorption, plasma, photochemical catalytic oxidation etc..It is wherein the most universal with activated carbon adsorption, individually adsorb skill
Since discarded adsorbent belongs to hazardous waste, most enterprises irregularly replace art, perform practically no function, be used alone active carbon by
Gradually it is prohibited.Burning or Production by Catalytic Combustion Process, pyroreaction condition (200-850 DEG C), energy consumption height, potential huge security risk.Light
Catalysis technique is due to the advantages such as oxidability is strong, low energy consumption and reaction condition is mild, in recent years in air purification field
Obtain extensive concern.But there are still many deficiencies for traditional photocatalysis, as photo-quantum efficiency is low, electron-hole is compound and catalysis
Agent inactivation etc., seriously restricts its practical application.Vacuum ultraviolet photocatalysis is that a kind of ultrahigh in efficiency, powerful air cleaning are new
Technology obtains extensive concern in recent years.The energy of vacuum UV lamp is high, can generate a large amount of ozone.But traditional catalyst pair
The absorption of light and the decomposition of ozone and utilization efficiency are lower.The innovation of catalysis material is the basic and source of photocatalysis technology innovation
Spring, to occupy leading position in the development and application of catalysis technique, it is necessary to carry out the innovation of catalysis material first.With dirt
The complication of dye source and pollutant component, the increasing of discharge amount of pollution, the low efficiencys of these technologies, secondary pollution, corrosion equipment,
The disadvantages of complex process, investment are greatly, operating cost is high gradually appears.To overcome these disadvantages, studies, develops new air pollution
Purification techniques and material are especially urgent.
To adapt to increasingly strict environmental requirement, Recent study develops some Novel environment-friendlymaterial materials and technology, but still
So there is the defects of having a single function, inefficiency.Chinese invention patent CN101164695 discloses a kind of loaded nano dioxy
The preparation method for changing titanium, belongs to inorganic functional material preparation field.Based on porous si molecular sieves, it is with nano-titanium dioxide
The method of the composite material of object, guest materials size are limited by the nanoscale duct of material of main part；Specific method: configuration concentration
Range is the inorganic titanium saline solution of 6.25mmol/mL~37.5mmol/mL, using water or aqueous solutions of organic acids as solvent；Using
Incipient impregnation method will introduce inside porous material, the decentralization of impregnated sample room temperature be set 24 hours, moving into has poly- four
In the hydro-thermal tank of fluorine liner, hydrolyzed 0.5~4h hours, then 500 DEG C~700 DEG C under the conditions of 80 DEG C~120 DEG C of temperature range
The roasting temperature time is 2 hours, obtains the composite material with certain photocatalytic activity.Composite material obtained is applied to organic
The light degradation of object and catalyst carrier material.Chinese invention patent CN102380385A discloses a kind of load type metal doping Jie
Porous titanium dioxide photochemical catalyst and its preparation method and application, it is heavy mutually to be contained by carrier and the titanium colloidal sol of metallic components
It is long-pending, organic formwork agent is added in mixed sols, the high-temperature calcination after drying, the load type metal for being made required doped meso-porous two
Titania photocatalyst, titanium dioxide keep anatase crystal, and partial size is in 10-30nm, and aperture is in 2-20nm, large specific surface area
(≥200m2/g).Chinese invention patent CN101444725 discloses a kind of preparation side of load type titanium dioxide photocatalytic film
Method, the method includes TiO 2 sol preparation, ultrasonic titanium dioxide coating film, Best-Effort request and drying and calcining four steps
Suddenly.Chinese invention patent CN102614877A, which is disclosed, is related to transition metal element and nonmetal doping nano-titanium dioxide
The preparation method of modified light catalyst, comprising steps of it is thin to form titanium dioxide on metallic substrates using anodizing first
Film, after eluting solvent drying, then by transition metal solution and the mixing of nonmetalloid solution, in neutral conditions, using electrolysis
Established titanium deoxid film is modified by method, and modified titanium deoxid film is heated to 400 DEG C -500 DEG C and obtains
The modified light catalyst.The multi-functional coupling that Chinese invention patent CN101590403 discloses a kind of chemical technology field is urged
Agent and preparation method thereof；The catalyst is by the catalysis of catalyst carrier and load on a catalyst support with high adsorption
