CN111359600A

CN111359600A - Load composite modified nano TiO2Waste water and waste gas pollutant treating ball

Info

Publication number: CN111359600A
Application number: CN202010455512.2A
Authority: CN
Inventors: 苏斌; 苏文雯; 苏文锦
Original assignee: Beijing Jinxiu New Technology Development Co ltd
Current assignee: Beijing Jinxiu New Technology Development Co ltd
Priority date: 2020-05-26
Filing date: 2020-05-26
Publication date: 2020-07-03
Anticipated expiration: 2040-05-26
Also published as: CN111359600B

Abstract

The invention relates to a wastewater and waste gas pollutant treatment ball loaded with composite modified nano TiO2, which comprises an active microporous ball and composite modified nano TiO2₂And photosensitizer or strong oxidant extracted from plant, the described composite modified nano TiO₂And a plant extract photosensitizer or a strong oxidizer are sequentially loaded on the active microporous balls. The invention modifies nanometer TiO compositely₂And a plant extract photosensitizer or a strong oxidant are sequentially loaded on the active microporous spheres to obtain active groups with high capacity of the treatment spheres, the diameter and the stacking layer thickness of the treatment spheres can be determined according to the concentration and the type of pollutants, waste gas can be treated and placed in a waste gas discharge channel, pollutants in the waste gas react with the active groups with high energy by utilizing the labyrinth principle, and the pollutants are finally converted into CO₂And H₂O, and the like.

Description

Load composite modified nano TiO2Waste water and waste gas pollutant treating ball

Technical Field

The invention relates to a loaded composite modified nano TiO₂The waste water and gas pollutant treating ball belongs to the field of waste water or fume purifying treatment facility.

Background

China is becoming the first major country of manufacturing industry, and the development of national economy is driven, but at the same time, the serious problem of waste gas pollution is brought, the types of waste gases discharged by different industries are different, and at present, because the components of industrial waste gases are more and more complex, the VOCs waste gas treatment method generally adopted by China can reduce the atmospheric pollution to a certain extent, but cannot effectively treat and thoroughly eradicate the waste gases. Meanwhile, due to the rapid development of the industrial industry, the exhaust emission in the atmosphere is remarkably increased. The waste gas decomposition difficulty is great, and under the effect of atmospheric flow, can constantly diffuse waste gas, and then enlarged the pollution range of waste gas, seriously pollute the natural environment, threaten people's healthy.

At present, 10 methods are mainly adopted for treating representative waste gas in China. (1) And a masking method: the principle is as follows: a more intense fragrance is used in conjunction with the odor to mask the odor so that it can be received by a person. The application range is as follows: the method is suitable for occasions needing to immediately and temporarily eliminate the influence of low-concentration malodorous gases, the malodorous intensity is about 2.5, and the sources are unorganized emission sources. The advantages are that: can eliminate the influence of the odor as soon as possible, and has great flexibility and low cost. The disadvantages are as follows: the malodorous components are not removed fundamentally, and the current environmental protection requirement cannot be passed.

(2) And a dilution diffusion method: the principle is as follows: the odorous gas is discharged to the atmosphere through a chimney or diluted with odorless air, and the concentration of the odorous substances is reduced to reduce odor. The application range is as follows: is suitable for treating middle and low concentration malodorous gas discharged by organizations. The advantages are that: low cost and simple equipment. The disadvantages are as follows: is easy to be limited by meteorological conditions, and the malodorous substances still exist fundamentally. At present, the environmental protection can not pass.

(3) Thermal combustion and catalytic combustion: the principle is as follows: the malodorous substances and the fuel gas are fully mixed at high temperature to realize complete combustion. The application range is as follows: it is suitable for treating high-concentration and small-gas-quantity combustible gas. The advantages are that: the purification efficiency is relatively high, and the malodorous substances are thoroughly oxidized and decomposed. The disadvantages are as follows: the equipment is easy to corrode, consumes fuel energy, has high treatment cost and is easy to form secondary pollution. The paint is widely applied to the industries of automobile coating, petrochemical industry, medicine and electronics at present.

(4) Water absorption method: the principle is as follows: the odor component is directly contacted with water by utilizing the characteristic that certain substances in the odor are easy to dissolve in water, thereby achieving the aim of deodorization by dissolving in water. The application range is as follows: water-soluble, organized sources of malodorous gases. The current environmental protection requirement can not pass. The advantages are that: simple process, convenient management, low equipment operation cost and secondary pollution, and the washing liquid needs to be treated. The disadvantages are as follows: the purification efficiency is low, the purification agent can be used in combination with other technologies, and the treatment effect on mercaptan, fatty acid and the like is poor.

(5) The principle of the liquid medicine absorption method: the odor components are removed by utilizing the characteristic that certain substances in the odor and the liquid medicine generate chemical reaction. The application range is as follows: is suitable for treating odor with large air volume and high and medium concentration. The advantages are that: can treat some odor components with pertinence, and has mature process. The disadvantages are as follows: low purification efficiency, consumption of absorbent, easy formation and secondary pollution. The current environmental protection requirement can not pass.

(6) And an adsorption method: the principle is as follows: the malodorous substance is transferred from the gas phase to the solid phase by utilizing the adsorption function of the adsorbent. The application range is as follows: it is suitable for treating low-concentration malodorous gas with high purification requirement. The advantages are that: the purification efficiency is relatively high, and multi-component malodorous gas can be treated. The disadvantages are as follows: the process is complex, the adsorbent is expensive, the regeneration is difficult, and the malodorous gas to be treated is required to have lower temperature and dust content.

(7) And a washing type activated sludge deodorization method: the principle is as follows: the malodorous substance is fully contacted with the mixed liquid containing the suspended matter slurry to be removed from the malodorous gas in the absorber, and the washing liquid is sent to the reactor to degrade the dissolved malodorous substance through the metabolic activity of the microorganism growing in suspension. The application range is as follows: has a wide application range, can treat odor with large air quantity, and has the advantages of easy control of operation conditions and small occupied area. The disadvantages are as follows: the equipment cost is high, the operation is complex and nutrient substances need to be added. The current environmental protection requirement can not pass.

(8) And an aeration type activated sludge deodorization method: the principle is as follows: the malodorous substances are dispersed into the mixed liquid containing the activated sludge in an aeration mode, and the malodorous substances are degraded by the microbes growing in a suspension manner, so that the application range is wide. The application range is as follows: at present, Japan is already used for odor treatment in a fecal treatment plant and a sewage treatment plant. The advantages are that: after the activated sludge is domesticated, the removal rate of malodorous components not exceeding the limit load can reach more than 99.5 percent. The disadvantages are as follows: the application of the method is limited by the strength of aeration.

(9) And the three-phase multi-medium catalytic oxidation process comprises the following steps: the principle is as follows: specially-made solid composite filler is filled in the reaction tower, and a multi-medium catalyst is compounded in the filler. When the malodorous gas passes through the packing layer under the action of the induced draft fan, the malodorous gas is fully contacted with the liquid-phase compound oxidant sprayed out in a divergent mist shape through the special nozzle on the surface of the solid-phase packing, and the pollution factors in the malodorous gas are fully decomposed under the catalytic action of the multi-medium catalyst. The application range is as follows: the method has wide application range, is particularly suitable for treating large-gas-volume and medium-high-concentration waste gas, and has good removal rate on hydrophobic pollutants. The advantages are that: the occupied area is small, the investment is low, and the operation cost is low; the management is convenient, and the device can be used immediately after being opened. The disadvantages are as follows: impact load resistance, difficult influence of pollutant concentration and temperature change, and certain amount of medicament consumption.

(10) And a low-temperature plasma technology: the principle is as follows: during the dielectric barrier discharge process, the plasma generates particles rich in extremely high chemical activity, such as electrons, ions, free radicals, excited molecules and the like. The pollutants in the exhaust gas react with the active groups with higher energy and are finally converted into CO₂And H₂O and the like, thereby achieving the purpose of purifying the waste gas. The application range is as follows: the method has wide application range and high purification efficiency, and is particularly suitable for multi-component malodorous gases which are difficult to treat by other methods, such as the industries of chemical industry, medicine and the like. The advantages are that: the electronic energy is high, and the device can almost meet common faults and solution measures of all the malodorous gas separation tank pulse bag-type dust collectors. The operation cost is relatively low, the reaction is fast, the equipment is started and stopped very fast, and the equipment can be started at any time. The disadvantages are as follows: the one-time investment is high, and the maintenance and replacement cost is high.

Disclosure of Invention

The invention aims to solve the technical problem of providing a load composite modified nano TiO₂The waste water and waste gas pollutant treatment ball solves the defects that the existing treatment equipment has high investment, high maintenance and replacement cost, is greatly influenced by environmental medicinal preparations, or has complex treatment process and the like.

The technical scheme for solving the technical problems is as follows: load composite modified nano TiO₂Is subjected toThe waste gas pollutant treating ball includes active microporous ball and composite modified nanometer TiO₂And photosensitizer or strong oxidant extracted from plant, the described composite modified nano TiO₂And a plant extract photosensitizer or a strong oxidizer are sequentially loaded on the active microporous balls.

The invention has the beneficial effects that: because the invention modifies the composite modified nano TiO₂And a plant extract photosensitizer or a strong oxidant are sequentially loaded on the active microporous spheres to obtain active groups with high capacity of the treatment spheres, the diameter and the stacking layer thickness of the treatment spheres can be determined according to the concentration and the type of pollutants, waste gas can be treated and placed in a waste gas discharge channel, pollutants in the waste gas react with the active groups with high energy by utilizing the labyrinth principle, and the pollutants are finally converted into CO₂And H₂Substances such as O may float on the gas-liquid interface (liquid interface where exhaust gas is generated). Or can be used as a medium for waste gas and sewage treatment by various facilities and equipment; the treatment ball pair can almost quickly treat all kinds of waste gas; if the waste gas is in the same reactor, the organic combination of adsorption, catalysis and decomposition separation can be realized, i.e. the reactant is adsorbed on the microporous ball and is adsorbed on the composite modified nano TiO₂The reaction product is separated from the catalyst at the same time.

