CN109052546A - A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water - Google Patents
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water Download PDFInfo
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- CN109052546A CN109052546A CN201810801305.0A CN201810801305A CN109052546A CN 109052546 A CN109052546 A CN 109052546A CN 201810801305 A CN201810801305 A CN 201810801305A CN 109052546 A CN109052546 A CN 109052546A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water methods, illumination is carried out to the organic dye waste water of addition light-catalyzed reaction gel mould and realizes absorption method-photocatalytic degradation method Combined Treatment, light-catalyzed reaction gel mould includes light-catalyzed reaction site and polar group, the peripheral region in light-catalyzed reaction site is strong absorption polar group region, the charge in strong absorption polar group region and non-strong absorption polar group region is positive or is negative, the current potential in strong absorption polar group region is higher than the current potential in non-strong absorption polar group region, strong absorption polar group region is constituted or is gathered by weakly stable polar group by adsorbing polar group by force and constituted.A kind of absorption method of the invention-photocatalytic degradation method Combined Treatment organic dye waste water method, under common sunshine environment can efficient degradation azo dyes molecule, catalytic degradation dye molecule is high-efficient, percent of decolourization is high, the removal rate of dyestuff is high, at low cost, there is fabulous promotional value.
Description
Technical field
The invention belongs to Organic Dyestuff Wastewater Treatment field, being related to a kind of absorption method-photocatalytic degradation method Combined Treatment has
The method of machine waste water from dyestuff.
Background technique
In recent years, researcher achieves major progress to the research of semiconductor light-catalyst, there is catalysis under visible light
The photochemical catalyst of performance has become current most remarkable environmental progress scavenging material, is widely used in each of environmental protection
The treatment of Organic Wastewater field of the organic pollutants such as dyestuff or pesticide in field, such as processing waste water.
Dyestuff is a kind of important fine chemical product, closely related with the clothing, food, lodging and transportion -- basic necessities of life of the mankind.Dye species are various,
Dyestuff in molecule containing azo group (- N=N-) structure is referred to as azo dyes.Azo dyes are current most species and use
The most wide a class of dyes in way.With the fast development of dye industry, waste water from dyestuff has become current most important pollution source of water body
One of, if waste water from dyestuff is unprocessed it is directly discharged in environment that the health of contactee can be seriously affected.Therefore, azo
Waste water from dyestuff before discharging must be handled it, it is made to be degraded into the substance of environmental sound.Due to complicated component,
The features such as high organic content, coloration are big and toxicity is big, azo dyes waste water has become industrial wastewater difficult to deal with.Mesh
Before, it explores effective azo dyes wastewater treatment method and has become the project actively studied both at home and abroad.
In order to solve azo dyes waste water to pollution brought by environment, domestic and foreign scholars do the processing of waste water from dyestuff
A large amount of research work, and achieve certain progress.The method of existing degradation azo dyes waste water includes physics at present
Method, chemical method and bioanalysis.Wherein physical method is by modes such as ultrasonic wave or high pressure pulse discharges to the dyestuff in waste water point
Son is degraded, but its higher cost, limits its further popularization and application；Although bioanalysis operating cost is low, degradation
Rate is slower, also can not meet current demand.And chemical method is after chemical substance is added in waste water by oxidation or reduction
Means destroy the structure of azo dyes molecule to achieving the purpose that degradation, this method economical and effective the most.
The method of most common azo dyes catalytic degradation is photocatalytic oxidation in chemical method, is to utilize ultraviolet light
Excite TiO2Semiconductor material is degraded.Although this method degradation rate height but the big discounting of degradation effect under common sunshine environment
Button.
It would therefore be highly desirable to a kind of method for studying energy efficient degradation azo dyes under common sunshine environment.
Summary of the invention
The purpose of the invention is to overcome above-mentioned problems of the prior art, one kind is provided in common sunshine environment
Absorption method-photocatalytic degradation method Combined Treatment organic dye waste water method of lower energy efficient degradation azo dyes.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, it is solidifying to addition light-catalyzed reaction
The organic dye waste water of glue film carries out illumination and realizes absorption method-photocatalytic degradation method Combined Treatment；
The light-catalyzed reaction gel mould includes light-catalyzed reaction site and polar group, the light-catalyzed reaction site
Peripheral region is strong absorption polar group region, and the region adsorbed by force other than polar group region in light-catalyzed reaction gel mould is
Non- strong absorption polar group region；
The charge in the strong absorption polar group region and non-strong absorption polar group region is positive or is negative；
The current potential in the strong absorption polar group region is higher than the current potential in non-strong absorption polar group region；
The strong absorption polar group region is constituted or is gathered by weakly stable polar group by adsorbing polar group by force and constituted.
