CN108187631A - A kind of preparation method of improved material for air purification - Google Patents

A kind of preparation method of improved material for air purification Download PDF

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Publication number
CN108187631A
CN108187631A CN201810046370.7A CN201810046370A CN108187631A CN 108187631 A CN108187631 A CN 108187631A CN 201810046370 A CN201810046370 A CN 201810046370A CN 108187631 A CN108187631 A CN 108187631A
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air purification
preparation
graphene oxide
prepared
adds
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CN201810046370.7A
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不公告发明人
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Wenzhou Luxin Package Materials Co Ltd
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Wenzhou Luxin Package Materials Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057Surface area, e.g. B.E.T specific surface area
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J35/61
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/06Polluted air

Abstract

The present invention relates to a kind of preparation method of material for air purification, which includes carrier material and active metal;The carrier material adulterates graphene oxide and CeO using lignin as basic material2, form a kind of carrier of composite material, the material for air purification being prepared using the present processes, it is strong to adsorb ability of air, and contaminant degradation can be promoted, so as to improve the purification efficiency of material for air purification, with efficient air purification effect, and service life is long.

Description

A kind of preparation method of improved material for air purification
Technical field
This application involves the preparation methods of a kind of material for air purification more particularly to a kind of containing lignin and graphene The preparation method of material for air purification.
Background technology
With the increasingly raising and the quickening of urbanization process of people's living standard, a large amount of rows of motor vehicle exhaust It puts and waits factors, the getting worse of air environmental pollution and deterioration.Such as house decoration material, ornament materials in daily life Equally there is also certain pollution gas, and contain a large amount of carcinogen, such as formaldehyde, benzene,toluene,xylene, ammonia People’s lives health Deng, serious threat.With the exacerbation of atmosphere pollution, people continually develop air purifying preparation, in the market There are all kinds of air purifying preparations.
Existing air purification is mainly TiO with catalysis material2Based on photochemical catalyst, but catalytic efficiency is very low, because It is the key that solve the problems, such as that this, which selects suitable carrier material or compound other elements,.Common carrier is activated carbon and silica gel Support and the effect of gas absorption are functioned only as Deng, carrier, does not play the effect for pushing catalytic efficiency.Simultaneously for harmful gas Body treatment effect is to be improved.
Lignin and its derivative widely should at present due to having a large amount of surface active groups and specific surface area For fields such as heavy metal adsorption, Dye Adsorptions;Chinese patent CN201210595078.3 discloses one kind with lignin simultaneously TiO for carrier2Type air purifying preparation obtains preferable degradation effect.Chinese patent CN201410007028.8 is disclosed The air purifying preparation of a kind of appendix active metal or reactive metal oxides, shows excellent air purification effect.But for The material for air purification of high-efficient and lasting is still the active demand of this field institute.
Present inventor studies the air purifying preparation using lignin as carrier, develops the air of the application Scavenging material has many advantages, such as that degradation capability is strong, and service life is long, has a vast market.
Invention content
The object of the present invention is to provide a kind of material for air purification, are changed by the carrier components to air purifying preparation Into, effectively to improve air purification effect, can be directed to air in a variety of harmful ingredients degrade, while can also extend Service life.