On the basis of the technical scheme, the invention can be further improved as follows.

The invention loads the composite modified nano TiO as described above₂The wastewater and waste gas pollutant treating ball of (1), further, the active microporous ball is any one of hollow glass microsphere, floating bead, hollow microsphere, vitrified microsphere, sinking bead, glass fiber ball, nickel ball, silica ball, alumina ball, zeolite, molecular sieve, silica gel ball, active carbon ball, ceramic ball, cement ball and sand ball. The diameter of the microporous hollow sphere is 0.5-19mm, the pore diameter distribution of the micropores is 20nm-20um, the ignition loss is less than or equal to 6.0, the water content (normal temperature) is less than or equal to 18 percent, the stacking density is less than or equal to 0.75g/mL, the specific surface area is more than or equal to 220 square meters/g, the pore volume is more than or equal to 0.65mL/g, and the crushing strength is more than or equal to 8.0N-100N/particle.

The invention loads the composite modified nano TiO as described above₂Waste water and gas pollution ofThe plant extract photosensitizer is any one or more of porphyrin, chlorophyll, xanthene, erythrosine B, eosin, humic acid, quinoline, anthocyanin, anthocyanidin, fluorescein, rose bengal, thionine, phthalocyanine, porphyrine and rose bengal, and the strong oxidant is any one of hydrogen peroxide, sodium chlorate, sodium perchlorate, calcium hypochlorite, sodium percarbonate, ferric permanganate, potassium ferrate, sodium thiosulfate, potassium dichromate, trichloroisocyanuric acid, sodium acetate, lead dioxide, cobalt trifluoride, sodium ferrate, periodic acid, sodium bismuthate, sodium persulfate, potassium persulfate, chlorine dioxide, dichloroisocyanuric acid and salts thereof.

The invention provides a loaded composite modified nano TiO₂The preparation method of the waste water and gas pollutant treatment ball comprises the following steps:

step (1), carrying out surface modification on the microporous ball to prepare an active microporous ball;

step (2) preparing composite modified nano TiO₂Sol;

step (3), soaking the active microporous ball in the composite modified nano TiO₂Sol drying for a predetermined time

Dry roasting to obtain the load composite modified nano TiO₂Hollow spheres;

step (4), the load composite modified nanometer TiO prepared in the step (3) is used₂The hollow ball is soaked in

The plant extract is taken out and dried in a photosensitizer or a strong oxidant for a predetermined time to obtain the loaded composite modified nano TiO₂The waste water and gas pollutant treatment ball.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treatment ball further comprises the following steps of:

step (101), the microporous ball is washed and dried, then placed in 8% -20% acid solution, and soaked for 5-25%

Washing the dipped active microporous balls with water and drying to obtain acid-treated microporous balls;

and (102) soaking the acid-treated microporous spheres in an aluminum salt solution, washing with clear water, adding the acid-treated microporous spheres into a hydrolytic coupling agent alcohol solution with the pH value of 3-4, reacting at the constant temperature of 60-80 ℃ for a certain time, washing with toluene, and drying in vacuum at the temperature of 50-65 ℃ to obtain the surface-modified active microporous spheres. The constant temperature reaction is carried out for 2-6 hours, preferably 2 hours, and vacuum drying can be carried out for 24-48 hours, preferably 24 hours. The aluminum salt solution is preferably aluminum chloride, aluminum sulfate or aluminum nitrate, the concentration of the aluminum salt solution is preferably 30%, and the acid radical ion of the acid solution is required to be the same as the acid radical ion of the aluminum salt, so that the stability of a subsequent preparation system can be ensured.

The adoption of the further beneficial effects is as follows: the smaller the particle size of the common microporous ball particle is, the higher the adsorption capacity is, but the smaller the particle size is, the lower the particle strength is, the service life of the microporous ball particle is influenced, so that surface modification is needed to obtain a proper particle size to meet the requirement of the composite modified nano TiO₂And the requirement of good adsorption capacity of the plant extract photosensitizer or the strong oxidant.

The microporous ball is subjected to surface modification, and the compatibility between the particles and the dispersion medium enables the microporous ball and the dispersion medium to achieve a good infiltration state. The surface activity of the active microporous hollow sphere is improved, the surface tension of the microporous sphere is reduced, the surface energy is improved, the physical and chemical adsorption performance is improved, and conditions are created for coupling and grafting in the forming process of the final product of the whole system.

The active microporous ball has pore size distribution of 20nm-20um, pressure swing adsorption function and oxygen-enriched air, pores exist in the microporous hollow ball in a coherent form, and the active microporous ball has two action mechanisms when adsorbing pollutants, namely physical adsorption and chemical adsorption. The physical adsorption depends on the characteristic that the specific surface area of the pores of the active microporous ball is large, pollutants in the waste gas are trapped in the active microporous ball, and pollutant molecules are limited in the active microporous ball by utilizing the characteristic that the sizes of the pores and the molecular radius are equivalent. The chemical adsorption depends on the C atoms with defects in crystal lattices, oxygen-containing functional groups and polar surface oxides of the active microporous spheres, and the chemical characteristics obtained after treatment can be used for pertinently fixing pollutants on the inner surface and the outer surface of the active microporous spheres.

The invention loads the composite modified nano TiO as described above₂Further, in the step (2), the ratio of the coupling agent to the alcohol in the coupling agent alcohol solution is 20mL to 100mL/L, that is, the volume of the coupling agent to the alcohol is (20 mL to 100 mL): 1000 mL; and (2) washing the aluminum salt solution after soaking by using clear water, dropwise adding an acid water solution to the pH value of 3-4, hydrolyzing for 30-90 minutes at room temperature to obtain a uncoupling agent solution, and adding 50-150 g/L of the active microporous hollow spheres into the uncoupling agent solution for constant-temperature reaction. Preferably, the ratio of the coupling agent to the alcohol is 40-60mL/L, namely 40-60mL of the coupling agent, and the using amount of the alcohol is 1L;

the invention loads the composite modified nano TiO as described above₂Further, the acid in the acid solution is one or more of nitric acid, sulfuric acid, hydrochloric acid, boric acid, formic acid, tartaric acid, citric acid, tannic acid, acetic acid, oxalic acid, malic acid, mugineic acid, succinic acid, punicic acid, vanillic acid, benzoic acid, salicylic acid, coumaric acid, ferulic acid, syringic acid, citric acid, caffeic acid, benzoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, etc., preferably oxalic acid, the inventor finds that phosphoric acid cannot be used as a hydrolysis catalyst because white floc is rapidly produced in the hydrolysis process by using phosphoric acid as a hydrolysis catalyst, i.e., a condensate without coupling activity is formed; oxalic acid is preferred.

In the step (2), an acid water solution is dropwise added to the pH value of 3-4, the acid water solution can be an 8% -20% oxalic acid water solution, the hydrolysis is carried out for 1 hour at 40-60 ℃ (preferably 45 ℃), the coupling effect is best, the coating rate of the coupling agent is greater than 60%, and when the coating rate is less than 1 hour, the hydrolysis is not sufficient, the coupling effect is not good, and when the coating rate is greater than 1 hour, the condensation of a side coupling hydrolysate is intensified, a condensation compound without coupling activity is formed, the coupling effect is reduced, and the subsequent composite modified nano TiO can be caused to be subsequently₂The loading rate of the sol is significantly reduced.

The method can obtain active microporous ball, i.e. active microporous hollow ball, with porous structure, high dispersity, high specific surface area, good adsorptivity, good thermal stability and good load capacitySurface activity, large pore volume, high water absorption, small bulk density, good mechanical property and capability of well loading composite modified nano TiO₂Plant extract photosensitizer or strong oxidizer.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treatment ball further comprises the steps that the diameter of the active microporous ball is 0.5-19mm, the pore diameter distribution of micropores is 20nm-20um, the ignition loss is less than or equal to 6.0, the water content at normal temperature is less than or equal to 18%, the bulk density is less than or equal to 0.75g/mL, the specific surface area is more than or equal to 220 square meters/g, the pore volume is more than or equal to 0.65mL/g, and the crushing strength is more than or equal to 8.0N-100N/.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and exhaust gas pollutant treating ball is further characterized in that the coupling agent is a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, an organic chromium complex coupling agent or a phosphate coupling agent. Silane coupling agents are preferred, and specific silane coupling agents can be selected from A151, A171, A172 or KH570, preferably KH 570.

Hydrolyzing silane coupling agent to form silanol, and then compounding the silanol and the load modified nano TiO₂The hydroxyl on the surface of the nano oxide in the hollow sphere reacts, and the hydrolysis speed can be accelerated under acidic or alkaline conditions. The preferred coupling agent is KH570, which has a stable hydrolysis rate because the hydrolyzable group of KH570 is methoxy. The silane oligomer can have strong affinity and reactivity with active hydroxyl on the surface of the nano oxide, so that the coupling reaction can be carried out at a lower temperature, and the coupling efficiency can be reduced by excessive coupling agents due to condensation reaction, so that the ratio of the coupling agents to the alcohol is 40-60mL/L, preferably 50 mL/L.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treating ball, further, the composite modified nano TiO₂The sol is rare earth doped TiO₂The composite material sol is obtained by the following method:

step (201) of adding dropwise anhydrous ethanol and glacial acetic acid to n-butyl titanate under stirring

Dispersing and stirring the mixed solution to obtain a solution A; the n-butyl titanate: anhydrous ethanol: glacial acetic acid = (8: 40: 11) - (20: 25: 4); the dispersion stirring in this step is preferably 2 hours;

step (202), adding 20mg-100mg/L of rare earth salt into ionized water, uniformly stirring, namely adding 20-100 mg of rare earth salt into 1L of deionized water, adding 5mL-100mL/L of nitric acid, namely adding 5mL-100mL of nitric acid into 1L of rare earth salt deionized water mixed solution, stirring and mixing by a dispersion machine to obtain a solution B, and preferably stirring and mixing for 2 hours;

and (203) dropwise adding the solution B into the solution A under the condition of high-speed stirring, uniformly stirring to obtain transparent sol after dropwise adding, and preferably continuously stirring for 4 hours after dropwise adding.