As a preferred technical scheme:
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, it is described organic
The concentration of organic dyestuff is 50~400mg/L in waste water from dyestuff；The organic dyestuff is in methylene blue, methyl orange and active red
More than one；The time that the light-catalyzed reaction gel mould reaches swelling equilibrium is 20~30min；Light after swelling equilibrium is urged
Changing reaction gel film is 120~150min to the time of equilibrium adsorption of organic dyestuff.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, it is described organic
The quality and area ratio of dyestuff and light-catalyzed reaction gel mould are 0.5~1.5:22.5g/cm2.Organic dyestuff is anti-with photocatalysis
Answer the limited proportion of gel mould that can guarantee abundant adsoption catalysis of the light reaction gel mould for organic dyestuff within this range.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, the light are urged
Change reaction gel film has good catalytic performance under LED light, and the illumination uses 9W white LED lamp；After 7~10h of illumination,
The degradation rate of organic dyestuff is 98% or more.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, the light are urged
Change reaction gel film has good catalytic performance under sunlight, and the illumination uses sunlight；After 24~36h of illumination, have
The degradation rate of engine dyeing material is 98% or more.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, the weak suction
Attached polar group and the polar group in non-strong absorption polar group region are identical polar group；
The light-catalyzed reaction gel mould is mainly made of substrate and light-catalyzed reaction system；
The substrate is the network gel with hole, contains adsorption site, the adsorption potential of the substrate on the substrate
Point adsorption photochemical catalysis reaction system is simultaneously fixed in hole；
The substrate contains non-strong absorption polar group；
The light-catalyzed reaction system contains polar group and light-catalyzed reaction site, the polarity in light-catalyzed reaction system
Group is strong absorption polar group or weakly stable polar group.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, the light are urged
The content for changing light-catalyzed reaction system in reaction gel film is 2.37~2.47wt%；The content of light-catalyzed reaction system is low, then
Catalyst content is low, and the photocatalysis performance that the additive amount of too low catalyst will lead to laminated film is low, simultaneously because catalyst
Itself there is certain color, so that the color of film is too deep, the absorption and conversion for light become for excessively high catalyst addition meeting
It is weak, it equally will affect light-catalysed performance；The water absorption rate of the substrate is 88~92%, and substrate is macromolecule hydrogel film,
Its material is sodium alginate, potassium alginate, sodium carboxymethylcellulose, carboxymethyl cellulose, potassium carboxymethylcellulose, mono carboxylic shell
Glycan, mono carboxylic chitosan sodium, lentinan, lentinan sodium, xylose, xylose sodium or carboxymethyl starch；The non-strong absorption
Polar group is-COO-。
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, photocatalysis are anti-
Answering system is the nanometer particle congery of micella cladding, and stability is determined by zeta potential, when its absolute value is greater than 30mV, for stabilization
Micelle volume, the light-catalyzed reaction system is mainly made of catalyst and wrapping layer, and wrapping layer is wrapped in the table of catalyst
Face, the catalyst surface contain light-catalyzed reaction site, and the wrapping layer forms strong absorption polar group region, the catalysis
The mass ratio of agent and wrapping layer is 1.40~12.46:100.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, the catalysis
Agent is nano silver, nano zine oxide, nano-titanium dioxide or doped nano titanium dioxide, the average grain diameter of the catalyst are as follows:
6~22nm of nano silver, 10~30nm of nano zine oxide, nano-titanium dioxide or doped nano titanium dioxide.
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as described above, the package
Layer by free oleic acid ammonium complex compound alkyl chain and the oleic acid ammonium complex compound for being adsorbed on catalyst surface alkyl chain phase interpenetrating
It inserts and is formed；Polar group in the light-catalyzed reaction system is that ammonium oleate end group ionizes the group to be formed.
Organic dye waste water is handled using the light-catalyzed reaction gel mould with different catalysts content, specifically such as
Under:
By taking methylene blue/methyl orange as an example, methylene blue/methyl orange high concentration dye mother solution of 40mg/L is configured, is tested
It is preceding to take 25mL dye mother solution in 100mL volumetric flask respectively, deionized water is added and is diluted to scale, at this time to degradation of dye concentration
For 10mg/L, normal temperature storage is spare.Light-catalyzed reaction gel mould is cut into 25mm*25mm, impregnates 20min in deionized water
Reach swelling equilibrium, then, the above-mentioned 10mg/L of 50mL taken to wait for degradation of dye liquid, make under low speed magnetic agitation film with wait react
Solution comes into full contact with absorption, and monitors solution absorbance with ultraviolet-visible spectrophotometer, obtain the time of adsorption saturation with
And absorption-time graph.The solution of adsorption saturation is placed under sunlight/LED lamplight and is irradiated, and is divided with ultraviolet-visible light
The concentration of dye molecule, obtains degradation-time graph in the monitoring of light photometer and recording solution.