Agent composition, the component and weight percent of the catalyst are as follows: the major catalyst 55.0%~98.0% with photocatalytic activity,
Surplus is the metal oxide promoters with redox catalysis ability；The preparation method packet of the multifunctional coupling catalyst
It includes following steps: preparing precursor solution using major catalyst and co-catalyst；Precursor solution is adsorbed by dip loading to height
In the catalyst carrier of property；50~500 DEG C of heat dryings, obtain multifunctional coupling catalyst.Chinese invention patent
CN104258873A discloses a kind of preparation method of composite ozone catalyst for catalytic oxidation, belongs to environmental catalysis and water process neck
Domain.Its preparation step is as follows: the NaOH solution cleaning of haydite, dilute nitric acid solution being impregnated, deionized water is cleaned into water outlet
It is dried for standby after property；Using butyl titanate as presoma, it is mixed with dehydrated alcohol and inhibitor glacial acetic acid, is added appropriate
Water, obtained solution Sol A；A certain amount of manganese nitrate, ferric nitrate are added in dehydrated alcohol, wiring solution-forming B；By solution B
It is slowly dropped in solution Sol A, stirs, be fully hydrolyzed butyl titanate, obtain solution colloidal sol C；By ready haydite
It is immersed in solution colloidal sol C, after solution evaporation, drying, is placed in Muffle kiln roasting.Chinese invention patent CN101590403
Disclose a kind of multifunctional coupling catalyst and preparation method thereof of chemical technology field；The catalyst is by with high adsorption
The catalyst composition of catalyst carrier and load on a catalyst support, the component and weight percent of the catalyst are as follows: tool
There is the major catalyst 55.0%~98.0% of photocatalytic activity, surplus is that the metal oxide with redox catalysis ability helps
Catalyst；The preparation method of the multifunctional coupling catalyst includes the following steps: using before major catalyst and co-catalyst preparation
Drive solution；Precursor solution is passed through on dip loading to the catalyst carrier of high adsorption；50~500 DEG C of heat dryings, obtain
Multifunctional coupling catalyst.Chinese invention patent CN102240567A discloses mixing for a kind of room temperature or low-temperature catalyzed removal ozone
Miscellaneous manganese oxide molecular sieve integral catalyst and preparation method thereof is related to catalysis and field of environment protection.It is characterized in that using
Ceramic honeycomb monolith makees carrier, using the manganese oxide molecular sieve containing doping iron as active component.The manganese oxide molecular sieve of doping iron
It is characterized by having the structure of Hollandite- type manganese oxide octahedral molecular sieve (OMS), pore size is about that OMS introduces iron
The manganese oxide molecular sieve of ion formation doping iron.Removal ozone catalyst is prepared using redox-circumfluence method."TiO2/
The photocatalysis of Mn-ZSM-5 composite catalyst-ozone coupling is degraded acetaldehyde " report using ion-exchange is prepared for Mn-ZSM-5
Catalyst series, and TiO is prepared for using infusion process2/ Mn-ZSM-5 series composite catalyst.
Summary of the invention
The first purpose of this invention is to provide a kind of Multifunctional environment purification composite material, the material specific surface area and
Catalytic oxidation activity is high, active component high degree of dispersion, purification efficiency efficient stable.
Second object of the present invention is to provide the preparation method of above-mentioned Multifunctional environment purification composite material, the preparation
Method and process is succinct, condition is controllable, TiO2With transition metal oxide can growth in situ, kind be brilliant on molecular sieve carrier simultaneously,
It is repeated high, at low cost.
Final object of the present invention be to provide above-mentioned Multifunctional environment purification composite material photochemical catalytic oxidation with
Application in catalytic ozonation synergistic purification pollutant.
The first purpose of this invention is achieved through the following technical solutions: a kind of Multifunctional environment purification composite wood
Material, it includes molecular sieve carrier, TiO which, which is a kind of,2And the catalyst of a small amount of transition metal oxide, the TiO2
It is supported on the molecular sieve carrier with transition metal oxide.
The load capacity of transition metal oxide of the present invention is 0.05~10%, TiO2Load capacity is 1~30%.
Further, the load capacity of transition metal oxide of the present invention is 3~8%, TiO2Load capacity be 5~
15%.
As a kind of preferred embodiment of the invention, transition metal oxide of the present invention, which preferably comprises, to be contained
One or more of transition metal oxide of Cu, Mn, Co, Ni, Ce, Zn and Fe.Presoma is sulfate, nitrate, vinegar
Hydrochlorate or chloride.