Lignin and its derivative, can with suction-operated due to having a large amount of surface active groups and specific surface area For the carrier components of air purifying preparation, on the one hand the skeletal support of air purifying preparation can be provided, on the other hand contribute to shape Into loose porous structure, so as to enhance the effect of absorption air;In addition, being modified by introducing graphene oxide, improve It is catalyzed the efficiency and service life of pernicious gas degradation.It is improved by above-mentioned both sides, enhances the air purifying preparation of the present invention Degradation capability and degradation efficiency.Inventor has found by practice, when using lignin as basic material, and adulterates graphene oxide And CeO2, a kind of carrier of composite material is formed, the carrier adsorption ability of air is strong, and can effectively facilitate catalytic degradation dirt Contaminate gas.
In order to solve the above technical problems, invention provides a kind of material for air purification, which is characterized in that the material for air purification Including carrier material and active metal, the carrier material contains lignin, graphene oxide and CeO2
As preferred scheme is invented, in herein described material for air purification, the active metal is Pt, Pd, Ag In one or more mixtures.
Preferably, the active metal is Pt, Pd.
It is furthermore preferred that the active metal is Pd.
Further, the material for air purification is prepared by following methods:Prepare the solubility of active metal Then the aqueous solution of salt adds in carrier material, and add in DMF or pyrrolidones back flow reaction 8-15h, after reaction, washing, Alcohol is washed, and is dried to obtain the material for air purification for loading active metal.
Further, the carrier material is to be prepared via a method which to obtain:By beta-cyclodextrin, cerous nitrate and third Acrylamide or crotonamide are dissolved in water, with alkali adjusting PH to alkalinity, 1-2h are stirred at -10 DEG C -0 DEG C, then adds in lignin, And a certain amount of polyvinylpyrrolidone is added in, 3-4h is stirred at room temperature and obtains colloid, then, graphene oxide is added in, in 100- 5-10h is stirred at 200 DEG C, filters to obtain precipitation, calcining 4-10h at 500~700 DEG C will be deposited in and obtain carrier material.
Further, the graphene oxide is prepared by Hummers methods.Preferably, according to such as lower section It is prepared by method:Graphite powder is added in the concentrated sulfuric acid, sodium nitrate is added in, with KMnO4For oxidant, graphite oxide is first made, Then graphene oxide is made by ultrasonic disperse.
Further, the material for air purification of the application is prepared via a method which:
1) graphene oxide is prepared using Hummers methods:Graphite powder is added in the concentrated sulfuric acid, adds in sodium nitrate, with KMnO4For oxidant, graphite oxide is first made, graphene oxide is then made by ultrasonic disperse;
2) carrier material is prepared:Beta-cyclodextrin, cerous nitrate and acrylamide or crotonamide are dissolved in water, with alkali adjust PH to Alkalinity stirs 1-2h at -10 DEG C -0 DEG C, then adds in lignin, and adds in a certain amount of polyvinylpyrrolidone, and room temperature is stirred It mixes 3-4h and obtains colloid, then, graphene oxide made from addition step 1) stirs 5-10h at 100-200 DEG C, filters Precipitation will be deposited in calcining 4-10h at 500~700 DEG C and obtain carrier material;
3) supported active metals:The aqueous solution of the soluble-salt of active metal is prepared, then adds in the load that step 2) is prepared Body material adds in DMF or pyrrolidones back flow reaction 8-15h, and after reaction, washing, alcohol are washed, and it is active to be dried to obtain load The material for air purification of metal.
The present invention also provides the preparation methods of the material for air purification of the application, include the following steps:
1) carrier material is prepared:Beta-cyclodextrin, cerous nitrate and acrylamide or crotonamide are dissolved in water, with alkali adjust PH to Alkalinity stirs 1-2h at -10 DEG C -0 DEG C, then adds in lignin, and adds in a certain amount of polyvinylpyrrolidone, and room temperature is stirred It mixes 3-4h and obtains colloid, then, add in graphene oxide, 5-10h is stirred at 100-200 DEG C, filter to obtain precipitation, will be deposited in 4-10h is calcined at 500~700 DEG C and obtains carrier material;
2) supported active metals:The aqueous solution of the soluble-salt of active metal is prepared, then adds in the load that step 1) is prepared Body material adds in DMF or pyrrolidones back flow reaction 8-15h, and after reaction, washing, alcohol are washed, and it is active to be dried to obtain load The material for air purification of metal.
Further, the graphene oxide described in step 1) is prepared using Hummers methods.
Further, the operation that graphene oxide is prepared using Hummers methods is as follows:Graphite powder is added to dense sulphur In acid, sodium nitrate is added in, with KMnO4For oxidant, graphite oxide is first made, graphite oxide is then made by ultrasonic disperse Alkene.