The rare earth sol prepared by the method has stable load capacity on the active microporous spheres, and simultaneously ensures the effective load of a photosensitizer or a strong oxidizer of a subsequent plant extract. The rare earth doped TiO formed by the method₂Product, increase of TiO₂The oxygen storage capacity of the catalyst; inhibit the phase change of the active microporous ball and the sintering of the active component, and is beneficial to TiO₂Dispersion of the catalyst, etc.

Due to TiO₂The photocatalytic activity of the catalyst is determined by the light absorption capacity, the charge separation efficiency and the transfer rate of a photon-generated carrier, and during the preparation of the method, the doping of rare earth ions can inhibit the speed of forming sol-gel, so that the aim of refining solid particles is fulfilled.

In the invention, glacial acetic acid with a certain proportion is added, the glacial acetic acid plays a role of an inhibitor in the system, the speed of forming sol-gel is too slow when too much glacial acetic acid is added, the experimental progress is influenced, Ti (OH) precipitation appears when too little glacial acetic acid is added, and the preparation method is unfavorable for preparing the nano material.

The invention loads the composite modified nano TiO as described above₂The method for preparing the ball for treating pollutants in waste water and waste gas comprises the following steps of preparing a rare earth salt, wherein the rare earth salt is nickel nitrate, cerium nitrate, yttrium nitrate, ytterbium nitrate, erbium nitrate, cerium ammonium nitrate, lanthanum cerium nitrate, neodymium nitrate, europium nitrate, bismuth chloride, praseodymium chloride, indium chloride, cerium chloride, lanthanum chloride, yttrium chloride, gadolinium chloride, thulium amide, samarium chloride, cerium acetate and lanthanum acetateAny one or more of dysprosium acetate, holmium acetate, erbium acetate, thulium acetate, lanthanum carbonate, lanthanum cerium praseodymium neodymium carbonate, cerium carbonate and lanthanum cerium carbonate.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treating ball, further, the composite modified nano TiO₂Sol is graphene oxide composite TiO₂The composite material sol is obtained by the following method:

step (201), dispersing 100mg-500mg/L graphene oxide in deionized water, and performing ultrasonic separation

Dispersing and homogenizing to obtain a graphene oxide solution; dissolving tetrabutyl titanate in isopropanol to prepare a mixed solution A, wherein the volume ratio of tetrabutyl titanate to isopropanol is (1: 10) - (1: 30);

step (202), dropwise adding a graphene oxide solution into the mixed solution while stirring to obtain a mixed solution B, wherein the mixed solution A is: the volume ratio of the graphene solution is (1: 1) - (1: 3); dropwise adding a reducing agent into the mixed solution B under the stirring condition of 10g-50g/L, condensing, refluxing and continuously stirring to obtain the graphene composite TiO₂And (3) composite material sol. The time of the condensation reflux can be selected from 100-120 ℃ and the reflux is continuously stirred for 8-10 hours.

Graphene composite TiO prepared by the method₂The composite material improves the load performance of the sol on the premise of keeping the stability of the whole system, and is not easy to fall off in the subsequent recovery; the method obtains graphene composite TiO₂The composite material has excellent catalytic capability, 1) and the larger specific surface area of the composite material improves the adsorption capability of the material to organic pollutants. 2) And the formation of the heterojunction at the interface of the composite material improves the recombination between the photo-generated electrons and the holes. Compared with pure TiO₂The fermi level of the composite material may shift in a more positive direction, thereby increasing the utilization of longer wavelength photons. 3) After the surface of the graphene absorbs photons, electrons are injected into the TIO₂The conduction band, forming reactive excitons for degradation of organic contaminants, further increases the utilization of longer wavelength photons. 4) TiO2, TiO₂After the graphene is compounded, photo-generated electrons generated by excitation can be quickly transmitted to the surface through the graphene, the compounding probability of the electrons and holes is reduced, and the photon utilization rate is improved. On the other hand, depending on the huge specific surface area of graphene, an electron acceptor can be adsorbed to the surface of graphene, and the photocatalytic reaction rate is accelerated.

The graphene is enriched with sp2 hybridized carbon, and in the photocatalysis process, chemical bonds formed by the sp2 hybridized carbon are easier to polarize, so that the graphene has a large Raman cross section. When the titanium dioxide is excited by visible light, the pi state can generate resonance enhancement, the absorption intensity of the titanium dioxide in a visible light area is improved, and the photocatalysis effect of the titanium dioxide is expanded to the visible light area.

The graphene titanium dioxide composite obtained by the method has stable load performance, wherein the large specific surface area of the graphene enables organic dye molecules to be in photocatalyst TiO₂The enrichment effect of the surface is further enhanced, which is beneficial to the photocatalytic reaction; on the other hand, the graphene in the compound obtained by the method is used as a charge trapping center, so that the separation efficiency of electrons and holes in titanium dioxide is enhanced, and the photocatalysis effect is promoted.

The invention loads the composite modified nano TiO as described above₂The reducing agent is unsymmetrical dimethylhydrazine, hydrazine carbonate, hydrazine sulfate, hydrazine nitrate, dihydrazine carbonate, dithiohydrazine, semicarbazide, isoniazide, hydrazine hydrate, nitrofural, sodium borohydride, potassium borohydride, ammonium borohydride, lithium borohydride, manganese borohydride, sodium cyanoborohydride, lithium aluminum hydride, carbohydrazide, modified lignin, thiourea dioxide, steam ethanol, gaseous SO₂、NaHSO₄Dimethylene acetamide, ethylenediamine, EDTA, hydroiodic acid, vitamins, glucose, chitosan, gallic acid, L-glutathione, amino acids, aluminum powder, sodium citrate, zymolase, nicotinamide adenine dinucleotide phosphate, pectin, flavone, ascorbic acid, celeryAny one of vegetable extract and luteolin. Sodium borohydride is preferably selected as the reducing agent.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treating ball, further, the composite modified nano TiO₂TiO modified by deposition of nano metal particles by sol₂The composite material sol is obtained by the following method:

step (201), 10mg-100mg/L of nano metal particles and 100mg-300mg/L of stabilizing agent are added

Sequentially stirring and dispersing in absolute ethyl alcohol, ultrasonically dispersing, stirring and heating, slowly adding n-butyl titanate, and slowly adding 300 mL/L100-plus-300 mL/L n-butyl titanate, namely sequentially dispersing 10mg-100mg of nano metal particles, 100mg-300mg of stabilizer and 300mL of 100-plus-300 mL n-butyl titanate in 1L absolute ethyl alcohol to prepare nano metal particle dispersion liquid; the mass volume concentration of the nano metal particles dispersed in the absolute ethyl alcohol is preferably 50 mg/L; the mass volume concentration of the stabilizer dispersed in the absolute ethyl alcohol is preferably 200 mg/L; the volume concentration of the added amount of the n-butyl titanate is preferably 200 mL/L.

Step (202), stirring and dropping 20mL-100mL/L of absolute ethanol into deionized water to prepare ethanol solution, stirring and dropping the nano metal particle dispersion liquid into the ethanol solution, and stirring to prepare nano metal particle deposition modified TiO₂Stirring the composite material sol for 0.5h preferably; namely 20mL-100mL of absolute ethyl alcohol is stirred and dropped into 1L of anhydrous deionized water; the volume ratio of the nano metal particle dispersion liquid to the ethanol solution is 1: 1.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treating ball is further characterized in that the nano metal particles are Pt, Au, Ag, Pd, Cu, N, Rh, Ir, Ru and Os, and the particle size of the nano metal particles is less than 100 nm;

the stabilizer is polyvinylpyrrolidone, poly-2-vinylpyrrolidone, polyvinyl alcohol, poly-2-hydroxypropyl methacrylate, polymethyl methacrylate, poly-4-vinylpyrrolidone, poly-N-vinylformamide, poly-N-vinylacetamide, poly-N-vinylaisobutyramide, polystyrene sulfonic acid, sodium polystyrene sulfonate, polyacrylic acid, sodium polyacrylate, poly-2-acrylamide-2-methylpropanesulfonic acid, polystyrene b-poly-4-vinylpyrrolidone, polystyrene-b-polymethyl methacrylate, polystyrene-b-polyethylene oxide, polystyrene-b poly-2-vinylpyrrolidone, polystyrene-g-polyacrylic acid, poly-2-vinylpyrrolidone-b-polybutadiene, poly-2-vinylpyrrolidone-b-polyvinylpyrrolidone, poly-2-vinylpyrrolidone, Any one of polyvinylpyrrolidone-b-polyethylene oxide, polyethylene glycol-b-polymethyl methacrylate, polyacrylic acid-b-polyacrylamide, polyacrylic acid-b-polyhydroxyethyl acrylate, polyethylene oxide-b-polyethyleneimine, branched polyethylene oxide-b-polyethyleneimine and polymethyl methacrylate-g-polyacrylic acid, polydiallyldimethylammonium chloride, poly 2-hydroxy-3-methacrylate trimethyl ammonium chloride, polyacrylamide, chitosan and polyaniline. The stabilizer is preferably chitosan.