Absorption-time plot and degradation-time plot such as Fig. 1 and 2 under finally obtained different catalysts content
Shown, in figure, blank, Ag-0.5, Ag-1.0, Ag-1.5 and Ag-1.8 are respectively catalyst (nano silver) and macromolecule water-setting
The mass ratio of glue film is the light-catalyzed reaction gel mould of 0:100,0.5:100,1.0:100,1.5:100,1.8:100 (g/g)
Absorption-the time graph and degradation-time graph that organic dye waste water is handled.
It can be seen from the figure that the adsorbance of film has the tendency that reduction, the absorption of blank film with the increase of catalyst
Property it is most strong, but with the increase of catalyst, degradation efficiency is consequently increased, the absorption of the comprehensive film of the present invention and degradation it is dual
Function, so that the azo dyes molecule in the organic dye waste water handled using method of the invention is under common sunshine environment
It can be by catalytic degradation rapidly and efficiently.
Invention mechanism:
Light-catalyzed reaction gel mould of the invention, non-strong absorption polar group region be absorption-rich region, it is adsorbable simultaneously
The dye molecule under a large amount of decentralized environments is stored, strong polar group region of adsorbing is absorption-conversion zone, can be by dye molecule
The small molecule without toxicity is resolved into, after the completion of the dye molecule catalytic degradation reaction on light-catalyzed reaction site, due to
The current potential in strong absorption polar group region is higher than the current potential in non-strong absorption polar group region, non-strong absorption polarity on thin-film carrier
Group region absorption dye molecule under the action of concentration gradient and electrostatic attraction, can Spontaneous migration to by force adsorb polar group
On the light-catalyzed reaction site of region package, achievees the effect that continue reaction, reaction efficiency is greatly improved, to make
The azo dyes molecule obtained in organic dye waste water can be by catalytic degradation rapidly and efficiently under common sunshine environment.
The utility model has the advantages that
(1) a kind of absorption method of the invention-photocatalytic degradation method Combined Treatment organic dye waste water method, in photocatalysis
In reaction system, gel film material has the function of being enriched with and store, and is directly reacted compared under aqueous environment, coagulates
Glue thin film system can store the dye molecule largely under evenly dispersed environment, greatly improve reaction efficiency；
(2) a kind of absorption method of the invention-photocatalytic degradation method Combined Treatment organic dye waste water method, photocatalysis are anti-
It answers gel mould itself translucency good, compared to water body internal-response, reduces the resistance of sewage and catalyst carrier itself to light
Gear effect, can be such that lighting effect maximizes；
(3) a kind of absorption method of the invention-photocatalytic degradation method Combined Treatment organic dye waste water method, in aqueous solution
Under environment, when the dye molecule on supported catalyst after the reaction was completed, the dye molecule adsorbed on thin-film carrier is in concentration gradient
Under the action of electrostatic attraction, it can achieve the effect that continue reaction, make on Spontaneous migration to nanocatalyst adsorption site
Reaction continual can carry out, and the supported catalyst in reaction is not easily to fall off, and the gel mould after reaction can be recycled repeatedly,
Recycling, reduces production cost, there is fabulous commercial introduction value；
(4) a kind of absorption method of the invention-photocatalytic degradation method Combined Treatment organic dye waste water method, catalytic degradation
High-efficient, the percent of decolourization height of dye molecule, the removal rate height of dyestuff are at low cost.
Detailed description of the invention
Fig. 1 is absorption-time plot that organic dyestuff is handled under different catalysts concentration；
Fig. 2 is degradation-time plot that organic dyestuff is handled under different catalysts concentration；
Fig. 3 is the structural schematic diagram of the light-catalyzed reaction gel mould of the embodiment of the present invention 1；
Fig. 4 is the side view under the SEM of the light-catalyzed reaction gel mould of the embodiment of the present invention 1；
Fig. 5 is the exterior view under the SEM of the light-catalyzed reaction gel mould of the embodiment of the present invention 1；
Fig. 6 is the scale diagrams of light-catalyzed reaction gel mould prepared by embodiment 1；
Fig. 7 is the schematic diagram that lighting process is carried out to the light-catalyzed reaction gel mould of embodiment 1；
Wherein, 1-LED lamp, 2- light-catalyzed reaction gel mould.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
The structural schematic diagram of light-catalyzed reaction gel mould is as shown in figure 3, light-catalyzed reaction gel mould is mainly by water absorption rate
91% and the macromolecule hydrogel film with network structure and light-catalyzed reaction system composition, light in light-catalyzed reaction gel mould
The content of catalystic converter system is 2.40wt%, and adsorption site is contained on macromolecule hydrogel film, and adsorption site absorption light is urged
Change reaction system and be fixed in hole, macromolecule hydrogel film contains non-strong absorption polar group-COO-,-COO-Shape
Cheng Feiqiang adsorbs polar group region, wherein the material of macromolecule hydrogel film is potassium alginate, light-catalyzed reaction system master
It will be by the alkyl of the alkyl chain of nano silver and free oleic acid ammonium complex compound and the oleic acid ammonium complex compound for being adsorbed on nanometer silver surface
The mutually interspersed wrapping layer composition formed of chain, wrapping layer are wrapped in the surface of nano silver, and the average grain diameter of nano silver is 9nm, is received
Rice silver surface contains light-catalyzed reaction site, and the mass ratio of nano silver and wrapping layer is 6.64:100, and wrapping layer forms strong absorption
Polar group region, the strong group for adsorbing polar group region are that ammonium oleate end group ionizes the group to be formed, and adsorb polar group by force
The current potential in group region is higher than the current potential in non-strong absorption polar group region.Non- strong absorption polar group region is absorption-storage area
Domain, adsorbable and store the organic contamination molecule under a large amount of decentralized environments, strong polar group region of adsorbing is absorption-reaction zone
Domain, it is adsorbable and be catalyzed organic contamination molecular degradation, when the organic contamination molecule on light-catalyzed reaction site after the reaction was completed, by
Current potential in absorption polar group region by force is higher than the current potential in non-strong absorption polar group region, non-strong absorption pole on thin-film carrier
Property group region absorption organic pollutant molecule under the action of concentration gradient and electrostatic attraction, pass through collaboration effect of mass transmitting pass
It is handed on the light-catalyzed reaction site of strong absorption polar group region package, achievees the effect that continue reaction, greatly mention
High reaction efficiency.
