CN101766996A - Preparation method of composite photocatalytic material for fresh-keeping of fruit and vegetable - Google Patents
Preparation method of composite photocatalytic material for fresh-keeping of fruit and vegetable Download PDFInfo
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- CN101766996A CN101766996A CN200910028641A CN200910028641A CN101766996A CN 101766996 A CN101766996 A CN 101766996A CN 200910028641 A CN200910028641 A CN 200910028641A CN 200910028641 A CN200910028641 A CN 200910028641A CN 101766996 A CN101766996 A CN 101766996A
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Abstract
The invention discloses a preparation method of a composite photocatalytic material for fresh-keeping of fruits and vegetables and a process thereof, comprising preparation of sol through acidic hydrolysis with titanium ester as a raw material, or preparation of absorption type composite photocatalytic material through ultrasonic dispersion of nano titanium dioxide in water and water heating treatment after adding activated carbon fiber, wherein the titanium dioxide is the main catalyst of the absorption type composite photocatalytic material, and the activated carbon fiber is the carrier and the supporting mass thereof. The prepared material can transform ethylene, ethanol, acetaldehyde and the like generated in breathing of fruits and vegetables in processing plants and refrigerators for the fruits and vegetables, and hydrogen sulfide, ammonia and other common volatile contaminants generated in rotting of the fruits and vegetables into harmless materials through photocatalytic reaction under the ultraviolet irradiation. Simultaneously, the invention has the function of killing bacteria and microbes, thereby ensuring that the fruits and vegetables are fresh and safe to eat.
Description
Technical field:
Technical field under the present invention is the preparation of catalysis material, particularly belongs to the preparation method of the matching used composite photocatalyst material of a kind of preserving fruit and vegetable utilizing.
Background technology:
The Nano semiconductor photocatalysis technology has been obtained remarkable progress in recent years, and many nano semiconductor materials are as titanium dioxide (TiO
2), zinc oxide (ZnO), tin ash (SnO
2), cadmium sulfide (CdS) etc. all is found the organic or inorganic pollutant of can degrading effectively, wherein titanium dioxide have that chemical property is stable, strong, the anti-photocathode burn into of oxidation-reduction quality indissoluble, nontoxic, low cost and other advantages.Relevant is that the document of the degradation of contaminant of photochemical catalyst has Alberici R.M. with titanium dioxide, " titanium dioxide gas-phase photocatalysis degraded volatile organic contaminant " (Photocatalytic destructionof VOCs in the gas-phase using Titanium Dioxide.Appl.Catal.B:Environ that Jardim W.F. delivers on " applied catalysis ", 1997,14,55～68), most studies is to use Powdered photochemical catalyst at present, yet in use there is the reunion inactivation in Powdered photochemical catalyst, problems such as separation is relatively poor with recovery difficulty and titanium dioxide adsorption capacity, and photocatalysis efficiency is low.It is carrier immobilized that some researchers have carried out titania powder, " inert carrier has improved the effect of gas phase Propionaldehyde degradation rate after titanium dichloride loadization " (Effect of inert supports for titaniumdioxide loading on enhancement of photodecomposition rate of gaseous propionaldehyde.J.Phys.Chem.1995 that this type of document has Yoneyama H. to deliver on " physical chemistry magazine ", 99 (21), 9986～9991) and Chuan Dao just flourish, middle gift department, patent (the deodoriser of angle Tian Zhaofu etc., CN1035438,1989), though these method parts have solved powder immobilization problem, but common used sol-gel legal system film and load, because crystal transfer and volume contraction in the dry run, crackle appears in made film and load layer easily, with problems such as carrier bonding are not firm, affect the catalytic efficiency and the practicality of catalyst.
In preserving fruit and vegetable utilizing processing and storage, need the sanitary condition of strictness, and the respiration of fruits and vegetables to produce ethene,
Gas such as ethanol, acetaldehyde, the rotten corruption of fruits and vegetables will produce waste gas such as hydrogen sulfide, ammonia, and the accumulation of these waste gas influences the fresh-keeping and storing of other fruits and vegetables.Technology is in the past used as chemical absorbents such as potassium permanganate, and purification rate is slower, and cost is higher; Have and use acticarbon, there is the maximum adsorption saturation capacity in charcoal absorption, reaches the possibility that the maximum adsorption saturation capacity has desorb.And the light catalytic purifying method, can directly carry out redox reaction, perhaps utilize the oxidising agent (as hydroxyl radical free radical) of oxygen and water generates to come destroy contaminants indirectly, and the active agent of oxidation reaction is by pollutant itself or derives from water and air, to the elimination of degrading fully of most of organic and inorganic pollutions, and to comprising dust, suspended particles such as pollen, microorganism is comprised mould, bacterium, the elimination of also degrading such as virus, and the non-existent stoichiometry problem of catalysis material, can be used multiple times, and consume seldom, be specially adapted to the air cleaning in the semiclosed and enclosed environment such as garden stuff processing workshop and freezer etc.