The selection of the stabilizer is based on the deposition of TiO by the active micropore ball loaded with the nano metal particles₂The metal nano particles of the composite material have unique thermal property, electrical property, magnetic property and optical property and strong agglomeration tendency due to the characteristics of small size, large specific surface area and the like. Whether metal nanoparticles are stabilized within the nanoscale is therefore critical to their ability to exhibit unique properties. The metal nanoparticles have the properties based on the small size, so that a metal nanoparticle system has high specific surface energy and strong agglomeration tendency; once agglomeration occurs, the metallic nanoparticle system loses all of the unique properties of many nanoparticle systems and thus loses practical utility. Therefore, it is important to prevent the aggregation, and adding a specific amount of a stabilizer to generate an electrostatic repulsive force or a steric hindrance repulsive force between the metal nanoparticles to stabilize the metal nanoparticles and prevent the aggregation is an effective method. The structure of the polymer is different, the stabilizing action and mechanism of the polymer are different, the invention selects the polymer to have good stabilizing action on the metal nano particles, and the stabilizing mechanism of the steric hindrance is mainly utilized.

The invention relates to TiO modified by nano metal particle deposition₂The composite material sol system not only tends to improve the electron-hole pair separation in ultraviolet lightIon, the surface plasmon resonance effect of metal particles under visible light irradiation can also generate electron-hole pairs; for undoped semiconductor TiO₂Under the irradiation of visible light, an absorption peak does not exist originally, but an sp peak appears after a layer of metal particles is deposited on the surface of the metal particles; although the absorption under visible light is very small compared with that of ultraviolet light, the utilization rate of the full spectrum is greatly improved; in the solar spectrum, ultraviolet light accounts for only 3% of the full spectrum, while visible light accounts for 50% of the full spectrum. Under the irradiation of light, electron-hole pairs are generated inside the metal particles, the electron-hole pairs are separated by the conduction band of the semiconductor with electron migration, and residual holes exist in the metal, and the electrons and the holes respectively have reducibility and oxidizability, so that the photocatalysis process is promoted.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treating ball, further, the composite modified nano TiO₂Sol is semiconductor coupled TiO₂The composite material sol is obtained by the following method:

step (201), nanometer TiO is added₂Ultrasonically dispersing in absolute ethyl alcohol according to the proportion of 20g/L-200g/L to obtain a mixed solution C; preferred nano TiO₂Ultrasonically dispersing in absolute ethyl alcohol according to 20g/L, namely ultrasonically dispersing 20g in 1L of absolute ethyl alcohol;

step (202), dropwise adding the prepared cadmium salt solution into the mixed solution C (the volume ratio of the metal salt solution to the mixed solution C can be selected to be 1: 1) to obtain a mixture D, then slowly dropwise adding the sodium salt solution and the potassium salt solution which can react with the metal salt and then are roasted to form the metal oxide or sulfide or selenide into the mixed solution D, stirring for reaction, and homogenizing to obtain the semiconductor modified TiO₂And (3) composite material sol. The molar concentration of the metal salt solution is 0.1-0.5moL/L, preferably 0.2moL/L, namely, each L of the solution contains 0.1-0.5moL of metal salt; the molar concentration of the sodium salt and potassium salt solution of the sulfide or selenide is 0.1-0.5moL/L, and preferably 0.2 moL/L.

The following steps can be specifically adopted: mixing nano TiO₂Ultrasonically dispersing in anhydrous ethanol at a ratio of 20-200 g/L to obtain 0.2moLDropping the cadmium salt solution drop by drop to disperse the solution evenly, and then adding K₂And slowly dripping 0.2moL/L of the S solution into the mixed solution, stirring and reacting for 12 hours, and introducing into a homogenizer for homogenizing for 10min to obtain a mixed liquid.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the metal in the metal salt solution is any one of Zn, Cd, W, Sn, Cd, Pb or Fe; the metal oxide formed by roasting is ZnO and WO₃、SnO₂、PbS、Fe₂0₃The sulfide is CdS, and the selenide is CdSe.

The preparation method of the wastewater and waste gas pollutant treatment ball loaded with the composite modified nano TiO2, further, the step (4) specifically comprises the following steps:

carrying out composite modification on the nano TiO prepared in the step (3)₂Soaking the hollow spheres in plant extract photosensitizer solution at a concentration of 50g-100g/L for 20-30 hr, and vacuum drying to obtain load composite modified nanometer TiO₂The wastewater and waste gas pollutant treatment ball;

or the load composite modified nano TiO prepared in the step (3)₂The hollow ball is soaked in strong oxidant dipping solution with the mass fraction of 1-10 percent to load composite modified nano TiO₂The mass ratio of the hollow sphere to the strong oxidant dipping solution is (1: 2) - (1: 4), the hollow sphere and the strong oxidant dipping solution are soaked and stirred for 2-5h, the mixture is statically soaked for 20-30 h, and the load composite modified nano TiO is obtained after vacuum drying₂The waste water and gas pollutant treatment ball.

The invention loads the composite modified nano TiO as described above₂Preparation of waste water and waste gas pollutant treating ball

The preparation method further comprises adding one or more of porphyrin, chlorophyll, xanthene, erythrosine B, eosin, humic acid, quinoline, anthocyanin, anthocyanidin, fluorescein, rose bengal, thionine, phthalocyanine, porphyrine and rose bengal into the plant extract photosensitizer solution. The plant extract photosensitizer solution used in the step (4) is an alcohol solution with the mass volume concentration of 30g-100g/L, namely 30g-100g of plant extract photosensitizer can be dissolved in 1L of absolute ethyl alcohol.

The strong oxidant is any one of hydrogen peroxide, sodium chlorate, sodium perchlorate, calcium hypochlorite, sodium percarbonate, ferric permanganate, potassium ferrate, sodium thiosulfate, potassium dichromate, trichloroisocyanuric acid, sodium acetate, lead dioxide, cobalt trifluoride, sodium ferrate, periodic acid, sodium bismuthate, sodium persulfate, potassium persulfate, chlorine dioxide, dichloroisocyanuric acid and salts thereof.

The method solves the problem of difficult loading of the plant extract and the strong oxidant, and the photosensitization effect of the photosensitizer of the plant extract is to extend TiO₂The primary pathway of excitation wavelength range; it mainly utilizes TiO₂Strong adsorption effect on photoactivator, and adsorbing onto TiO in physical or chemical state by loading plant extract photosensitizer₂A surface; the substances have larger excitation factors under visible light, and under the irradiation of the visible light, the adsorbed photoactive molecules absorb photons to be excited to generate free electrons, and then the excited photoactive molecules inject the electrons into TiO₂On the conduction band of (2); enlarging TiO₂The range of the excitation wavelength enables the organic matter to be degraded by visible light.

The invention utilizes the photosensitizer of the loaded plant extract to compound and modify nano TiO₂In the system, the following advantages are provided: (1) most organic sensitizers have a unique ring-conjugated delocalized system, and have a wide visible light wavelength response range and strong electron donating ability. (2) The organic sensitizer has easily modified molecular structure and can realize effective regulation and control of absorption band and electron supply capability. (3) The organic sensitizer can be chemically bonded to the inorganic TiO₂And the phase separation and crystallization trends are avoided, so that the optical stability is ensured. (4) Most of the sensitizers are compounded with TiO by sensitization₂The catalyst can realize self-sensitization degradation. (5) Can realize the co-sensitization of inorganic modification and organic modification or two organic sensitizers, thereby greatly expanding the absorption range of the organic sensitizers in visible light wave bands and improving the separation efficiency of photo-generated electrons and holes.

The invention discloses photosensitization composite modified TiO₂Can degrade alkane, olefin, fatty alcohol, phenols, carboxylic acid, aromatic compounds and halide in water and air, and degrade dye, surface active, herbicide, pesticide, cyanide, nitrite and other substances into nontoxic micromolecule substances by photocatalysis, thereby eliminating the pollution of the micromolecule substances to the environment.

The invention is based on the selection of the strong oxidant, the electronic structure of the molecule of the strong oxidant is in an unsaturated state, and the oxidation performance of the strong oxidant is shown in that the strong oxidant attacks atoms or atomic groups rich in electrons or supplying electrons and strongly grazes electrons to cause the electrons to lose activity or change properties. Therefore, the material can react with various inorganic matters, organic matters and the like to become a non-toxic and harmless substance. For example, chlorine dioxide can react with iron, manganese, lead, nickel, cadmium, chromium, sulfides, cyanides, etc., natural salts, and also with a wide variety of organic substances, such as naphthalene, anthracene, phenol, humic acid, small molecule organic acids, aniline, benzoquinone, phenol, amino acids, formaldehyde, diacetals, amines, thiols, thiourea, nitrophenol, etc., to render it non-toxic and harmless.

The invention relates to a load composite modified nano TiO impregnated by photosensitization or strong oxidizer₂Generates weak electric field and super strong oxidation-reduction property generated by visible light catalytic effect to completely oxidize and decompose organic pollutants into harmless substances.

The invention loads the composite modified nano TiO as described above₂The preparation method of the wastewater and waste gas pollutant treatment ball further comprises the step (3) of soaking the active microporous ball in the sol for 5-50h, taking out, drying at 60-80 ℃ for 2-4h, finally heating to 300-600 ℃ at the speed of 10 ℃/min in the air atmosphere, and keeping the temperature for 4h to obtain the load composite modified nano TiO₂The hollow ball.

In particular, rare earth doped TiO₂In the preparation of the composite material sol, step (3), the active microporous balls are soaked in the corresponding sol for 48 hours and then taken out, the sol is aged for 48 hours at room temperature to become gel, dried for 4 hours at 80 ℃, finally heated to 500 ℃ at the speed of 10 ℃/min in the air atmosphere, and the temperature is maintained for 4 hours, thus obtaining the load composite modified nano TiO₂Hollow ball, in particular to load composite rare earth doped modified TiO₂The hollow micropore ball has photocatalytic performance.

Graphene oxide composite TiO₂In the preparation process of the composite material sol, step (3), the active microporous balls are soaked in the corresponding sol for 20h and then taken out, dried at 60 ℃ for 4h and finally heated to 450 ℃ at the speed of 10 ℃/min under the air condition, and the temperature is maintained for 4h, so that the load composite modified nano TiO is obtained₂Hollow spheres, in particular to graphene oxide loaded composite modified TiO₂The hollow micropore ball has photocatalytic performance.