SEM side view and the exterior view difference of light-catalyzed reaction gel mould obtained are as shown in Figures 4 and 5, can be with from figure
Find out, the film surface structure under ionomer system is smooth, and inside shows multilayer parallel structure, and mechanical strength is high, high score
The porous structure that sub- polysaccharide film forming procedure leaves also makes it have good adsorption capacity；
Light-catalyzed reaction gel mould cut out after dimensional drawing as shown in fig. 6, light-catalyzed reaction gel mould a length of 30cm, it is wide
For 20cm, with a thickness of 100 μm；
(2) as shown in fig. 7, adding the organic dye waste water light of light-catalyzed reaction gel mould 2 using 1 pair of 9W white LED lamp
Absorption method-photocatalytic degradation method Combined Treatment is realized according to 8h, and wherein the concentration of organic dyestuff is 200mg/ in organic dye waste water
The quality and area ratio of L, organic dyestuff and light-catalyzed reaction gel mould are 1:22.5g/cm2, organic dyestuff is methylene blue,
The time that light-catalyzed reaction gel mould reaches swelling equilibrium is 25min, and the light-catalyzed reaction gel mould after swelling equilibrium is to methylene
The time of equilibrium adsorption of base indigo plant is 135min.
After the above method is handled, the degradation rate of methylene blue is 99.5%.
Embodiment 2
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 92% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.47wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
For sodium alginate, light-catalyzed reaction system mainly by nano silver and free oleic acid ammonium complex compound alkyl chain and be adsorbed on nanometer
The mutually interspersed wrapping layer composition formed of the alkyl chain of the oleic acid ammonium complex compound of silver surface, wrapping layer are wrapped in the table of nano silver
The average grain diameter in face, nano silver is 6nm, and nanometer silver surface contains light-catalyzed reaction site, the mass ratio of nano silver and wrapping layer
For 12.46:100, wrapping layer forms strong absorption polar group region, and the strong group for adsorbing polar group region is ammonium oleate end group
The group formed is ionized, the strong current potential for adsorbing polar group region is higher than the current potential in non-strong absorption polar group region；
(2) absorption is realized using organic dye waste water illumination 7h of the 9W white LED lamp to addition light-catalyzed reaction gel mould
Method-photocatalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 50mg/L, organic dyestuff and light in organic dye waste water
The quality and area ratio for being catalyzed reaction gel film are 0.5:22.5g/cm2, organic dyestuff is methyl orange, light-catalyzed reaction gel
The time that film reaches swelling equilibrium is 20min, when the light-catalyzed reaction gel mould after swelling equilibrium is to the adsorption equilibrium of methyl orange
Between be 120min.
After the above method is handled, the degradation rate of methyl orange is 98%.
Embodiment 3
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 90% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.38wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region；Wherein, the material of macromolecule hydrogel film
For sodium carboxymethylcellulose, light-catalyzed reaction system is mainly by the alkyl chain and absorption of nano silver and free oleic acid ammonium complex compound
In the mutually interspersed wrapping layer composition formed of the alkyl chain of the oleic acid ammonium complex compound of nanometer silver surface, wrapping layer is wrapped in nano silver
Surface, the average grain diameter of nano silver is 18nm, and nanometer silver surface contains light-catalyzed reaction site, the matter of nano silver and wrapping layer
Amount ratio is 3.44:100, and wrapping layer forms strong absorption polar group region, and the group in strong absorption polar group region is ammonium oleate
End group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is higher than the current potential in non-strong absorption polar group region；
(2) absorption is realized using organic dye waste water illumination 10h of the 9W white LED lamp to addition light-catalyzed reaction gel mould
Method-photocatalytic degradation method Combined Treatment, wherein in organic dye waste water organic dyestuff concentration be 400mg/L, organic dyestuff with
The quality and area ratio of light-catalyzed reaction gel mould are 1.5:22.5g/cm2, organic dyestuff is active red, and light-catalyzed reaction is solidifying
The time that glue film reaches swelling equilibrium is 30min, adsorption equilibrium of the light-catalyzed reaction gel mould after swelling equilibrium to active red
Time is 150min.
