CN108031449A - A kind of improved material for air purification and its application - Google Patents
A kind of improved material for air purification and its application Download PDFInfo
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- CN108031449A CN108031449A CN201810046378.3A CN201810046378A CN108031449A CN 108031449 A CN108031449 A CN 108031449A CN 201810046378 A CN201810046378 A CN 201810046378A CN 108031449 A CN108031449 A CN 108031449A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
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- B01D2255/104—Silver
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4837—Lignin
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Abstract
The present invention is improved for existing air purifying preparation, there is provided a kind of material for air purification, the material for air purification include carrier material and active metal；The carrier material adulterates graphene oxide and CeO using lignin as basic material2, a kind of carrier of composite material is formed, carrier material absorption ability of air is strong, and can promote contaminant degradation, so as to improve the purification efficiency of material for air purification.There is efficient air purification effect using air purifying preparation made of the material for air purification of the present invention, and service life is grown.
Description
Technical field
This application involves a kind of material for air purification, more particularly to a kind of air purification material containing lignin and graphene
Material and its application.
Background technology
With quickening, a large amount of rows of motor vehicle exhaust of the increasingly raising of people's living standard, and urbanization process
Factors, the getting worse of air environmental pollution and the deterioration such as put.Such as house decoration material, ornament materials in daily life
Equally there is also certain pollution gas, and contain substantial amounts of carcinogen, such as formaldehyde, benzene,toluene,xylene, ammonia
Deng serious threat the life health of people.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 solved 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 promoting catalytic efficiency.At the same time for harmful gas
Body treatment effect has much room for improvement.
Lignin and its derivative due to substantial amounts of surface active groups and specific surface area, widely should at present
For fields such as heavy metal adsorption, Dye Adsorptions；Chinese patent CN201210595078.3 discloses one kind with lignin at the same time
For the TiO of carrier2Type air purifying preparation, obtains preferable degradation effect.Chinese patent CN201410007028.8 is disclosed
A kind of air purifying preparation 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 area institute.
Present inventor studies the air purifying preparation using lignin as carrier, develops the air of the application
Scavenging material, has the advantages that degradation capability is strong, and service life is long, has a vast market.
The content of the invention
The object of the present invention is to provide a kind of material for air purification, by changing to the carrier components of air purifying preparation
Into effectively to improve air purification effect, a variety of harmful components in air being directed to and be degraded, while can also be extended
Service life.
Lignin and its derivative, can due to substantial amounts of surface active groups and specific surface area, having suction-operated
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 strengthen 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 degraded.Improved by above-mentioned both sides, strengthen 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, it is characterised in that the material for air purification
Including carrier material and active metal, the carrier material contains lignin, graphene oxide and CeO2。
As preferable 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
The aqueous solution of salt, then adds carrier material, and adds 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 being loaded with 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 alkalescence, 1-2h are stirred at -10 DEG C -0 DEG C, then adds lignin,
And a certain amount of polyvinylpyrrolidone is added, 3-4h is stirred at room temperature and obtains colloid, then, graphene oxide is added, in 100-
5-10h is stirred at 200 DEG C, filtering to precipitate, and will be deposited in calcining 4-10h at 500~700 DEG C 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, 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 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
Alkalescence, stirs 1-2h at -10 DEG C -0 DEG C, then adds lignin, and adds a certain amount of polyvinylpyrrolidone, and room temperature is stirred
Mix 3-4h and obtain colloid, then, graphene oxide made from addition step 1), stirs 5-10h at 100-200 DEG C, filter
Precipitation, will be deposited in calcining 4-10h at 500~700 DEG C and obtains carrier material；
3) supported active metals：The aqueous solution of the soluble-salt of active metal is prepared, then adds the load that step 2) is prepared
Body material, adds 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.
Present invention also offers the preparation method 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
Alkalescence, stirs 1-2h at -10 DEG C -0 DEG C, then adds lignin, and adds a certain amount of polyvinylpyrrolidone, and room temperature is stirred
Mix 3-4h and obtain colloid, then, add graphene oxide, stir 5-10h at 100-200 DEG C, filtering to precipitate, and 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 the load that step 1) is prepared
Body material, adds 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, 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, this area can be used any
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 ethanol, acetone, propyl alcohol, by material for air purification (g):Water or organic solvent (ml)=1:30~60 is mixed
Close, obtain 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 many advantages compared to existing material for air purification：
1) basic material using lignin as carrier, helps to form loose porous structure, so as to strengthen the work of absorption air
With；
2) it is modified by introducing graphene oxide in the carrier, improves the efficiency of catalysis pernicious gas degraded and use the longevity
Life, so as to strengthen the degradation capability and degradation efficiency of the air purifying preparation of the present invention；
3) air purifying preparation service life of the invention length, air purification ability is stablized, and Applicable temperature scope is wider.
Embodiment
To make technical scheme and its technique effect clearer, clear and definite, example below is enumerated to the present invention
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：Added in reaction bulb
The 400ml concentrated sulfuric acids, under ice bath, add 20g graphite powders, stir 5min, then add 10g sodium nitrate, 55g is slowly added dropwise
KMnO4, temperature control stirs within 5 DEG C reacts 1.5h, then the stirring reaction 1h within 50 DEG C；It is slowly added to reaction solution
1L water, stirring reaction 0.5h, adds water 650ml again within 100 DEG C, then adds 300ml hydrogen peroxide (30%) stirring reaction
After 0.5h, 700ml (10%) hydrochloric acid is added.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.