Nano metal particle deposition modified TiO₂In the preparation process of the composite material sol, step (3), the active hollow spheres are soaked in the corresponding sol for 10 hours and then taken out, dried for 4 hours at 80 ℃, dried, finally heated to 400 ℃ at the speed of 10 ℃/min under the air condition, and kept at the temperature for 4 hours, so that the load composite modified nano TiO is obtained₂Hollow spheres, in particular TiO modified by deposition of loaded nano metal particles₂The hollow micropore ball has photocatalytic performance.

Semiconductor coupled TiO₂In the preparation process of the composite material sol, step (3), the active microporous balls are soaked in the mixed liquid of the step (1) for 6 hours and then taken out, the carrier loaded with the mixed liquid is dried for 2 hours in a ventilating way, then is dried for 2.5 hours at the temperature of 80 ℃, finally is heated to 300-600 ℃ at the speed of 20 ℃/min in the air atmosphere, and is kept at the temperature for 4 hours, so that the loaded composite modified nano TiO is obtained₂Hollow spheres, in particular TiO modified by coupling of load semiconductors₂The hollow micropore ball has photocatalytic performance.

The invention loads composite modified nano TiO₂The hollow sphere can be recycled, and the inventor finds that the surface modification of the microporous sphere obviously affects the loaded composite modified nano TiO in the experimental process₂The recycling condition of the gel layer on the hollow sphere is that when oxalic acid is preferably used as a hydrolysis catalyst of a silane coupling agent in the step (101), the coupling agent plays a role of an interfacial agent in the surface modification of the microporous sphere, and the suitability degree of the coating rate determines the subsequent composite modified TiO₂The load performance of (d); it was found that KH570 was hydrolyzed with oxalic acid and recovered after useWhen the composite modified nano TiO is cleaned by 8-20% acid water solution₂The wastewater and exhaust gas pollutant treating ball (the acid in the acid water solution may be any one of oxalic acid, nitric acid, sulfuric acid, hydrochloric acid, boric acid, formic acid, tartaric acid, citric acid, tannic acid, acetic acid, oxalic acid, malic acid, mugineic acid, succinic acid, punicic acid, vanillic acid, benzoic acid, salicylic acid, coumaric acid, ferulic acid, syringic acid, citric acid, caffeic acid, benzoic acid, stearic acid, oleic acid, linoleic acid and linolenic acid), can maintain the integrity of the supported composite modified nano TiO₂Performance of hollow spheres, i.e. loaded composite modified nano-TIO₂The gel layer is not influenced, and when the gel layer is repeatedly used, the plant extract or the strong oxidant in the step (4) is only needed to be soaked and loaded to obtain the new loaded composite modified nano TiO₂The wastewater and waste gas pollutant treatment ball reduces the treatment process and cost, and the load composite modified nano TiO obtained by the treatment method is tested₂The hollow sphere can be repeatedly cleaned and recycled for more than 34 times, and the cleaning process can cause the load composite modified nano TiO to be treated by other acid hydrolysis coupling agents₂The hollow ball gel layer is damaged to different degrees, so that the cycle range use times are different.

Drawings

FIG. 1 shows the present invention of loaded composite modified nanometer TiO₂The waste water and waste gas pollutant treating ball is used for treating pipeline waste gas;

FIG. 2 shows the present invention of loaded composite modified nanometer TiO₂The schematic diagram of the wastewater, waste gas and pollutant treating ball for treating liquid surface waste gas;

FIG. 3 shows the present invention of loaded composite modified nano TiO₂The wastewater and waste gas pollutant treating ball is used for treating wastewater.

In the drawings, the components represented by the respective reference numerals are listed below:

1. the device comprises a treatment ball 2, a smoke exhaust pipeline 3, a treatment ball layer 4, a liquid level for generating waste gas 5, a sewage pool 6, a treatment ball positioning net 7 and sewage to be treated.

Detailed Description

The principles and features of this invention are described in conjunction with the following embodiments, which are given by way of illustration only and are not intended to limit the scope of the invention.

Example 1

And (3) surface modification of the microporous ball:

carrier Activity AL₂0₃The surface of the microporous hollow ball is modified, alumina microporous ball with the diameter of 0.5-19mm is washed by water and dried, the dried active alumina is put into a reaction kettle, 1000L of dilute sulfuric acid solution with the volume concentration of 20 percent is led in, and the dipping is carried out for 5 minutes; washing and drying the impregnated activated alumina by water to obtain acid-treated microporous balls; soaking the acid-treated microporous balls in 50kg of aluminum sulfate solution (the mass volume concentration of the aluminum sulfate solution is 10-30% of the water solution) for 30h, discarding the solution, and washing with clear water for 3-5 times; adding 20L of silane coupling agent KH570 to 1000L of anhydrous ethanol solution, adding oxalic acid dropwise to pH3, hydrolyzing at 45 deg.C for 50min to obtain hydrolyzed coupling agent alcoholic solution, adding 50kg of Al₂0₃Adding the microporous hollow spheres into an alcoholic solution of a hydrolytic coupling agent, heating in a water bath to 70 ℃, reacting for 2 hours, filtering, washing with toluene, and vacuum drying at 60 ℃ for 24 hours to obtain surface modification active AL₂0₃The microporous ball is surface modified active microporous ball, the pore size distribution of the micropores is 20nm-20um, the ignition loss is less than or equal to 6.0, the water content (normal temperature) is less than or equal to 18 percent, the stacking density is less than or equal to 0.75g/mL, the specific surface area is greater than or equal to 220 square meters/g, the pore volume is greater than or equal to 0.65mL/g, and the crushing strength is greater than or equal to 8.0N-100N/particle.

Example 2

Active AL₂0₃Microporous ball loaded semiconductor coupled TiO₂Composite material with photocatalytic performance

(1) 20kg of nano TiO₂Ultrasonically dispersing in 1000L absolute ethyl alcohol, dropwise adding 200moL of cadmium sulfate solution into the solution to uniformly disperse the solution, and then adding K₂Slowly dropping 200moL of the S solution into the mixed solution, stirring and reacting for 12 hours, and introducing into a homogenizer for homogenizing for 10min to obtain a mixed liquid;

(2) example 1 surface modification of active AL₂0₃Soaking the microporous hollow spheres in the mixed liquid (1) for 6h, taking out, and drying the carrier loaded with the mixed liquid in a ventilating way for 2hDrying at 80 ℃ for 2.5h, finally heating to 300-600 ℃ at the speed of 20 ℃/min in the air atmosphere, and keeping the temperature for 4h to obtain the load composite modified nano TiO₂Hollow spheres, i.e. loaded semiconductor-coupled TiO₂The hollow micropore ball has photocatalytic performance.

Example 3

(1) 150kg of nano TiO₂Ultrasonically dispersing in 1000L absolute ethyl alcohol, dropwise adding 200moL of cadmium sulfate solution into the solution to uniformly disperse the solution, and then adding K₂Slowly dropping 200moL of the S solution into the mixed solution, stirring and reacting for 12 hours, and introducing into a homogenizer for homogenizing for 10min to obtain a mixed liquid;

(2) example 1 surface modification of active AL₂0₃Soaking the microporous hollow spheres in the mixed liquid (1) for 6h, taking out, drying the carrier loaded with the mixed liquid for 2h in a ventilating way, drying the carrier at the temperature of 80 ℃ for 2.5h, finally heating the carrier to 300-600 ℃ at the speed of 20 ℃/min in the air atmosphere, and keeping the temperature for 4h to obtain the loaded composite modified nano TiO₂Hollow spheres, i.e. loaded semiconductor-coupled TiO₂The hollow micropore ball has photocatalytic performance.

Example 4

Active AL₂0₃Microporous hollow ball loaded rare earth doped TiO₂Composite material with photocatalytic performance

(1) Adding n-butyl titanate into the mixture of absolute ethyl alcohol and glacial acetic acid dropwise while stirring, wherein the titanic acid

N-butyl ester: anhydrous ethanol: the volume ratio of glacial acetic acid is 8: 40: 11, stirring for 2 hours by a dispersion machine to form a solution A; respectively adding 25mg/L of rare earth bismuth chloride and lanthanum chloride into ionized water, uniformly stirring, adding 50mL/L of nitric acid, stirring by a dispersion machine for 2 hours, and fully mixing to obtain a solution B; and dropwise adding the solution B into the solution A under high-speed stirring, and continuously stirring for 4 hours after the dropwise addition is finished to obtain uniform and transparent sol.

(2) Example 1 active AL₂0₃Soaking the microporous hollow ball in the sol for 48hTaking out, aging the sol at room temperature for 48h to obtain gel, drying at 80 deg.C for 4h, heating to 500 deg.C at 10 deg.C/min in air atmosphere, and maintaining the temperature for 4h to obtain rare earth doped TiO₂The hollow micropore ball has photocatalytic performance.

Example 5

Active AL₂0₃TiO deposited by microporous hollow sphere loaded with nano metal particles₂Composite material with photocatalytic performance

(1) Sequentially stirring and dispersing 50mg/L of nano-silver particles and 200mg/L of chitosan in absolute ethyl alcohol, ultrasonically dispersing for 30min, heating to 80 ℃, stirring, and slowly adding 200mL/L of n-butyl titanate to prepare nano-silver particle dispersion liquid; then, dripping a mixed solution of absolute ethyl alcohol and deionized water according to 60 mL/L; stirring the silver particle dispersion liquid, dripping the silver particle dispersion liquid into the ethanol and deionized mixed solution, and stirring the mixture for 0.5h after the system is gelatinized to obtain gel.

(2) Example 1 active AL₂0₃Soaking the microporous hollow sphere in the sol for 10h, taking out, drying at 80 ℃ for 4h, heating to 400 ℃ at a speed of 10 ℃/min in the air, and keeping the temperature for 4h to obtain the silver-loaded particle deposited TiO₂The hollow micropore ball has photocatalytic performance.