Summary of the invention:
The objective of the invention is for the adsorption capacity that overcomes titanium dioxide relatively poor, titanium dioxide and carrier bonding are insecure, the deficiency that photocatalysis efficiency is lower, and provide a kind of preparation method, make titanium dioxide and carrier bonding firmly, improved the matching used composite photocatalyst material of preserving fruit and vegetable utilizing of adsorption capacity and photocatalysis efficiency.
The technical scheme that the preparation method of the matching used composite photocatalyst material of preserving fruit and vegetable utilizing of the present invention adopts is:
Utilize the hydrothermal treatment consists method that titanium dichloride load is prepared titanium dioxide/NACF composite photo-catalyst to NACF, after the drying, being prepared into titanium dioxide is that main catalyst, active carbon are the absorbent-type composite photocatalyst scavenging material of carrier and supporting mass.
Used titanium dioxide is main catalyst, and crystal formation is a Detitanium-ore-type, and purity is not less than 99%.The preparation method of titanium dioxide has two kinds, method one: prepare TiO 2 sol by titanate esters by sol-gel process, method two: nano titanium dioxide powder ultrasonic dispersion in water prepares tio_2 suspension.The average grain diameter of the titanium dioxide in colloidal sol or the suspension is 1～100nm.
Titanium dioxide and absorbent-type NACF are compound, the coal-based or fruit shell carbon in active carbon source.Specific area is at 1000～1800m
2/ g.
The preparation method of the composite catalyst of the used titanium dioxide/NACF of the present invention, be to utilize the preparation of hydrothermal treatment consists method to contain titanium dioxide/NACF composite catalyst, that is: NACF carries out hydrothermal treatment consists with colloidal sol or suspension, the temperature of hydrothermal treatment consists is 100～200 ℃, and the time is 5～15 hours.The ratio of the amount of the titanium dioxide that the addition of NACF and colloidal sol or water slurry are contained is: 10～40: 60～90% (quality %), the amount of dry back titanium dioxide is 0.5～1.0mg/cm
2The hydrothermal treatment consists method makes TiO 2 particles in the colloidal sol realize the particle of crystal transfer and crystallization excellence in the hydrothermal treatment consists process, and the volume contraction of colloidal sol when reducing film forming like this reduces the generation of crackle, has reduced follow-up heat treatment temperature.NACF has improved the uniformity of titanium dioxide on NACF with the suspension hydrothermal treatment consists of colloidal sol or titanium dioxide simultaneously, has increased the caking property of titanium dioxide and NACF, and composite quality is improved.Preparation process of the present invention is seen accompanying drawing 1.
The present invention compares with existing correlation technique has outstanding feature and progress:
1. realized the crystal transfer and the particle slaking of titanium dioxide in the hydrothermal treatment consists process, the volume contraction of colloidal sol in the time of can reducing film forming like this reduces the generation of crackle, improves with the caking property of NACF and has reduced follow-up heat treatment temperature.The hydrothermal treatment consists method makes titanium dioxide/NACF compound evenly, firm, stable high.
2. titanium dioxide/NACF composite photocatalyst material has absorption property and photocatalysis performance, titanium dioxide and active carbon have mutual synergy in the photocatalytic process, active carbon has improved photocatalysis efficiency, the photocatalysis of titanium dioxide makes active carbon regeneration, makes material to reuse for a long time.
3. preparation technology is simple for titanium dioxide/NACF composite catalyst, and cost is lower, is easy to be pressed into different shape, is convenient to the replacing of material.The prepared catalysis material of this method has better stability, catalytic activity and mechanical strength.
The sample of catalysis material of the present invention carries out the photocatalysis evaluation in the intermittent cyclic system.As light source, testing used sample size is 3g with ultraviolet light in light-catalyzed reaction.Under common experiment condition: 25 ± 1 ℃ of temperature, relative humidity 40～45%, carry out ethene and benzene photocatalysis experiment, the initial concentration of therein ethylene and benzene is 20ppm, and sample of the present invention is 99% to the conversion ratio of fourth ethene 20min, is 99% to the conversion ratio of the photocatalysis 40min of benzene, contrast the photocatalysis efficiency that all is doubled with sample 3, the photocatalysis effect of ethene is seen accompanying drawing 2, and the photocatalysis effect of benzene is seen accompanying drawing 3
Description of drawings:
Fig. 1 is titanium dioxide/NACF composite catalyst preparation technology sketch.
Fig. 2 is the photocatalysis design sketch of ethene.Abscissa is light application time (min), and ordinate is the concentration (ppm) of ethene.In the picture in picture ● representative sample 1, ■ representative sample 2, ▲ representative sample 3.
Fig. 3 is the photocatalysis design sketch of benzene.Abscissa is light application time (min), and ordinate is the concentration (ppm) of benzene.Among the figure ● representative sample 1, ■ representative sample 2, ▲ representative sample 3.