The invention further relates to the material for air purification is used to prepare air purifying preparation, it is arbitrary that this field may be used It is prepared by a kind of conventional method, for example, material for air purification prepared by the present invention can be mixed with water or organic solvent, Organic solvent can be ethyl alcohol, acetone, propyl alcohol, by material for air purification (g):Water or organic solvent (ml)=1:30~60 is mixed It closes, obtains thick slurry, then carry out repeatedly lifting drying, you can obtain air purifying preparation.
The invention further relates to the application being used for the material for air purification in air purification, air purification of the invention Material can degrade a variety of pernicious gases, suitable for the air purification of all kinds of pollution environment, have good air purification effect.
Material for air purification provided by the invention has various advantages compared to existing material for air purification:
1) using lignin as the basic material of carrier, help to form loose porous structure, so as to enhance the work of absorption air With;
2) it is modified by introducing graphene oxide in the carrier, improves the efficiency of catalysis pernicious gas degradation and uses the longevity Life, so as to enhance the degradation capability and degradation efficiency of the air purifying preparation of the present invention;
3) air purifying preparation service life of the invention is long, and air purification ability is stablized, and Applicable temperature range is wider.
Specific embodiment
To make technical scheme of the present invention and its technique effect clearer, clear and definite, example below is enumerated to the present invention Specific embodiment is further described, but is not intended to limit the present invention.
The required graphene oxide of the present invention is prepared using Hummers methods well known in the art:It is added in reaction bulb The 400ml concentrated sulfuric acids under ice bath, add in 20g graphite powders, stir 5min, then add in 10g sodium nitrate, 55g is slowly added dropwise KMnO4, temperature control 1.5h is stirred to react within 5 DEG C, be then stirred to react 1h within 50 DEG C;It is slowly added to reaction solution 1L water is stirred to react 0.5h within 100 DEG C, adds water 650ml again, then adds in 300ml hydrogen peroxide (30%) and is stirred to react After 0.5h, 700ml (10%) hydrochloric acid is added in.Low-speed centrifugal, washing, the graphite oxide after washing is dispersed in water, ultrasound shake 1h is swung, then under 2500r/min rotating speeds, 0.5h is centrifuged, takes upper suspension up to graphene oxide.
1 Pt/CeO of embodiment2Type material for air purification
Beta-cyclodextrin, cerous nitrate and crotonamide are dissolved in water, obtain each component concentration (mol/L) be respectively 0.25,0.2, 0.22 solution, ammonium hydroxide adjust pH to 10,1.5h are stirred at 0 DEG C, then add in appropriate lignin, and add in a small amount of poly- second Alkene pyrrolidone is stirred at room temperature 4h and obtains colloid, adds in graphene oxide, 6h is stirred at 100 DEG C, filters to obtain precipitation, will be heavy The calcining 10h at 500 DEG C that forms sediment obtains carrier material;
Supported active metals Pt:Prepare H2PtCl6Aqueous solution, by 0.2% Pt loadings, add in the carrier material being prepared Material, the back flow reaction 10h in DMF after reaction, are first washed with water, are washed again with ethyl alcohol, be dried to obtain Pt/CeO2Type air Scavenging material.
2 Pd/CeO of embodiment2Type material for air purification
Beta-cyclodextrin, cerous nitrate and crotonamide is soluble in water, obtain each component concentration (mol/L) be respectively 0.5 5, 0.4th, 0.3 mixed solution, ammonium hydroxide adjust pH to 9,2h are stirred at -5 DEG C, then add in lignin, and add in a small amount of gather Vinylpyrrolidone is stirred at room temperature 3h and obtains colloid, adds in graphene oxide, continues to stir 6h at 150 DEG C, filters heavy It forms sediment, calcining 8h at 600 DEG C will be deposited in and obtain carrier material;
Supported active metals Pd:Prepare PdCl2Aqueous solution, by 0.6% Pd loadings, add in the carrier material being prepared With pyrrolidones back flow reaction 12h, after reaction, first it is washed with water, is washed again with ethyl alcohol, be dried to obtain Pd/CeO2Type air Scavenging material.
3 Ag/CeO of embodiment2Type material for air purification
Beta-cyclodextrin, cerous nitrate and acrylamide are dissolved in water, obtain each component concentration (mol/L) be respectively 0.6,0.5, 0.6 mixed solution, ammonium hydroxide adjust pH to 10,1h are stirred at 0 DEG C, then adds in lignin, and adds in a small amount of polyethylene Pyrrolidones is stirred at room temperature 4h and obtains colloid, then, adds in graphene oxide, 5h is stirred at 200 DEG C, filters to obtain precipitation, will It is deposited in calcining 4h at 700 DEG C and obtains carrier material;