After the above method is handled, the degradation rate of active red is 98.2%.
Embodiment 4
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 88% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.37wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
For potassium carboxymethylcellulose, light-catalyzed reaction system is mainly by the alkyl chain and absorption of nano silver and free oleic acid ammonium complex compound
In the mutually interspersed wrapping layer composition formed of the alkyl chain of the oleic acid ammonium complex compound of nanometer silver surface, wrapping layer is wrapped in nano silver
Surface, the average grain diameter of nano silver is 22nm, and nanometer silver surface contains light-catalyzed reaction site, the matter of nano silver and wrapping layer
Amount ratio is 1.40:100, and wrapping layer forms strong absorption polar group region, and the group in strong absorption polar group region is ammonium oleate
End group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is higher than the current potential in non-strong absorption polar group region；
(2) it is realized and is inhaled using organic dye waste water illumination 7.5h of the 9W white LED lamp to addition light-catalyzed reaction gel mould
Attached method-photocatalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 100mg/L, organic dyestuff in organic dye waste water
Quality and area ratio with light-catalyzed reaction gel mould are 0.8:22.5g/cm2, organic dyestuff is methylene blue and methyl orange
Mixture (mass ratio 1:1), the time that light-catalyzed reaction gel mould reaches swelling equilibrium is 22min, the light after swelling equilibrium
Being catalyzed reaction gel film is 130min to the time of equilibrium adsorption of methylene blue and methyl orange.
After the above method is handled, the degradation rate of methylene blue is 98.5%, and the degradation rate of methyl orange is 98.3%.
Embodiment 5
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 90% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.38wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, contain on macromolecule hydrogel film
Non- strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
Matter is carboxymethyl cellulose, and light-catalyzed reaction system is mainly by the alkyl chain of nano-titanium dioxide and free oleic acid ammonium complex compound
It is formed with the mutually interspersed wrapping layer formed of alkyl chain for the oleic acid ammonium complex compound for being adsorbed on nano-titanium dioxide surface, wrapping layer
It is wrapped in the surface of nano-titanium dioxide, the average grain diameter of nano-titanium dioxide is 20nm, and light is contained on nano-titanium dioxide surface
The mass ratio of catalysis reaction site, nano-titanium dioxide and wrapping layer is 1.42:100, and wrapping layer forms strong absorption polar group
Region, the strong group for adsorbing polar group region are that ammonium oleate end group ionizes the group to be formed, strong absorption polar group region
Current potential is higher than the current potential in non-strong absorption polar group region；
(2) it is realized and is inhaled using organic dye waste water illumination 8.5h of the 9W white LED lamp to addition light-catalyzed reaction gel mould
Attached method-photocatalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 150mg/L, organic dyestuff in organic dye waste water
Quality and area ratio with light-catalyzed reaction gel mould are 0.9:22.5g/cm2, organic dyestuff be methylene blue, methyl orange and
The mixture (mass ratio 1:1:1) of active red, the time that light-catalyzed reaction gel mould reaches swelling equilibrium is 28min, and swelling is flat
Light-catalyzed reaction gel mould after weighing apparatus is 126min to the time of equilibrium adsorption of methyl orange, methylene blue and active red.
After the above method is handled, the degradation rate of methylene blue is 98.5%, and the degradation rate of methyl orange is 98.3%, living
Property red degradation rate be 98.6%.
Embodiment 6
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 88% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.42wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, contain on macromolecule hydrogel film
Non- strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
Matter is carboxymethyl starch, and light-catalyzed reaction system is mainly by the alkyl chain and suction of nano zine oxide and free oleic acid ammonium complex compound
It is attached to the mutually interspersed wrapping layer composition formed of alkyl chain of the oleic acid ammonium complex compound of surface of nanometer zinc oxide, wrapping layer is wrapped in
The average grain diameter on the surface of nano zine oxide, nano zine oxide is 10nm, and surface of nanometer zinc oxide contains light-catalyzed reaction site,
The mass ratio of nano zine oxide and wrapping layer is 3.45:100, and wrapping layer forms strong absorption polar group region, adsorbs polarity by force
The group in group region is that ammonium oleate end group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is higher than non-strong absorption
The current potential in polar group region；
(2) absorption is realized using organic dye waste water illumination 9h of the 9W white LED lamp to addition light-catalyzed reaction gel mould
Method-photocatalytic degradation method Combined Treatment, wherein in organic dye waste water organic dyestuff concentration be 250mg/L, organic dyestuff with
The quality and area ratio of light-catalyzed reaction gel mould are 1:22.5g/cm2, organic dyestuff is methylene blue, and light-catalyzed reaction is solidifying
The time that glue film reaches swelling equilibrium is 27min, and the light-catalyzed reaction gel mould after swelling equilibrium is flat to the absorption of methylene blue
The weighing apparatus time is 140min.