Example 6

Active AL₂0₃Microporous hollow sphere loaded graphene oxide composite TiO₂Composite material with photocatalytic performance

(1) Dispersing 300mg/L graphene oxide in deionized water; dispersing for 120min by ultrasonic; introducing into a homogenizer for 10min to obtain a uniformly dispersed graphene oxide solution; dissolving tetrabutyl titanate with a volume ratio (tetrabutyl titanate: isopropanol =1: 20) in isopropanol to prepare a mixed solution; dropwise adding graphene oxide according to the volume ratio (mixed solution: graphene solution =1: 2) while stirring; sodium borohydride was added dropwise with stirring at 50g/L, and the gel was obtained by reflux condensation at 120 ℃ and continuous stirring for 8 h.

(2) Example 1 active AL₂0₃Soaking the microporous hollow spheres in the sol for 20h, taking out, drying at 60 deg.C for 4h, and air dryingHeating to 450 ℃ at the speed of 10 ℃/min, and keeping the temperature for 4h to obtain the graphene oxide-loaded composite TiO₂The hollow micropore ball has photocatalytic performance.

Example 7

Load composite modified nano TiO₂Hollow ball impregnated strong oxidant potassium permanganate

Respectively soaking 100kg of the supported composite modified nano TiO2 hollow spheres prepared in the

embodiments

2 and 3 in 300kg of potassium permanganate solution with the mass fraction of 3%, soaking and stirring for 3h, standing and soaking for 24h, taking out the materials, and drying the materials at the temperature of 60 ℃ for 4h to obtain the supported composite modified nano TiO₂The wastewater and waste gas pollutant treating balls are respectively marked with A1 and A11.

Example 8

Load composite modified nano TiO₂Hollow ball impregnated strong oxidant sodium chlorate

Example 4 rare earth doped TiO₂80kg of microporous balls with photocatalytic performance are soaked in 200kg of sodium chlorate solution with the mass fraction of 10%, soaked and stirred for 4h, kept still for soaking for 48h, taken out and dried for 6h at the temperature of 60 ℃, and the rare earth doped TiO load is₂The potassium permanganate dipped microporous hollow sphere A2 has photocatalytic performance.

Example 9

Load composite modified nano TiO₂Hollow ball impregnated with strong oxidant potassium ferrate

The loaded graphene oxide TiO prepared in example 6₂100kg of microporous hollow spheres with photocatalytic performance are soaked in 250kg of potassium ferrate solution with the mass fraction of 20%, the mixture is soaked and stirred for 10h, the mixture is statically soaked for 36h, and the mixture is taken out and dried for 6h at the temperature of 80 ℃. Loaded graphene oxide TiO₂The microporous hollow ball A3 is dipped with photocatalysis performance.

Example 10

Load composite modified nano TiO₂Photosensitizer of plant extract dipped in hollow sphere

The loaded composite modified nano TiO prepared in the examples 2 to 6₂Soaking the hollow spheres in 80g/L anthocyanin solution for 20-30 hours according to 50g-100g/L, and drying in vacuum to obtain the load composite modified nano TiO₂Respectively marking the waste water and the waste gas pollutants of the treatment ballsDenoted as B1, B2, B3, B4, and B5.

The anthocyanin of the embodiment can be obtained by the following method: taking petals of Carthamus Tinctorius, cleaning, air drying, placing into a mortar, mashing, adding 200g/L ethanol solution, submerging for 45min, transferring into a dispersion machine, continuously adding ethanol solution with about the same volume, ultrasonically extracting for 40min, and filtering to obtain ethanol solution of anthocyanidin, which is used as sensitizing plant extract and contains 40g/L of anthocyanidin.

Application example 1

As shown in figures 1 to 3, the loaded composite modified nano TiO is arranged according to the labyrinth principle₂After surface modification and loading, the microporous ball has the characteristics of extremely high specific surface area, regular and ordered pore structure, narrow pore size distribution, continuously adjustable pore size and the like, so that the microporous ball can complete adsorption and separation of macromolecules; gas which does not enter the micropores diffuses along the outer surface of the microporous hollow sphere. The catalyst plays a role in oxidation reduction, particularly catalytic reaction, by a strong oxidant on the outer surface.

Load composite modified nano TiO₂The wastewater and waste gas pollutant treating balls A1 and A11 have CdS and TiO with excellent stability and low visible light response rate₂And potassium permanganate are compounded together, so that the respective defects can be overcome. Photons with low energy in visible light irradiate the surface of CdS to make the electron absorption energy on the valence band of CdS jump, and the conduction band energy of CdS is higher to make the photo-generated electrons transfer to TiO₂On the guide strip and adsorbed on the TiO₂The photo-generated holes on the CdS valence band are not compounded with electrons to form a substance with strong oxidability, and the substance participates in a photocatalytic reaction with potassium permanganate on the surface of the processing ball to degrade polluted gas and toxic organic pollutants.

The strong oxidizing property of potassium permanganate is utilized to oxidize and decompose harmful gas with reducibility in the air, so that the aim of purifying the air is achieved, and the harmful gas such as hydrogen sulfide, sulfur dioxide, chlorine, formaldehyde, nitric oxide and the like is removed with high efficiency. The hollow sphere has pores with the diameter of 20nm-20um and exists in the sphere in a coherent form;there are two mechanisms of action when adsorbing contaminants, one is physical adsorption and one is chemical adsorption. The physical adsorption depends on the characteristic of large specific surface area of the porous active hollow sphere, so that pollutants in the polluted gas are trapped in the active sphere, and pollutant molecules are limited in the active hollow sphere by utilizing the characteristic that the size of micropores is equivalent to the size of the radius of the molecules. The chemical adsorption depends on C atoms with defects on crystal lattices on the surface of the active hollow sphere, oxygen-containing functional groups and polar surface oxides, and by utilizing the chemical characteristics of the C atoms, the oxygen-containing functional groups and the polar surface oxides, pollutants are pertinently fixed on the inner surface of the active hollow sphere, and the TiO is coupled with a semiconductor₂The photocatalysis decomposes the contaminants.

Load composite modified nano TiO₂The treatment examples of the wastewater and waste gas pollutant treatment balls A1 and A11

1. Normal temperature 25 ℃ semiconductor coupling TiO₂The activity of the composite material for soaking the potassium permanganate microporous balls to treat pollutants is nanoribbon Ti0₂50 times of the total weight of the powder.

2. Semiconductor coupled TiO₂The composite material is soaked in potassium permanganate microporous balls to treat dye RhB and colorless molecules 2, 4-DC molecules, and the removal rate is 67.5% within 15 h; the TVOC decreases with increasing illumination time, which shows that the oxidation of organic matter is not a simple discoloration but the conversion of carbon atoms in the dye molecule to CO when visible light is present₂The process of (1). Compared with TiO alone₂And the TVOC removal rate of CdS only reaches 14.5 percent and 25.4 percent respectively.

3. And (3) removing berberine by dipping the potassium permanganate microporous balls by the semiconductor coupling TiO2 composite material. Soaking a certain amount of the processing balls A1 and A11 in the berberine solution for 2-10 hours, and the removing effect is remarkable and can reach more than 80%; the pH has little influence on the reaction, and the treatment balls A1 and A11 can be arranged in a sewage pool as shown in figure 3, and the treatment ball positioning net 6 is adopted to position the treatment balls so as to remove the pollutants in the sewage 7 to be treated.

4. The removal efficiency of harmful gases such as hydrogen sulfide, sulfur dioxide, chlorine, formaldehyde, nitric oxide and the like reaches more than 98 percent, which is 2 times of the removal efficiency of the traditional potassium permanganate ball; the treatment pellets a1 and a11 may be arranged as shown in fig. 1, possibly in a certain layer 3 of treatment pellets inside the smoke evacuation duct 2.

The invention loads composite modified nano TiO₂The waste water and gas pollutant treating ball utilizes the labyrinth principle, the pollutant in the waste gas reacts with the active group with higher energy of the treating ball, and finally the pollutant is converted into CO₂And H₂O, and the like. As shown in fig. 1 to 3, the amount and the bulk density of the specific treatment balls can be increased or decreased according to the concentration and the type of the pollutants.

Application example 2

Load composite modified nano TiO₂The waste water and gas pollutant treating ball A2 is rare earth doped loaded TiO₂Photocatalytic performance for treating NO by dipping potassium permanganate microporous balls_XThe processing ball processes NO_XThe application principle of (1): on the rare earth doping load TiO₂Rare earth elements into Ti0₂The lattice causes lattice distortion, resulting in Ti0₂Oxygen vacancies formed by surface oxygen atoms escaping from crystal lattices become capture centers of photo-generated electrons, so that the recombination of photo-generated carriers is effectively inhibited, and the photocatalytic activity is improved manyfold. NO_XThe active sites for the decomposition reaction are the adjacent 2 oxygen vacancies close to the surface of the perovskite-type oxide. NOX adsorbs on the oxygen vacancies and gets 1 electron from the B site cation adjacent to the oxygen vacancy to form NO-, which is oxidized to a higher valence state, thereby promoting the redox cycle. For and La1-xkxMnO₃By first-class catalyst of NO_XThe research of reduction reaction shows that the active center of the catalyst is still transition metal ions or groups formed by the transition metal ions and lattice oxygen, and the action of La, alkali metal and the like is still to reduce the oxygen bond energy and is beneficial to NO_XThereby improving the activity source of the catalyst. To N₂The research on the decomposition rate of O in ABO type catalyst containing rare earth or alkaline earth metal shows that N₂The rate of decomposition of O is controlled by the rate of oxygen desorption. On each rare earth oxide. The activation energy and decomposition rate are nearly identical to the exchange reaction of lattice oxygen, which suggests that the mobility of lattice oxygen plays an important role in catalytic activity.