As another preferred embodiment of the invention, molecular sieve carrier of the present invention includes but is not limited to powder
Last shape, spherical, column or honeycomb.
When molecular sieve carrier is powdered, carrying transition metal oxide and TiO2Being made after powder catalyst can be with
It is coated to cordierite honeycomb carrier, filter screen or foaming metal and is prepared into integral catalyzer on the net, can also add appropriate
Binder granulating and forming.
Second object of the present invention is achieved through the following technical solutions: above-mentioned Multifunctional environment purifies composite wood
A kind of preferred preparation method of material, comprising the following steps:
(1) transition metal salt presoma is chosen, transition metal salt precursor solution is prepared, under stirring, by molecule
Sieve carrier pours into the transition metal salt precursor solution, and turbid solution is made；
(2) butyl titanate, concentrated acid, acetyl class organic solvent are added in the turbid solution, after stirring, solution A is made；
(3) dehydrated alcohol is taken, water deionized water is added, is mixed, B solution is made；
(4) B solution is added drop-wise in solution A, is vigorously stirred mixing, form stable sol system；
(5) sol system in step (4) is placed into ageing, slowly polymerize between micelle after sol system is aged,
TiO2Simultaneously then the growth in situ on molecular sieve carrier, the gel of formation three-dimensional space network structure dry with metal oxide
After dry and roasting, Multifunctional environment is made and purifies composite material.
In the preparation method of above-mentioned Multifunctional environment purification composite material:
Transition metal salt precursor solution is prepared using dehydrated alcohol in step (1), the dehydrated alcohol with it is molecular sieve supported
The dosage relation of body is preferably 3~8mL:1g；The transition metal salt presoma quality m=[(0.05~10%) ×
mMolecular sieve supported weight×MTransition metal salt precursor molecule amount×nMetallic atom number in metal oxide]/(MTransition metal oxide molecular weight×nMetallic atom number in transition metal salt presoma)；Described
Transition metal salt presoma is to include one of Cu, Mn, Co, Ni, Ce, Zn and Fe transition metal or a variety of sulfate, nitre
Hydrochlorate, acetate or chloride.
Volumetric usage V=[(1~30%) × m of butyl titanate described in step (2)Molecular sieve supported weight×MButyl titanate molecular weight]/
(MTitania molecule amount×ρButyl titanate)；The volume ratio of the butyl titanate and the concentrated acid and acetyl class organic solvent is preferred are as follows: 10~
150:1~5:1；The concentrated acid is preferably concentrated hydrochloric acid and/or concentrated nitric acid, and the acetyl class organic solvent is preferably acetyl second
Acid or acetylacetone,2,4-pentanedione.
The volume ratio of dehydrated alcohol and deionized water is preferably 1~3.5:1 in step (3).
The volume ratio of B solution described in step (4) and the solution A is preferably 1:3~20.
Drying temperature is preferably 60~150 DEG C in step (5), and drying time is preferably 1~6h；Maturing temperature is preferably
300~800 DEG C, calcining time is preferably 1~5h.
Composite material, transition metal oxide and TiO are purified using the Multifunctional environment that the method for the present invention prepares2?
High degree of dispersion on molecular sieve carrier, large specific surface area not only absorb ultraviolet light and generate good Photocatalytic oxidation activity, simultaneously also
Energy efficient-decomposition ozone simultaneously decomposes generation active oxidation pollutant using ozone, and realizes photochemical catalytic oxidation and catalytic ozonation
Synergistic purification pollutant.
Wherein transition metal oxide can also promote TiO2High degree of dispersion and the activated centre decomposed and utilized as ozone,
The TiO of high degree of dispersion2Activated centre as photocatalytic activity.