After the above method is handled, the degradation rate of methylene blue is 98.8%.
Embodiment 7
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 91% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.45wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
For mono carboxylic chitosan, light-catalyzed reaction system is mainly by the alkyl of doped nano titanium dioxide and free oleic acid ammonium complex compound
The mutually interspersed wrapping layer formed of alkyl chain of chain and the oleic acid ammonium complex compound for being adsorbed on doped nano titanium dioxide surface forms,
Wrapping layer is wrapped in the surface of doped nano titanium dioxide, and the average grain diameter of doped nano titanium dioxide is 30nm, dopen Nano
Titanium dioxide surface contains light-catalyzed reaction site, and the mass ratio of doped nano titanium dioxide and wrapping layer is 7.22:100, packet
Covering layer forms strong absorption polar group region, and the strong group for adsorbing polar group region is that ammonium oleate end group ionizes the base to be formed
Group, the strong current potential for adsorbing polar group region are higher than the current potential in non-strong absorption polar group region；
(2) absorption method-light is realized to the organic dye waste water illumination of addition light-catalyzed reaction gel mould using sunlight for 24 hours
Catalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 260mg/L, organic dyestuff and photocatalysis in organic dye waste water
The quality and area ratio of reaction gel film are 1.1:22.5g/cm2, organic dyestuff is methylene blue, light-catalyzed reaction gel mould
The time for reaching swelling equilibrium is 30min, when the light-catalyzed reaction gel mould after swelling equilibrium is to the adsorption equilibrium of methylene blue
Between be 130min.
After the above method is handled, the degradation rate of methylene blue is 99%.
Embodiment 8
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
The macromolecule hydrogel film and light-catalyzed reaction body that light-catalyzed reaction gel mould is mainly 91.5% by water absorption rate
System forms, and the content of light-catalyzed reaction system is 2.43wt% in light-catalyzed reaction gel mould, contains on macromolecule hydrogel film
There is adsorption site, adsorption site adsorption photochemical catalysis reaction system is simultaneously fixed in hole, and macromolecule hydrogel film contains
Non- strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
Matter is mono carboxylic chitosan sodium, and light-catalyzed reaction system is mainly by the alkyl chain of nano zine oxide and free oleic acid ammonium complex compound
It is formed with the mutually interspersed wrapping layer formed of alkyl chain for the oleic acid ammonium complex compound for being adsorbed on surface of nanometer zinc oxide, wrapping layer packet
It is rolled in the surface of nano zine oxide, the average grain diameter of nano zine oxide is 28nm, and surface of nanometer zinc oxide contains light-catalyzed reaction
The mass ratio of site, nano zine oxide and wrapping layer is 7.26:100, and wrapping layer forms strong absorption polar group region, strong to adsorb
The group in polar group region is that ammonium oleate end group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is higher than non-strong
Adsorb the current potential in polar group region；
(2) absorption method-light is realized using organic dye waste water illumination 36h of the sunlight to addition light-catalyzed reaction gel mould
Catalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 280mg/L, organic dyestuff and photocatalysis in organic dye waste water
The quality and area ratio of reaction gel film are 1.2:22.5g/cm2, organic dyestuff is active red, and light-catalyzed reaction gel mould reaches
Time to swelling equilibrium is 28min, and the light-catalyzed reaction gel mould after swelling equilibrium is to the time of equilibrium adsorption of active red
145min。
After the above method is handled, the degradation rate of active red is 99.3%.
Embodiment 9
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 92% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.46wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
For lentinan, light-catalyzed reaction system mainly by nano silver and free oleic acid ammonium complex compound alkyl chain and be adsorbed on nanometer
The mutually interspersed wrapping layer composition formed of the alkyl chain of the oleic acid ammonium complex compound of silver surface, wrapping layer are wrapped in the table of nano silver
The average grain diameter in face, nano silver is 18nm, and nanometer silver surface contains light-catalyzed reaction site, the mass ratio of nano silver and wrapping layer
For 8.23:100, wrapping layer forms strong absorption polar group region, and the strong group for adsorbing polar group region is ammonium oleate end group
The group formed is ionized, the strong current potential for adsorbing polar group region is higher than the current potential in non-strong absorption polar group region；
(2) absorption method-light is realized using organic dye waste water illumination 30h of the sunlight to addition light-catalyzed reaction gel mould
Catalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 350mg/L, organic dyestuff and photocatalysis in organic dye waste water
The quality and area ratio of reaction gel film are 1.3:22.5g/cm2, organic dyestuff is active red, and light-catalyzed reaction gel mould reaches
Time to swelling equilibrium is 28min, and the light-catalyzed reaction gel mould after swelling equilibrium is to the time of equilibrium adsorption of active red
140min。
After the above method is handled, the degradation rate of active red is 98.9%.