Supported active metals Ag:Prepare AgNO3Aqueous solution, by 0.6% Ag loadings, add in the carrier material being prepared With pyrrolidones back flow reaction 10h, after reaction, first it is washed with water, is washed again with ethyl alcohol, be dried to obtain Ag/CeO2Type air Scavenging material.
4 Pd/CeO of embodiment2Type material for air purification
Beta-cyclodextrin, cerous nitrate and acrylamide is soluble in water, obtain each component concentration (mol/L) be respectively 0.5,0.4, 0.5 mixed solution, ammonium hydroxide adjust pH to 9,2h are stirred at 0 DEG C, then adds in lignin, and adds in a small amount of polyethylene pyrrole Pyrrolidone is stirred at room temperature 3h and obtains colloid, adds in graphene oxide, continues to stir 6h at 150 DEG C, filters to obtain precipitation, will be heavy The calcining 8h at 600 DEG C that forms sediment obtains carrier material;
Supported active metals Pd:Prepare PdCl2Aqueous solution, by 0.6% Pd loadings, add in the carrier material being prepared With pyrrolidones back flow reaction 12h, after reaction, first it is washed with water, is washed again with ethyl alcohol, be dried to obtain Pd/CeO2Type air Scavenging material.
Reference examples 1
Method according to embodiment 2 prepares material for air purification, but does not add in graphene oxide in the preparation of carrier material, Its process is same as Example 2.
Reference examples 2
Method according to embodiment 2 prepares material for air purification, but does not add in lignin in the preparation of carrier material, other mistakes Journey is same as Example 2.
Reference examples 3
Method according to embodiment 2 prepares material for air purification, but does not add in lignin and oxidation in the preparation of carrier material Graphene, other processes are same as Example 2.
Embodiment 5
The material for air purification that above-described embodiment 1-4 and reference examples 1-3 are prepared, by material for air purification (g):Ethyl alcohol (ml)=1:45 mixing, stir to get thick slurry, then carry out 4 lifting drying, obtain 7 kinds of air purifying preparations, successively Labeled as A, B, C, D, E, F, G.
Embodiment 6
7 kinds of air purifying preparations (etc. weight) prepared by embodiment 5, which are fitted into reactor, purifies the air of pollution, air In pollutant be respectively formaldehyde, benzene, ammonia, hydrogen sulfide, NO, NO2, one kind in CO, the initial concentration of wherein pollutant is 100mg/L over the course of 15 mins using the concentration of chromatographic pollutant, calculates degradation rate, clean-up effect such as table 1:Table 1
From embodiment 6 as can be seen that the air purifying preparation of the present invention had the ability of efficient degradation of contaminant, at 15 minutes It is interior, more than 90% can be reached substantially to the degradation rate of most of pollutant, and there is good removing energy to a variety of pernicious gases Power.
Embodiment 7
The service life of the material for air purification of the application is tested using accelerated test, experimental method:Embodiment 5 is made Standby 7 kinds of air purifying preparations (etc. weight), which are respectively placed in reactor, to be purified, by persistently supplementing reactor harmful gas Body makes the harmful gas concentration in reactor maintain more than 30% always, and the pernicious gas used is the 1 of formaldehyde and benzene:1 is mixed Gas is closed, continuous purification takes out air purifying preparation, tested as described in Example 5, wherein pollutant is initial after 60 days A concentration of 100mg/L over the course of 15 mins using the concentration of chromatographic pollutant, calculates degradation rate, as a result such as table 2: Table 2
From table 2 it can be seen that the material for air purification of the present invention (is far above in a concentration of more than 30% high density pollution gas Normal pollution condition) in continuous purification after 60 days, still maintain good purification efficiency, be held essentially constant.Therefore, using this Air purifying preparation service life prepared by the material for air purification of invention is long, has good application market.
Although present invention has been a degree of descriptions, it will be apparent that, do not departing from the spirit and scope of the present invention Under the conditions of, the appropriate variation of each condition can be carried out.It is appreciated that the present invention is not limited to the embodiment, and it is attributed to right It is required that range, include the equivalent replacement of each factor.