The preparation method of the Multifunctional environment purification composite material further preferred as one kind of the invention, including it is following
Step:
(1) transition metal salt presoma is dissolved into dehydrated alcohol, transition metal salt precursor solution is made；
(2) under stirring, molecular sieve carrier is poured into above-mentioned precursor solution, turbid solution is made；
(3) butyl titanate, concentrated nitric acid and/or concentrated hydrochloric acid, acetoacetate or acetylacetone,2,4-pentanedione are added in above-mentioned turbid solution, stirs
30~90min is mixed, solution A is made；
(4) a certain amount of dehydrated alcohol, deionized water are sufficiently mixed, B solution is made；
(5) solution A is added dropwise in B solution, is vigorously stirred mixing, form stable sol system；
(6) 1~10h of ageing is placed, is slowly polymerize between the aged micelle of colloidal sol, TiO2With transition metal oxide in carrier
Upper growth in situ forms the gel of three-dimensional space network structure, and 1~6h is then dried at 60~150 DEG C；
(7) dry catalyst is placed in Muffle furnace, 1~5h is roasted under the conditions of 300~800 DEG C.
Final object of the present invention is achieved through the following technical solutions: above-mentioned Multifunctional environment purification is compound
Application of the material in photochemical catalytic oxidation and catalytic ozonation synergistic purification pollutant.
Further, above-mentioned Multifunctional environment purification composite material has photochemical catalytic oxidation and catalytic ozonation in preparation
The cleaning equipment of synergistic purification pollutant effect or the application in device.
For example, above-mentioned Multifunctional environment purification composite material is applied to indoor air purification equipment and fresh air air cleaning
In system or equipment, while it also can be widely applied to industrial organic exhaust gas and administer field especially there is photooxidation, photocatalysis
In the cleaning equipment or device of oxidation and catalytic ozonation synergistic purification pollutant effect.
Compared with prior art, the present invention has the advantage that
(1) in the present invention multifunctional composite preparation method process is simple, condition is controllable, TiO2It is same with transition metal
When growth in situ, kind are brilliant on carrier, repeatability is high, at low cost；
(2) there is high-ratio surface using the catalyst that the preparation method of the multifunctional composite in the present invention is prepared
The features such as long-pending, high catalytic oxidation activity, active component high degree of dispersion and purification stability and high efficiency；
(3) multifunctional composite in the present invention not only absorbs the good Photocatalytic oxidation activity of ultraviolet light generation, together
When efficient-decomposition ozone and can also be decomposed using ozone and generate highly reactive form of oxygen oxidation stain object, and realize photochemical catalytic oxidation and ozone
Catalysis oxidation synergistic purification pollutant, degradation is thorough, purification efficiency is high；
(4) multifunctional composite purification condition of the present invention is mild, energy consumption substantially reduces, securely and reliably, effectively avoids height
The drawbacks of warm high pressure etc. is run, being capable of the hard-degraded substance that can not aoxidize in independent ozone or catalytic oxidation system of deep oxidation
Such as " triphen " exhaust gas.
Detailed description of the invention
Fig. 1 is 1%MnO in the embodiment of the present invention 12- 20%TiO2/ molecular sieve TEM figure.
Specific embodiment
Embodiment 1
Multifunctional environment provided in this embodiment purifies composite material, which includes molecular sieve carrier, TiO2With
And a small amount of transition metal oxide MnO2, TiO2With transition metal oxide MnO2It is supported on molecular sieve carrier；Wherein transition gold
The load capacity for belonging to oxide is 1%, TiO2Load capacity is 20%, i.e., Multifunctional environment purifies composite material 1%MnO2- 20%
TiO2/ molecular sieve.
The Multifunctional environment purifies composite material 1%MnO2- 20%TiO2/ molecular sieve the preparation method is as follows:
(1) according to required load capacity, with 200mL dehydrated alcohol dissolution 0.846g manganese acetate (four acetate hydrate manganese) transition gold
Belong to salt precursor body, stirring to dissolution；Under stirring, 30g powdery zeolite molecular sieve is poured into acetic acid manganese solution, is stirred
Turbid solution is made in 60min；
(2) 26mL butyl titanate (butyl titanate) is added in turbid solution, 0.5mL concentrated hydrochloric acid, 0.25mL acetoacetate,
60min is sufficiently stirred, solution A is made；
(3) 8mL ethyl alcohol, 6mL deionized water are sufficiently mixed, B solution is made；
(4) B solution is added dropwise to dropwise in the solution A being vigorously stirred, is vigorously stirred mixing, stirring rate is about
350rpm/min forms stable sol system；
(5) ageing 12h is placed, slowly polymerize between the aged micelle of colloidal sol, forms the gel of three-dimensional space network structure, so
6h is dried at 100 DEG C afterwards；Dry catalyst is placed in Muffle furnace, roasts 3h under the conditions of 400 DEG C, multi-functional ring needed for being made
Border catalytic purification material, the multi-functional composite catalyst include molecular sieve carrier, TiO2And transition metal oxide, TiO2And mistake
It crosses metal oxide supported on the molecular sieve carrier, is named as 1%MnO2- 20%TiO2/ molecular sieve.