Embodiment 10
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 89% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.38wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
For lentinan sodium, light-catalyzed reaction system is mainly by the alkyl chain and suction of nano-titanium dioxide and free oleic acid ammonium complex compound
It is attached to the mutually interspersed wrapping layer composition formed of alkyl chain of the oleic acid ammonium complex compound on nano-titanium dioxide surface, wrapping layer package
On the surface of nano-titanium dioxide, the average grain diameter of nano-titanium dioxide is 25nm, and photocatalysis is contained on nano-titanium dioxide surface
The mass ratio of reaction site, nano-titanium dioxide and wrapping layer is 5.25:100, and wrapping layer forms strong absorption polar group region,
The group in strong absorption polar group region is that ammonium oleate end group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is high
Current potential in non-strong absorption polar group region；
(2) absorption method-light is realized using organic dye waste water illumination 32h of the sunlight to addition light-catalyzed reaction gel mould
Catalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 300mg/L, organic dyestuff and photocatalysis in organic dye waste water
The quality and area ratio of reaction gel film are 1.4:22.5g/cm2, organic dyestuff is methyl orange, and light-catalyzed reaction gel mould reaches
Time to swelling equilibrium is 20min, and the light-catalyzed reaction gel mould after swelling equilibrium is to the time of equilibrium adsorption of methyl orange
120min。
After the above method is handled, the degradation rate of methyl orange is 98.5%.
Embodiment 11
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
Light-catalyzed reaction gel mould mainly by water absorption rate be 91% macromolecule hydrogel film and light-catalyzed reaction system
It forms, the content of light-catalyzed reaction system is 2.41wt% in light-catalyzed reaction gel mould, is contained on macromolecule hydrogel film
Adsorption site, adsorption site adsorption photochemical catalysis reaction system are simultaneously fixed in hole, and macromolecule hydrogel film contains non-
Strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
For xylose, light-catalyzed reaction system is mainly received by the alkyl chain of nano-titanium dioxide and free oleic acid ammonium complex compound with being adsorbed on
The mutually interspersed wrapping layer composition formed of the alkyl chain of the oleic acid ammonium complex compound of rice titanium dioxide surface, wrapping layer are wrapped in nanometer
The average grain diameter on the surface of titanium dioxide, nano-titanium dioxide is 25nm, and light-catalyzed reaction position is contained on nano-titanium dioxide surface
The mass ratio of point, nano-titanium dioxide and wrapping layer is 7.2:100, and wrapping layer forms strong absorption polar group region, strong to adsorb
The group in polar group region is that ammonium oleate end group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is higher than non-strong
Adsorb the current potential in polar group region；
(2) absorption method-light is realized using organic dye waste water illumination 34h of the sunlight to addition light-catalyzed reaction gel mould
Catalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 380mg/L, organic dyestuff and photocatalysis in organic dye waste water
The quality and area ratio of reaction gel film are 1.4:22.5g/cm2, organic dyestuff is methyl orange, and light-catalyzed reaction gel mould reaches
Time to swelling equilibrium is 25min, and the light-catalyzed reaction gel mould after swelling equilibrium is to the time of equilibrium adsorption of methyl orange
130min。
After the above method is handled, the degradation rate of methyl orange is 99.1%.
Embodiment 12
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, its step are as follows:
(1) light-catalyzed reaction gel mould is prepared；
The macromolecule hydrogel film and light-catalyzed reaction body that light-catalyzed reaction gel mould is mainly 90.5% by water absorption rate
System forms, and the content of light-catalyzed reaction system is 2.44wt% in light-catalyzed reaction gel mould, contains on macromolecule hydrogel film
There is adsorption site, adsorption site adsorption photochemical catalysis reaction system is simultaneously fixed in hole, and macromolecule hydrogel film contains
Non- strong absorption polar group-COO-,-COO-Form non-strong absorption polar group region, wherein the material of macromolecule hydrogel film
Matter is xylose sodium, and light-catalyzed reaction system is mainly by the alkyl chain and absorption of nano-titanium dioxide and free oleic acid ammonium complex compound
In the mutually interspersed wrapping layer composition formed of the alkyl chain of the oleic acid ammonium complex compound on nano-titanium dioxide surface, wrapping layer is wrapped in
The average grain diameter on the surface of nano-titanium dioxide, nano-titanium dioxide is 20nm, and it is anti-that photocatalysis is contained on nano-titanium dioxide surface
Answer site, the mass ratio of nano-titanium dioxide and wrapping layer is 8:100, and wrapping layer forms strong absorption polar group region, strong to inhale
The group in attached polar group region is that ammonium oleate end group ionizes the group to be formed, and the strong current potential for adsorbing polar group region is higher than non-
The current potential in strong absorption polar group region；
(2) absorption method-light is realized using organic dye waste water illumination 32h of the sunlight to addition light-catalyzed reaction gel mould
Catalytic degradation method Combined Treatment, wherein the concentration of organic dyestuff is 360mg/L, organic dyestuff and photocatalysis in organic dye waste water
The quality and area ratio of reaction gel film are 1.5:22.5g/cm2, organic dyestuff is methylene blue, light-catalyzed reaction gel mould
The time for reaching swelling equilibrium is 26min, when the light-catalyzed reaction gel mould after swelling equilibrium is to the adsorption equilibrium of methylene blue
Between be 140min.