Load composite modified nano TiO₂Waste water and gas pollutantsThe ball-sorting B3 is used for purifying the flue gas of the glass melting furnace, and particularly, the processing balls B3 are stacked in a flue, the number of stacked layers is more than 10-50, the denitrification rate reaches more than 90%, and the concentration of NOx in the purified flue gas is below 60 ppm.

The closed cycle can be adopted in the application to process SO₂Removing pollutants such as dust particles and the like simultaneously; no external oxidant is used; the 5% steam is sprayed into the flue gas, so that the efficiency and the service life of the catalyst can be improved, and the investment and the operation cost of equipment are low.

A layer of processing balls can be paved on the surface of the building outer wall, and the rare earth is doped with load TiO₂The sodium chlorate-impregnated microporous ball with photocatalytic performance is applied to the surface layer of the outer wall of a building, can realize the integration of atmospheric purification and building material functions, and has wide application prospect.

Coking wastewater is industrial wastewater produced by separating coal tar with tens of thousands of components and coal carbonization products such as raw coke oven gas. The composition contains a large amount of inorganic substances (such as ammonia, sulfide, cyanide, chloride ion, thiocyanide ion, and compounds of elements such as silicon, calcium, iron, boron, magnesium, potassium, sodium, germanium, etc.), a large amount of organic substances (such as acidic organic substances such as phenol, cresol, etc., and basic nitrogen-containing organic substances such as pyridine, aniline, etc.), and a large amount of aromatic hydrocarbons.

Load composite modified nano TiO₂Example of treating waste water and waste gas pollutant treating ball A2

1. Load composite modified nano TiO₂The waste water and gas pollutant treating ball A2, namely rare earth doped loaded TiO₂The sodium chlorate-impregnated microporous hollow sphere with photocatalytic performance has the dosage of 10.0g/L, the initial mass concentration of the active carbon black of 40mg/L, illumination for 30min, the degradation rate of the active carbon black of 100 percent, colorless solution and good treatment effect.

3. Load composite modified nano TiO₂The adding amount of the waste water and waste gas pollutant treating ball A2 is 10.0g/L, the initial mass concentration of the ink waste water is 100mg/L, the ink waste water is placed for 24 hours under the condition of normal temperature and natural light, the degradation rate of the ink waste water can reach 100%, the solution is colorless, and the treatment effect is good.

4. Load composite modified nano TiO₂Waste water and gas pollutantsThe degradation rate of the physical sphere A2 on rhodamine B in 70min reaches more than 95 percent, various bacteria can be effectively killed, and the antibacterial rate is 99.99 percent.

5. And (3) carrying out the high yield cultivation under the normal temperature, wherein the formaldehyde concentration can be quickly reduced to 0.060 mg/m.

Application example 3

Load composite modified nano TiO₂The waste water and gas pollutant treating ball A3 is loaded with graphene oxide TiO₂The micro-porous ball is dipped with the photocatalytic performance.

Graphene oxide/TiO loaded with microporous hollow spheres₂The specific surface area of the composite material is 190 square meters per gram, the average pore diameter is 11.87nm, and the composite material can be prepared under visible light (C)>420nm) has obviously higher degradation effect on organic matters than pure TiO obtained under the same condition₂. On one hand, under the excitation of visible light, the composite photocatalyst has higher absorption strength in a visible light region due to the enhancement of sp hybridized carbon resonance in the graphene conjugated structure; on the other hand, due to the donor level effect generated by the graphene at the bottom of the semiconductor conduction band, the charge separation is promoted, and due to the weak electric field effect of the potassium ferrate, the redox effect is multiplied, and the enrichment degree of pollutants on the surface of the semiconductor is improved to a certain extent.

The graphene oxide has very excellent adsorption performance and can be compounded with a plurality of metals and metal oxides to obtain a composite material with excellent performance, because the graphene oxide carbon layer is rich in functional groups such as epoxy groups, hydroxyl groups, carboxyl groups and the like, and the potassium ferrate contains FeO₄ ^2-A compound in which the central atom Fe is present hexavalent and the standard electrode potentials under acidic and alkaline conditions are E0, FeO, respectively₄ ^2-/Fe³⁺=2.20V，E0，FeO₄ ^2--/Fe(OH)³=0.72V, is GO-supported graphene oxide TiO₂The microporous hollow spheres with photocatalytic performance provide reactive sites, and the hydrophilicity of the oxygen-containing functional groups enables the microporous hollow spheres to form a stable dispersion system in water; graphene TiO oxide under acidic or alkaline conditions₂The microporous hollow spheres with photocatalytic performance have strong oxidizability, and can be widely used for oxidation, disinfection and sterilization of water and wastewater. Thus, oxygenChemical graphene TiO₂The microporous hollow ball with photocatalytic performance is a novel, high-efficiency and nontoxic multifunctional water treatment agent. In the process of treating drinking water, eight characteristics of oxidation, adsorption, flocculation, precipitation, sterilization, disinfection, decoloration, deodorization and the like are integrated into a whole.

Load composite modified nano TiO₂Example of treating waste water and waste gas pollutant treating ball A3

1. Loaded graphene oxide TiO₂The microporous ball A3 with photocatalytic performance has stronger photocatalytic activity on rhodamine B pollutants in a visible light region; particularly 10kg of load composite modified nano TiO for wastewater containing water-soluble macromolecules₂The waste water and gas pollutant treating ball A3 is added into 200L of polyacrylamide petroleum waste water with the concentration of 2.0 g/L, and the viscosity reducing rate reaches 98.01 percent after the reaction is carried out for 30 min.

2. When the pH value is 6-6.5, 10g of load composite modified nano TiO is added into each liter of water₂The waste water and gas pollutant treating ball A3 can kill pathogenic bacteria, colibacillus, typhoid bacillus and viruses in water at normal temperature for 30min to reach the eliminating rate of 99.5-99.95%.

3. Load composite modified nano TiO₂The wastewater and waste gas pollutant treating ball A3 has good effect of removing BOD, COD, lead, cadmium, sulfur and the like in wastewater, and the content of the graphene oxide TiO is 10-20 g/L₂96% BOD is oxidized by the microporous hollow sphere with photocatalytic performance, 86% ammonia nitrogen and 75% phosphorus are removed, when the pH value is 5.5 and the turbidity of raw water is 28 degrees (the turbidity is left after sedimentation), 85.6% of trichloroethylene in the water can be removed by the processing ball A3 with the concentration of 30g/L, and the removal rate of naphthalene reaches 100%.

4. Load composite modified nano TiO₂The waste water and gas pollutant treating ball A3 is used for treating radioactive waste water and removing waste water containing arsenic, cyanogen ion, americium and plutonium.

The total α radiation can be controlled from 3.0 × 10 at pH of 11.5-12⁶Pci/L is reduced to 3.0 × 10³Pci/L or less (1 Pci =1012 ci);

for high-arsenic drinking water, such as high-arsenic drinking water with the concentration of 0.783mg/L-1.86mg/L, the composite modified nano TiO is loaded₂Is subjected toThe mass ratio of the adding amount of the waste gas pollutant treating ball A3 to the original high-arsenic drinking water is 15: 1, the arsenic residual quantity in the treated water sample can reach the national drinking water sanitary standard<0.01 mg/L.

Load composite modified nano TiO₂The wastewater and waste gas pollutant treating ball A3 has good effect of removing cyanide ion CN-. When CN is in aqueous solution^-At a mass concentration of 10mg/L, the CN removal treatment was carried out at 167g/L, and 10g of CN was contacted at pH 11.2 to remove most of the CN^-The residual concentration is 0.082mg/L-0.062mg/L, and the removal rate can reach 99.18% -99.38%. The treatment ball has good application effect in treating cyanide-containing wastewater.

Application example 4

Load composite modified nano TiO₂The waste water and waste gas pollutant treating ball B1-B5 is a photosensitization load TiO₂A photocatalytic microporous sphere.

Depositing TiO by treating ball B4 photosensitive nano silver particle₂The photo-catalytic hollow microporous ball is combined with light radiation with certain energy, so that the photosensitive semiconductor is excited under the irradiation of light to produce electron-hole pair, the dissolved oxygen and water molecules adsorbed on the semiconductor act with the electron-hole pair to produce free radical with strong oxidizing property of OH, etc., and the produced free radical is added to organic pollutant to make the pollutant mineralize completely or nearly completely and finally produce CO₂、H₂O and other ions, e.g. NO^3–、PO₄ ^2-、S0₄ ^2-、 Cl^–And the like.

Photosensitive nano silver particle deposition of TiO₂The photocatalytic microporous hollow sphere degradation can remove pollutants by using water vapor and oxygen in the air at room temperature, and has remarkable superiority compared with other heterogeneous catalytic oxidation methods which need to be carried out at higher temperature and have complicated operation steps; researches show that benzene series, halogenated alkane, aldehyde, ketone, acid and the like in the air can be effectively degraded and removed under the irradiation of ultraviolet light by the treatment ball C4; the degradation effect on benzene and benzene series is good, and the degradation rate of phenol is more than 95% under the condition of normal temperature visible light for 10 h.

Light-sensitiveDeposition of TiO by Nano-silver particles₂The photocatalytic microporous hollow sphere can degrade halogenated aliphatic hydrocarbon, halogenated aromatic hydrocarbon, organic acids, nitroaromatic, substituted aniline, polycyclic aromatic hydrocarbon, heterocyclic compounds, hydrocarbons, phenols, dyes, surfactants, pesticides and the like to finally generate inorganic micromolecular substances, eliminate the pollution to the environment and the harm to the health of human bodies, and for organic pollutant systems with the concentration of thousands of milligrams per liter in wastewater, the photosensitive nano silver particles deposit TiO₂The photocatalytic microporous hollow ball degradation can effectively degrade and remove pollutants to reach the specified environmental standard.