Catalyst high degree of dispersion obtained, specific surface area are up to 300m2/g.Its TEM figure is as shown in fig. 1.
Composite material 1%MnO is purified to the Multifunctional environment in embodiment 12- 20%TiO2/ molecular sieve carries out catalytic performance
Evaluation, condition is as follows: with electrodeless speed regulator control blower adjustment purification device (including shell, along gas flowing side in shell
To ultraviolet lamp group and multi-functional recombination catalyst layer is disposed with, similarly hereinafter, multi-functional recombination catalyst layer is by the multi-functional ring
Border purifies composite material 1%MnO2- 20%TiO2/ molecular sieve composition) wind speed, benzene, toluene inlet gas concentration are 2ppm, generate 185nm
The vacuum ultraviolet lamp group power of ultraviolet light is 10w, volume space velocity 15000h-1, the catalytic oxidation temperature is 25 DEG C.
Exhaust purification efficiency uses gas chromatographicanalyzer, and detecting factor is benzene, toluene and CO2.The results show that benzene, toluene removal rate
Always 83% is maintained, mineralization rate is up to 85%, and ozone is fully exploited no residual ozone, and degradation effect is stablized.
Composite material 1%MnO is purified to the Multifunctional environment in embodiment 1 using different Exhaust gas species and exhaust gas concentration2-
20%TiO2/ molecular sieve carries out catalytic performance test, and condition is as follows: adjusting purification device wind with electrodeless speed regulator control blower
Speed, benzene inlet gas concentration are 25ppm, and the vacuum ultraviolet lamp group power for generating 185nm ultraviolet light is 12w, volume space velocity 30000h-1, the catalytic oxidation temperature is 25 DEG C.Exhaust purification efficiency use gas chromatographicanalyzer, detecting factor be benzene and
CO2.The results show that benzene, removal rate maintain 100% always, mineralization rate is up to 93%, and ozone is fully exploited without residual
After-odour oxygen, degradation effect are stablized.
Embodiment 2
Multifunctional environment provided in this embodiment purifies composite material, which includes molecular sieve carrier, TiO2With
And a small amount of transition metal oxide NiO, TiO2It is supported on molecular sieve carrier with transition metal oxide NiO；Wherein transition gold
The load capacity for belonging to oxide NiO is 1%, TiO2Load capacity is 10%, i.e., Multifunctional environment purifies composite material 1%NiO-10%
TiO2/ molecular sieve.
The Multifunctional environment purifies composite material 1%NiO-10%TiO2/ molecular sieve the preparation method is as follows:
(1) according to required load capacity, 0.500g nickel acetate transition metal salt presoma is dissolved with 100mL dehydrated alcohol, is stirred
It mixes to dissolution；Under stirring, 15g powdery zeolite molecular sieve is poured into acetic acid manganese solution, stirs 60min；
(2) 6.5mL butyl titanate, 0.7mL concentrated hydrochloric acid is added, 60min is sufficiently stirred in 0.25mL acetoacetate, and it is molten that A is made
Liquid；
(3) 12mL ethyl alcohol, 6mL deionized water are sufficiently mixed, B solution is made；
(4) B solution is added dropwise in solution A, is vigorously stirred mixing, stirring rate is probably 400rpm/min, is formed steady
Fixed sol system；
(5) ageing 12h is placed, slowly polymerize between the aged micelle of colloidal sol, forms the gel of three-dimensional space network structure, so
1h is dried at 150 DEG C afterwards；Dry catalyst is placed in Muffle furnace, roasts 3h under the conditions of 500 DEG C, multi-functional ring needed for being made
Border catalytic purification material, the multi-functional composite catalyst include molecular sieve carrier, TiO2And transition metal oxide, TiO2And mistake
It crosses metal oxide supported on the molecular sieve carrier, is named as 1%NiO-10%TiO2/ molecular sieve.