Claims (8)

1. a kind of preparation method of material for air purification, which is characterized in that the material for air purification include carrier material and Active metal, the carrier material contain lignin, graphene oxide and CeO2;Include the following steps:Prepare the activity gold Then the aqueous solution of the soluble-salt of category adds in the carrier material, and add in DMF or pyrrolidones back flow reaction 8-15h, instead After answering, washing, alcohol are washed, and are dried to obtain the material for air purification for loading active metal.
2. the preparation method of material for air purification according to claim 1, which is characterized in that the carrier material is by as follows It is prepared by method:Beta-cyclodextrin, cerous nitrate and acrylamide or crotonamide are dissolved in water, PH is adjusted to alkalinity with alkali, -10 1-2h is stirred at DEG C -0 DEG C, lignin is then added in, and add in a certain amount of polyvinylpyrrolidone, 3-4h is stirred at room temperature and obtains Then colloid, adds in graphene oxide, 5-10h is stirred at 100-200 DEG C, filter to obtain precipitation, will be deposited in 500~700 DEG C Lower calcining 4-10h obtains carrier material.
3. according to the preparation method of claim 1-2 any one of them material for air purification, which is characterized in that further comprise The preparation of the graphene oxide is prepared using Hummers methods.
4. the preparation method of material for air purification according to claim 3, which is characterized in that the system of the graphene oxide Preparation Method is as follows:Graphite powder is added in the concentrated sulfuric acid, sodium nitrate is added in, with KMnO4For oxidant, oxidation stone is first made Then graphene oxide is made by ultrasonic disperse in ink.
5. according to the preparation method of claim 1-4 any one of them material for air purification, it is characterised in that the activity gold Belong to for one or more mixtures in Pt, Pd, Ag, preferably Pt, Pd, most preferably Pd.
6. according to the preparation method of claim 2-5 any one of them material for air purification, which is characterized in that carrier material In preparation process, alkali used is ammonium hydroxide.
7. according to the preparation method of claim 1-6 any one of them material for air purification, which is characterized in that including walking as follows Suddenly:1) carrier material is prepared:Beta-cyclodextrin, cerous nitrate and acrylamide or crotonamide are dissolved in water, with alkali adjust PH to Alkalinity stirs 1-2h at -10 DEG C -0 DEG C, then adds in lignin, and adds in a certain amount of polyvinylpyrrolidone, and room temperature is stirred It mixes 3-4h and obtains colloid, then, add in graphene oxide, 5-10h is stirred at 100-200 DEG C, filter to obtain precipitation, will be deposited in 4-10h is calcined at 500~700 DEG C and obtains carrier material;
2) supported active metals:The aqueous solution of the soluble-salt of active metal is prepared, then adds in the load that step 1) is prepared Body material adds in DMF or pyrrolidones back flow reaction 8-15h, and after reaction, washing, alcohol are washed, and it is active to be dried to obtain load The material for air purification of metal.
8. the preparation method of material for air purification according to claim 7, which is characterized in that further include following steps:It adopts Graphene oxide is prepared with Hummers methods:Graphite powder is added in the concentrated sulfuric acid, sodium nitrate is added in, with KMnO4For oxidation Agent is first made graphite oxide, graphene oxide then is made by ultrasonic disperse.
CN201810046370.7A 2018-01-17 2018-01-17 A kind of preparation method of improved material for air purification Pending CN108187631A (en)

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Publication number Priority date Publication date Assignee Title
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CN1820838A (en) * 2005-02-16 2006-08-23 周成一 Air purifying material and its preparing method
CN101703931A (en) * 2009-11-25 2010-05-12 中国农业大学 Load type palladium catalyst and preparation method thereof
CN106044744A (en) * 2016-05-31 2016-10-26 江苏大学 Preparation method and application of graphene-lignin-based composite hierarchical pore carbon plate material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1377729A (en) * 2001-04-05 2002-11-06 上海欧臣环境高科技有限责任公司 Purifying material capable of removing organic gas in air and its preparing method
CN1820838A (en) * 2005-02-16 2006-08-23 周成一 Air purifying material and its preparing method
CN101703931A (en) * 2009-11-25 2010-05-12 中国农业大学 Load type palladium catalyst and preparation method thereof
CN106044744A (en) * 2016-05-31 2016-10-26 江苏大学 Preparation method and application of graphene-lignin-based composite hierarchical pore carbon plate material

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