Embodiment 1Pt/CeO2Type 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 appropriate lignin, and add a small amount of poly- second
Alkene pyrrolidone, is stirred at room temperature 4h and obtains colloid, add graphene oxide, 6h is stirred at 100 DEG C, and filtering to precipitate, 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 the carrier material being prepared
Material, the back flow reaction 10h in DMF, after reaction, is first washed with water, is washed again with ethanol, be dried to obtain Pt/CeO2Type air
Scavenging material.
Embodiment 2Pd/CeO2Type 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 lignin, and add a small amount of gather
Vinylpyrrolidone, is stirred at room temperature 3h and obtains colloid, add graphene oxide, continues to stir 6h at 150 DEG C, filtering to sink
Form 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 the carrier material being prepared and pyrrolidones back flow reaction 12h, after reaction, be first washed with water, again
Washed with ethanol, be dried to obtain Pd/CeO2Type material for air purification.
Embodiment 3Ag/CeO2Type 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 lignin, and adds a small amount of polyethylene
Pyrrolidones, is stirred at room temperature 4h and obtains colloid, then, adds graphene oxide, 5h is stirred at 200 DEG C, and filtering to precipitate, 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 the carrier material being prepared
With pyrrolidones back flow reaction 10h, after reaction, first it is washed with water, is washed again with ethanol, be dried to obtain Ag/CeO2Type air
Scavenging material.
Embodiment 4Pd/CeO2Type 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 lignin, and adds a small amount of polyethylene pyrrole
Pyrrolidone, is stirred at room temperature 3h and obtains colloid, add graphene oxide, continues to stir 6h at 150 DEG C, and filtering to precipitate, 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 carry on a shoulder pole
Carrying capacity, adds the carrier material being prepared and pyrrolidones back flow reaction 12h, after reaction, is first washed with water, uses ethanol again
Washing, is dried to obtain Pd/CeO2Type material for air purification.
Reference examples 1
Method according to embodiment 2 prepares material for air purification, but does not add graphene oxide in the preparation of carrier material, its
Its process is same as Example 2.
Reference examples 2
Method according to embodiment 2 prepares material for air purification, but does not add 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 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):Ethanol
(ml)=1:45 mixing, stirring obtain 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% all the time, 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
Concentration is 100mg/L, over the course of 15 mins using the concentration of chromatographic pollutant, degradation rate is calculated, 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 the high density pollution gas that concentration is more than 30%
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 length prepared by the material for air purification of invention, has good application market.
Although present invention has been a degree of description, it will be apparent that, do not departing from the spirit and scope of the present invention
Under the conditions of, the appropriate change of each condition can be carried out.It is appreciated that the invention is not restricted to the embodiment, and it is attributed to right
It is required that scope, it includes the equivalent substitution of each factor.
Claims (10)
1. a kind of material for air purification, it is characterised in that the material for air purification includes carrier material and active metal, institute
State carrier material and contain lignin, graphene oxide and CeO2。
2. material for air purification according to claim 1, it is characterised in that the active metal is one in Pt, Pd, Ag
Kind or a variety of mixtures, preferably Pt, Pd, most preferably Pd.
3. according to claim 1-2 any one of them material for air purification, it is characterised in that the material for air purification is by such as
It is prepared by lower section method：The aqueous solution of the soluble-salt of the active metal is prepared, then adds the carrier material, and add DMF
Or pyrrolidones back flow reaction 8-15h, after reaction, washing, alcohol are washed, and are dried to obtain the air purification for being loaded with active metal
Material.
4. according to claim 1-3 any one of them material for air purification, it is characterised 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 alkalescence with alkali, -10
1-2h is stirred at DEG C -0 DEG C, then adds lignin, and adds a certain amount of polyvinylpyrrolidone, 3-4h is stirred at room temperature and obtains
Colloid, then, adds graphene oxide, stirs 5-10h at 100-200 DEG C, filtering to precipitate, and will be deposited in 500~700 DEG C
Lower calcining 4-10h obtains carrier material.
5. according to claim 1-4 any one of them material for air purification, it is characterised in that the graphene oxide uses
It is prepared by Hummers methods.
6. according to claim 1-5 any one of them material for air purification, it is characterised in that the graphene oxide is by as follows
It is prepared by method：Graphite powder is added in the concentrated sulfuric acid, sodium nitrate is added, with KMnO4For oxidant, graphite oxide is first made,
Then graphene oxide is made by ultrasonic disperse.
7. application of the material for air purification any one of claim 1-6 in air purifying preparation is prepared.
8. a kind of air purifying preparation, it is characterised in that prepared using claim 1-6 any one of them material for air purification.
9. a kind of preparation method of air purifying preparation, it is characterised in that using claim 1-6 any one of them air purification
Material is raw material, by material for air purification (g):Water or organic solvent (ml)=1:30~60 mixing, obtain thick slurry, so
Repeatedly lifting drying is carried out afterwards, you can obtains air purifying preparation.
10. preparation method according to claim 9, it is characterised in that the organic solvent is ethanol, acetone, propyl alcohol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110961098A (en) * | 2019-12-23 | 2020-04-07 | 延安大学 | Novel environment-friendly air purification composite material and preparation method thereof |
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| 唐新硕等: "《催化科学发展及其理论》", 31 March 2012, 浙江大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961098A (en) * | 2019-12-23 | 2020-04-07 | 延安大学 | Novel environment-friendly air purification composite material and preparation method thereof |
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