Catalyst performance evaluation: air inlet air speed is adjusted with Frequency Converter Control blower, control benzene inlet gas concentration is 500mg/m3,
185nm vacuum ultraviolet lamp group power is 1kw, volume space velocity 10000h-1, the catalytic oxidation temperature is 25 DEG C.It is useless
Gas purification efficiency uses gas chromatographicanalyzer, and detecting factor is benzene and CO2.The results show that benzene removal rate is greater than 95%, mineralising
Rate is up to 90%, and stablizes without residual ozone degradation effect.
Embodiment 3
Multifunctional environment provided in this embodiment purifies composite material, which includes molecular sieve carrier, TiO2With
And a small amount of transition metal oxide CoO, TiO2It is supported on molecular sieve carrier with transition metal oxide CoO；Wherein transition gold
The load capacity for belonging to oxide CoO is 0.5%, TiO2Load capacity is 5%, i.e., Multifunctional environment purifies composite material 0.5%CoO-
5%TiO2/ molecular sieve.
The Multifunctional environment purifies composite material 0.5%CoO-5%TiO2/ molecular sieve the preparation method is as follows:
(1) according to required load capacity, 0.250g cobalt acetate transition metal salt presoma, stirring are dissolved with 75mL dehydrated alcohol
To dissolution；Under stirring, 15g powdery zeolite molecular sieve is poured into acetic acid manganese solution, stirs 60min；
(2) 3.25mL butyl titanate, 0.5mL concentrated hydrochloric acid is added, 60min is sufficiently stirred in 0.25mL acetoacetate, and A is made
Solution；
(3) 10mL ethyl alcohol, 5mL deionized water are sufficiently mixed, B solution is made；
(4) B solution is added dropwise in solution A, is vigorously stirred mixing, stirring rate is probably 400r/min, is formed and is stablized
Sol system；
(5) ageing 12h is placed, slowly polymerize between the aged micelle of colloidal sol, forms the gel of three-dimensional space network structure, so
6h is dried at 60 DEG C afterwards；Dry catalyst is placed in Muffle furnace, roasts 5h under the conditions of 550 DEG C, multi-functional ring needed for being made
Border catalytic purification material, the multi-functional composite catalyst include molecular sieve carrier, TiO2And transition metal oxide, TiO2And mistake
It crosses metal oxide supported on the molecular sieve carrier, is named as 0.5%CoO-5%TiO2/ molecular sieve.
Composite material 0.5%CoO-5%TiO is purified to the Multifunctional environment in the present embodiment2/ molecular sieve carries out catalytic
It can evaluate, cleaning equipment is the same as embodiment 2, organic exhaust gas parameter: exhaust gas flow 500m3/ h, concentration 10ppm, catalyst
Volume space velocity is 80000h-1, organic exhaust gas is made of benzene, and exhaust gas temperature is 25 DEG C or so.Waste gas purification effect in the present embodiment
Rate is stablized, and maintains 100% or more always, and generate without residual ozone.
Embodiment 4
Organic exhaust gas parameter and Process operating parameters are with embodiment 3, the difference is that catalyst activity component uses Mn and Cu
Bi-component, MnO2Load capacity is that 0.5%, CuO load capacity is 0.1%, and catalyst is labeled as 0.5%MnO2- 0.1%CuO-5%
TiO2/ molecular sieve, other are with embodiment 5 in addition to step (1) for the preparation step of catalyst, specially according to required load capacity, use
75mL dehydrated alcohol dissolves 0.215g manganese acetate and 0.038g copper acetate transition metal salt presoma.
The experimental results showed that the efficiency for benzene of degrading is 100%, ozone degradation rate is 100%, mineralization rate 99%.
With catalyst 0.5%MnO2- 5%TiO2/ molecular sieve is compared, and 0.1%CuO further improves the mineralising of catalyst
Rate plays the role of regulating catalyst performance.
Embodiment 5
Preparation process, control parameter and the load capacity of catalyst such as embodiment 1, by active component be changed to Zn, Co, Ce, Mn,
Cu, Fe, presoma are changed to nitrate, and with embodiment 1, clean-up effect see the table below 1 for catalyst performance evaluation method and parameter.