The specific embodiment:
The present invention is described in further detail below in conjunction with embodiment:
Embodiment 1: prepare titanium dioxide/NACF compound catalyze material by colloidal sol
0.1mol (34g) dropwise be added in the aqueous solution of nitric acid of 360ml, 1M under the butyl titanate stirring at normal temperature, the limit drips, stir on the limit and control drips and mixing speed, drip off the back and continue to stir 2h, butyl titanate forms through hydrolysis and slightly is flaxen vitreosol, place a few hours, butanols that decomposites and colloidal sol layering are the faint yellow upper strata that floats on, tell the butanols layer, can obtain subdiaphanous colloidal sol.The colloidal sol of preparation adds the 3g NACF and joins in the pressure vessel, behind 160 ℃ of hydrothermal treatment consists 10h, takes out the NACF that contains titanium dioxide, obtains sample 1 after the drying.
Embodiment 2: prepare titanium dioxide/NACF compound catalyze material by titania powder
The 8g nano titanium dioxide powder adds 340mL water, and ultrasonic dispersion 20min obtains white suspension.Adding 3g NACF also joins in the pressure vessel, behind 160 ℃ of hydrothermal treatment consists 5h, obtains sample 2 with embodiment 1 identical operations.
Embodiment 3: prepare the titanium dioxide catalysis material by colloidal sol
Prepare TiO 2 sol with the method identical, be sprayed at after the hydrothermal treatment consists on the glass plate, do not add active carbon and obtain control sample 3 with embodiment 1.
Claims (5)
1. the preparation method of a composite photocatalytic material for fresh-keeping of fruit and vegetable, it is characterized in that: utilize the hydrothermal treatment consists method that titanium dichloride load is prepared titanium dioxide/NACF composite photo-catalyst to NACF, after the drying, being prepared into titanium dioxide is that main catalyst, NACF are the absorbent-type composite photocatalyst scavenging material of carrier and supporting mass.
2. catalysis material according to claim 1 is characterized in that titanium dioxide is Detitanium-ore-type, and its average grain diameter is 1～100nm; The preparation method of titanium dioxide has two kinds, method one: prepare TiO 2 sol by sol-gel process by titanate esters; Method two: nano titanium dioxide powder ultrasonic dispersion in water prepares tio_2 suspension.
3. catalysis material according to claim 1 is characterized in that NACF is the absorbent-type NACF, derives from coal-based, fruit shell carbon, and specific area is 1000～1800m
2/ g.
4. catalysis material according to claim 1, the preparation method who it is characterized in that titanium dioxide/NACF composite catalyst utilizes the preparation of hydrothermal treatment consists method to contain titanium dioxide/active carbon composite catalyst, and temperature is 100～200 ℃, and the time is 5～15 hours.
5. the preparation method of titanium dioxide according to claim 4/NACF composite catalyst is characterized in that the ratio of the titanium dioxide that NACF and colloidal sol or water slurry are contained is: 10～40: 60～90 (quality %).The amount of dry back titanium dioxide is 0.5～1.0mg/cm
2
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102388956A (en) * | 2011-11-16 | 2012-03-28 | 宁波海通食品科技有限公司 | Ultraviolet and nano zinc oxide combined sterilizing method for convenient vegetable dishes |
| CN102698729A (en) * | 2012-06-11 | 2012-10-03 | 遵义医学院 | Method for enhancing adhesiveness of nano TiO2 on surface of active carbon |
| CN105944708A (en) * | 2016-04-28 | 2016-09-21 | 安徽理工大学 | TiO2-C@TiO2-rGO transparent self-supporting film, and production method and application thereof |
| CN107051419A (en) * | 2017-05-10 | 2017-08-18 | 上海师范大学 | A kind of super long titanium dioxide nano wire/three-dimensional porous composite of NACF and preparation method and application |
| CN109078629A (en) * | 2018-08-20 | 2018-12-25 | 广东工业大学 | A kind of TiO of the growth of the controllability on carbon fiber paper2And its preparation method and application |
-
2009
- 2009-01-07 CN CN200910028641A patent/CN101766996A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102388956A (en) * | 2011-11-16 | 2012-03-28 | 宁波海通食品科技有限公司 | Ultraviolet and nano zinc oxide combined sterilizing method for convenient vegetable dishes |
| CN102388956B (en) * | 2011-11-16 | 2013-02-27 | 宁波海通食品科技有限公司 | Ultraviolet and nano zinc oxide combined sterilizing method for convenient vegetable dishes |
| CN102698729A (en) * | 2012-06-11 | 2012-10-03 | 遵义医学院 | Method for enhancing adhesiveness of nano TiO2 on surface of active carbon |
| CN105944708A (en) * | 2016-04-28 | 2016-09-21 | 安徽理工大学 | TiO2-C@TiO2-rGO transparent self-supporting film, and production method and application thereof |
| CN105944708B (en) * | 2016-04-28 | 2018-11-20 | 安徽理工大学 | TiO2-C@TiO2Transparent self-supporting film of-rGO and its preparation method and application |
| CN107051419A (en) * | 2017-05-10 | 2017-08-18 | 上海师范大学 | A kind of super long titanium dioxide nano wire/three-dimensional porous composite of NACF and preparation method and application |
| CN109078629A (en) * | 2018-08-20 | 2018-12-25 | 广东工业大学 | A kind of TiO of the growth of the controllability on carbon fiber paper2And its preparation method and application |
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Application publication date: 20100707 |