After the above method is handled, the degradation rate of methylene blue is 99.2%.
Claims (10)
1. a kind of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water method, it is characterized in that: to addition photocatalysis
The organic dye waste water of reaction gel film carries out illumination and realizes absorption method-photocatalytic degradation method Combined Treatment；
The light-catalyzed reaction gel mould includes light-catalyzed reaction site and polar group, around the light-catalyzed reaction site
Region is strong absorption polar group region；
The charge in the strong absorption polar group region and non-strong absorption polar group region is positive or is negative；
The current potential in the strong absorption polar group region is higher than the current potential in non-strong absorption polar group region；
The strong absorption polar group region is constituted or is gathered by weakly stable polar group by adsorbing polar group by force and constituted.
2. a kind of absorption method according to claim 1-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, the concentration of organic dyestuff is 50~400mg/L in the organic dye waste water；The organic dyestuff is methylene
One or more of blue, methyl orange and active red；The time that the light-catalyzed reaction gel mould reaches swelling equilibrium is 20~
30min；Light-catalyzed reaction gel mould after swelling equilibrium is 120~150min to the time of equilibrium adsorption of organic dyestuff.
3. a kind of absorption method according to claim 2-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, the quality and area ratio of the organic dyestuff and light-catalyzed reaction gel mould are 0.5~1.5:22.5g/cm2。
4. a kind of absorption method according to claim 3-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, the illumination uses 9W white LED lamp；After 7~10h of illumination, the degradation rate of organic dyestuff is 98% or more.
5. a kind of absorption method according to claim 3-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, the illumination uses sunlight；After 24~36h of illumination, the degradation rate of organic dyestuff is 98% or more.
6. a kind of absorption method according to claim 1-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, the polar group in the weakly stable polar group and non-strong absorption polar group region is identical polar group；
The light-catalyzed reaction gel mould is mainly made of substrate and light-catalyzed reaction system；
The substrate is the network gel with hole, and adsorption site is contained on the substrate, and the adsorption site of the substrate is inhaled
Attached light-catalyzed reaction system is simultaneously fixed in hole；
The substrate contains non-strong absorption polar group；
The light-catalyzed reaction system contains polar group and light-catalyzed reaction site, the polar group in light-catalyzed reaction system
To adsorb polar group or weakly stable polar group by force.
7. a kind of absorption method according to claim 6-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, the content of light-catalyzed reaction system is 2.37~2.47wt% in the light-catalyzed reaction gel mould；The substrate
Water absorption rate be 88~92%, substrate is macromolecule hydrogel film, and material is that sodium alginate, potassium alginate, carboxymethyl are fine
Tie up plain sodium, carboxymethyl cellulose, potassium carboxymethylcellulose, mono carboxylic chitosan, mono carboxylic chitosan sodium, lentinan, mushroom
Polysaccharide sodium, xylose, xylose sodium or carboxymethyl starch；The non-strong absorption polar group is-COO-。
8. a kind of absorption method according to claim 6-photocatalytic degradation method Combined Treatment organic dye waste water method,
It being characterized in that, the light-catalyzed reaction system is mainly made of catalyst and wrapping layer, and wrapping layer is wrapped in the surface of catalyst,
The catalyst surface contains light-catalyzed reaction site, and the wrapping layer forms strong absorption polar group region, the catalyst
Mass ratio with wrapping layer is 1.40~12.46:100.
9. a kind of absorption method according to claim 8-photocatalytic degradation method Combined Treatment organic dye waste water method,
Be characterized in that, the catalyst be nano silver, nano zine oxide, nano-titanium dioxide or doped nano titanium dioxide, it is described to urge
The average grain diameter of agent are as follows: 6~22nm of nano silver, nano zine oxide, nano-titanium dioxide or doped nano titanium dioxide 10~
30nm。
10. a kind of absorption method according to claim 8-photocatalytic degradation method Combined Treatment organic dye waste water method,
It is characterized in that, alkyl chain and the ammonium oleate network that is adsorbed on catalyst surface of the wrapping layer by free oleic acid ammonium complex compound
Close the mutually interspersed formation of alkyl chain of object；Polar group in the light-catalyzed reaction system is that ammonium oleate end group ionizes to be formed
Group.
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