The clean-up effect of Multifunctional environment purification composite material in 1 the present embodiment of table
| Catalyst | Zn | Co | Ce | Mn | Cu | Fe |
| Purification efficiency | 86% | 94% | 70% | 96% | 93% | 80% |
| Mineralization rate | 85% | 91% | 74% | 92% | 90% | 78% |
| Ozone utilization rate | 88% | 100% | 80% | 100% | 100% | 85% |
Embodiment 6
Multifunctional environment provided in this embodiment purifies composite material, which includes molecular sieve carrier, TiO2With
And a small amount of transition metal oxide CeO2, TiO2With transition metal oxide CeO2It is supported on molecular sieve carrier；Wherein transition gold
Belong to oxide CeO2Load capacity be 0.05%, TiO2Load capacity is 30%, i.e., Multifunctional environment purifies composite material 0.05%
CeO2- 30%TiO2/ molecular sieve.
The Multifunctional environment purifies composite material 0.05%CeO2- 30%TiO2The preparation method reference implementation example of/molecular sieve
1。
Organic exhaust gas parameter: exhaust gas flow 500m3/ h, concentration 10ppm, the volume space velocity of catalyst are 80000h-1,
Organic exhaust gas is made of benzene, and exhaust gas temperature is 25 DEG C or so.Exhaust purification efficiency in the present embodiment is stablized, and maintains always
100% or more, and generated without residual ozone.
Embodiment 7
Multifunctional environment provided in this embodiment purifies composite material, which includes molecular sieve carrier, TiO2With
And a small amount of transition metal oxide CuO, TiO2It is supported on molecular sieve carrier with transition metal oxide CuO；Wherein transition gold
The load capacity for belonging to oxide CuO is 10%, TiO2Load capacity is 1%, i.e., Multifunctional environment purifies composite material 10%CuO-1%
TiO2/ molecular sieve.
The Multifunctional environment purifies composite material 10%CuO-1%TiO2The preparation method reference implementation example 1 of/molecular sieve.
Organic exhaust gas parameter: exhaust gas flow 500m3/ h, concentration 10ppm, the volume space velocity of catalyst are 80000h-1,
Organic exhaust gas is made of benzene, and exhaust gas temperature is 25 DEG C or so.Exhaust purification efficiency in the present embodiment is stablized, and maintains always
100% or more, and generated without residual ozone.
Embodiment 8
Multifunctional environment provided in this embodiment purifies composite material, which includes molecular sieve carrier, TiO2With
And a small amount of transition metal oxide CoO, TiO2With transition metal oxide CoO, it is supported on molecular sieve carrier；Wherein transition gold
The load capacity for belonging to oxide CoO is 5%, TiO2Load capacity is 10%, i.e., Multifunctional environment purifies composite material 5%CoO-10%
TiO2/ molecular sieve.
The Multifunctional environment purifies composite material 5%CoO-10%TiO2The preparation method reference implementation example 1 of/molecular sieve.
Organic exhaust gas parameter: exhaust gas flow 500m3/ h, concentration 10ppm, the volume space velocity of catalyst are 80000h-1,
Organic exhaust gas is made of benzene, and exhaust gas temperature is 25 DEG C or so.Exhaust purification efficiency in the present embodiment is stablized, and maintains always
95% or more, and generated without residual ozone.
Therefore, the above-mentioned Multifunctional environment in the present invention can be purified into composite material and is applied to indoor air purification equipment
In fresh air air cleaning system or equipment, at the same also can be widely applied to industrial organic exhaust gas administer field especially have
In the cleaning equipment or device of photooxidation, photochemical catalytic oxidation and catalytic ozonation synergistic purification pollutant effect.
The present invention will be described for specific embodiment listed above.It should be pointed out that above embodiments are served only for this
Invention is described further, and does not represent protection scope of the present invention, other people prompts according to the present invention are made nonessential
Modification and adjustment, still fall within protection scope of the present invention.
Claims (8)
1. a kind of Multifunctional environment purifies composite material, it is characterized in that: it includes molecular sieve carrier, TiO that the composite material, which is a kind of,2
And the catalyst of a small amount of transition metal oxide, the TiO2The molecular sieve carrier is supported on transition metal oxide
On；
The load capacity of the transition metal oxide is 0.05~10%, TiO2Load capacity is 1~30%, the transition gold
The load capacity of category oxide and the TiO2Load capacity is and to refer to that quality percentage contains on the basis of the molecular sieve carrier
Amount；
The transition metal oxide includes one or more of the transition metal oxide containing Mn, Co, Ni and Ce；
The preparation method of the Multifunctional environment purification composite material, comprising the following steps:
(1) transition metal salt presoma is chosen, transition metal salt precursor solution is prepared, under stirring, by molecular sieve
Carrier pours into the transition metal salt precursor solution, and turbid solution is made；
(2) butyl titanate, concentrated acid, acetyl class organic solvent are added in the turbid solution, after stirring, solution A is made；
(3) dehydrated alcohol is taken, deionized water is added, is mixed, B solution is made；
(4) B solution is added drop-wise in solution A, is vigorously stirred mixing, form stable sol system；
(5) sol system in step (4) is placed into ageing, slowly polymerize between micelle after sol system is aged,
TiO2Simultaneously then the growth in situ on molecular sieve carrier, the gel of formation three-dimensional space network structure dry with metal oxide
After dry and roasting, Multifunctional environment is made and purifies composite material；
Maturing temperature is 300~800 DEG C in step (5), and calcining time is 1~5h.
2. the preparation method of Multifunctional environment purification composite material described in claim 1, it is characterized in that the following steps are included:
(1) transition metal salt presoma is chosen, transition metal salt precursor solution is prepared, under stirring, by molecular sieve
Carrier pours into the transition metal salt precursor solution, and turbid solution is made；
(2) butyl titanate, concentrated acid, acetyl class organic solvent are added in the turbid solution, after stirring, solution A is made；
(3) dehydrated alcohol is taken, deionized water is added, is mixed, B solution is made；
(4) B solution is added drop-wise in solution A, is vigorously stirred mixing, form stable sol system；
(5) sol system in step (4) is placed into ageing, slowly polymerize between micelle after sol system is aged,
TiO2Simultaneously then the growth in situ on molecular sieve carrier, the gel of formation three-dimensional space network structure dry with metal oxide
After dry and roasting, Multifunctional environment is made and purifies composite material.
3. the preparation method of Multifunctional environment purification composite material according to claim 2, it is characterized in that: step (1)
Middle to prepare transition metal salt precursor solution using dehydrated alcohol, the dosage relation of the dehydrated alcohol and molecular sieve carrier is 3
~8mL:1g；Quality m=[the molecular sieve supported weight of (0 .05~10%) × m × M mistake of the transition metal salt presoma
Cross metallic atom number in metal salt precursor molecule amount × n metal oxide]/(M transition metal oxide molecular weight × n mistake
Cross metallic atom number in metal salt presoma)；The transition metal salt presoma is the transition comprising Mn, Co, Ni and Ce
One of metal or a variety of sulfate, nitrate, acetate or chloride.
4. the preparation method of Multifunctional environment purification composite material according to claim 2, it is characterized in that: step (2)
Described in butyl titanate volumetric usage V=[the molecular sieve supported weight of (1~30%) × m × M butyl titanate molecular weight]/(M
Titania molecule amount × ρ butyl titanate)；The volume ratio of the butyl titanate and the concentrated acid and acetyl class organic solvent are as follows:
10~150:1~5:1；The concentrated acid be concentrated hydrochloric acid and/or concentrated nitric acid, the acetyl class organic solvent be acetoacetate or
Acetylacetone,2,4-pentanedione.
5. the preparation method of Multifunctional environment purification composite material according to claim 2, it is characterized in that: step (3)
The volume ratio of middle dehydrated alcohol and deionized water is 1~3 .5:1.
6. the preparation method of Multifunctional environment purification composite material according to claim 2, it is characterized in that: step (4)
Described in the volume ratio of B solution and the solution A be 1:3~20.
7. the preparation method of Multifunctional environment purification composite material according to claim 2, it is characterized in that: step (5)
Middle drying temperature is 60~150 DEG C, and drying time is 1~6h.
8. Multifunctional environment purification composite material described in claim 1 is in photochemical catalytic oxidation and catalytic ozonation synergistic purification
Application in " triphen " exhaust gas.
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| CN109046326B (en) * | 2018-08-29 | 2021-09-07 | 香港大学 | Vacuum ultraviolet light catalytic purification material and preparation method and application thereof |
| CN112717992A (en) * | 2020-11-23 | 2021-04-30 | 中国矿业大学(北京) | Manganese-titanium composite modified zeolite and application thereof |
| CN115090323B (en) * | 2022-06-30 | 2024-01-16 | 宁波方太厨具有限公司 | Catalyst for purifying air, preparation method and purifying assembly |
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