The photocatalytic degradation can be used for treating organic pollution, and can reduce some high-valence heavy metal ions to reduce the toxicity to the environment.

For complex pollution systems, such as sewage systems containing inorganic heavy metal ions and organic pollutants, photocatalytic degradation can remove the inorganic heavy metal ions and the organic pollutants simultaneously. Under the condition of illumination, Cr^6＋And p-chlorophenol can respectively perform reduction and oxidation to achieve photocatalytic purification.

Load composite modified nano TiO₂Example of treating waste water and waste gas pollutant treating ball B4

For the Cr-containing^6＋The test of the waste water shows that the load composite modified nano TiO₂The wastewater and waste gas pollutant treatment ball B4 can be used for treating wastewater, wherein 4100-200 kg of treatment ball B can be added into each ton of wastewater, and the wastewater is irradiated by sunlight for 3h and is Cr^6＋The concentration is reduced from 80 mg/L to 0.1 mg/L, and the degradation rate reaches 99.9 percent.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. Load composite modified nano TiO₂The ball for treating the pollutants in the waste water and the waste gas is characterized in that,

comprises active microporous balls and composite modified nano TiO₂And plant extractionPhotosensitizer or strong oxidizer, the composite modified nano TiO₂And a plant extract photosensitizer or a strong oxidizer are sequentially loaded on the active microporous balls.

2. The supported composite modified nano TiO of claim 1₂The wastewater and waste gas pollutant treating ball is characterized in that the active microporous ball is any one of hollow glass microspheres, floating beads, hollow microspheres, vitrified microspheres, sinking beads, glass fiber balls, nickel balls, silica balls, alumina balls, zeolite, molecular sieves, silica gel balls, active carbon balls, ceramic balls, cement balls and sand balls.

3. The supported composite modified nano TiO of claim 1₂The waste water and waste gas pollutant treating ball is characterized in that the plant extract photosensitizer comprises one or more of porphyrin, chlorophyll, xanthene, erythro-scarlet B, eosine, humic acid, quinoline, anthocyanin, anthocyanidin, fluorescein, rose bengal, thionine, phthalocyanine, porphyrine and rose bengal, and the strong oxidant is any one of hydrogen peroxide, sodium chlorate, sodium perchlorate, calcium hypochlorite, sodium percarbonate, ferric permanganate, potassium ferrate, sodium thiosulfate, potassium dichromate, trichloroisocyanuric acid, sodium acetate, lead dioxide, cobalt trifluoride, sodium ferrate, periodic acid, sodium bismuthate, sodium persulfate, potassium persulfate, chlorine dioxide, dichloroisocyanuric acid and salts thereof.

4. Load composite modified nano TiO₂The preparation method of the waste water and gas pollutant treatment ball is characterized by comprising the following steps:

step (2) preparing composite modified nano TiO₂Sol;

step (3), soaking the active microporous ball in the composite modified nano TiO₂Sol is dried and roasted for a preset time to obtain the loaded composite modified nano TiO₂Hollow spheres;

step (4), the load composite modified nanometer TiO prepared in the step (3) is used₂Soaking the hollow ball in plant extract photosensitizer or strong oxidant, taking out for a predetermined time, and drying to obtain the load composite modified nano TiO₂The waste water and gas pollutant treatment ball.

5. The supported composite modified nano TiO of claim 4₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the surface modification of the microporous ball comprises the following steps:

and (102) soaking the acid-treated microporous spheres in an aluminum salt solution, washing with clear water, adding the acid-treated microporous spheres into a hydrolytic coupling agent alcohol solution with the pH value of 3-4, reacting at the constant temperature of 60-80 ℃ for a preset time, washing with toluene, and drying in vacuum at the temperature of 50-65 ℃ to obtain the surface-modified active microporous spheres.

6. The supported composite modified nano TiO of claim 5₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the aluminum salt solution in the step (102) is soaked and washed by clear water, an acid water solution is dropwise added to the pH value of 3-4, room temperature hydrolysis is carried out for 30-90 minutes to obtain a decoupling agent solution, and 50g/L-150g/L of active microporous hollow balls are added into the decoupling agent solution for constant temperature reaction; the volume ratio of the coupling agent to the alcohol used in the process of obtaining the alcohol solution of the uncoupling agent is 20mL-100 mL/L.

7. The supported composite modified nano TiO of claim 6₂The preparation method of the waste water and gas pollutant treating ball is characterized in that the acid adopted in the acid solution is nitric acid, sulfuric acid, hydrochloric acid, boric acid, formic acid, tartaric acid, citric acid, tannic acid, acetic acid, oxalic acid, malic acid, mugineic acid, succinic acid and punicic acidOne or more of vanillic acid, benzoic acid, salicylic acid, coumaric acid, ferulic acid, syringic acid, citric acid, caffeic acid, benzoic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and the like.

8. The supported composite modified nano TiO of claim 5₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the diameter of the active microporous ball is 0.5-19mm, the pore diameter distribution of micropores is 20nm-20um, the ignition loss is less than or equal to 6.0, the water content at normal temperature is less than or equal to 18%, the bulk density is less than or equal to 0.75g/mL, the specific surface area is more than or equal to 220 square meters/g, the pore volume is more than or equal to 0.65mL/g, and the crushing strength is more than or equal to 8.0N-100N/particle.

9. The supported composite modified nano TiO of claim 5₂The preparation method of the wastewater and waste gas pollutant treating ball is characterized in that the coupling agent is any one of silane coupling agent, titanate coupling agent, aluminate coupling agent, organic chromium complex coupling agent or phosphate coupling agent.

10. The supported composite modified nano TiO of any one of claims 4 to 9₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the composite modified nano TiO is₂The sol is rare earth doped TiO₂The composite material sol is obtained by the following method:

Dispersing and stirring the mixed solution to obtain a solution A; the n-butyl titanate: anhydrous ethanol: glacial acetic acid volume ratio = (8: 40: 11) - (20: 25: 4);

step (202), adding 20mg-100mg/L of rare earth salt into ionized water, uniformly stirring, adding 5mL-100mL/L of nitric acid, and stirring and mixing by a dispersion machine to obtain a solution B;

and (203) dropwise adding the solution B into the solution A under the condition of high-speed stirring, and uniformly stirring to obtain transparent sol after dropwise adding.

11. The supported composite modified nano TiO of claim 10₂The preparation method of the ball for treating pollutants in waste water and waste gas is characterized in that the rare earth salt is any one or more than two of nickel nitrate, cerium nitrate, yttrium nitrate, ytterbium nitrate, erbium nitrate, cerium ammonium nitrate, lanthanum cerium nitrate, neodymium nitrate, europium nitrate, bismuth chloride, praseodymium chloride, indium chloride, cerium chloride, lanthanum chloride, yttrium chloride, gadolinium chloride, thulium amide, samarium chloride, cerium acetate, lanthanum acetate, dysprosium acetate, holmium acetate, erbium acetate, thulium acetate, lanthanum carbonate, lanthanum cerium praseodymium, lanthanum praseodymium neodymium carbonate, cerium carbonate and lanthanum cerium carbonate.

12. The supported composite modified nano TiO of any one of claims 4 to 9₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the composite modified nano TiO is₂Sol is graphene oxide composite TiO₂The composite material sol is obtained by the following method:

step (202), dropwise adding a graphene oxide solution into the mixed solution A while stirring to obtain a mixed solution B, wherein the mixed solution A: the volume ratio of the graphene solution is (1: 1) - (1: 3); dropwise adding a reducing agent into the mixed solution B under the stirring condition of 10g-50g/L, condensing, refluxing and continuously stirring to obtain the graphene composite TiO₂And (3) composite material sol.

13. The supported composite modified nano TiO of claim 12₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the reducing agent is unsymmetrical dimethylhydrazine, hydrazine carbonate, hydrazine sulfate, hydrazine nitrate, dihydrazine carbonate, dithiohydrazide, semicarbazide, isoniazide, chlorothalohydrazine, hydrazine hydrate, furanPenicillin, sodium borohydride, potassium borohydride, ammonium borohydride, lithium borohydride, manganese borohydride, sodium cyanoborohydride, lithium aluminum hydride, carbohydrazide, modified lignin, thiourea dioxide, steam ethanol, gaseous SO₂、NaHSO₄Any one of dimethylene acetamide, ethylenediamine, EDTA, hydroiodic acid, vitamins, glucose, chitosan, gallic acid, L-glutathione, amino acids, aluminum powder, sodium citrate, yeast enzyme, nicotinamide adenine dinucleotide phosphate, pectin, flavone, ascorbic acid, apigenin, and luteolin.

14. The supported composite modified nano TiO of any one of claims 4 to 9₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the composite modified nano TiO is₂TiO modified by deposition of nano metal particles by sol₂The composite material sol is obtained by the following method:

Sequentially stirring and dispersing in absolute ethyl alcohol, performing ultrasonic dispersion, stirring and heating, slowly adding n-butyl titanate, and slowly adding 300mL/L of 100-plus-one solution of n-butyl titanate to prepare nano metal particle dispersion liquid;

step (202), dripping the nano metal particle dispersion liquid into the mixed solution of absolute ethyl alcohol and deionized water by stirring according to the ratio of 20mL to 100mL/L, and stirring to prepare the nano metal particle deposition modified TiO₂And (3) composite material sol.

15. The supported composite modified nano TiO of claim 14₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the nano metal particles are Pt, Au, Ag, Pd, Cu, N, Rh, Ir, Ru or Os, and the particle size of the nano metal particles is less than 100 nm;

the stabilizer is polyvinylpyrrolidone, poly-2-vinylpyrrolidone, polyvinyl alcohol, poly-2-hydroxypropyl methacrylate, polymethyl methacrylate, poly-4-vinylpyrrolidone, poly-N-vinylformamide, poly-N-vinylacetamide, poly-N-vinylaisobutyramide, polystyrene sulfonic acid, sodium polystyrene sulfonate, polyacrylic acid, sodium polyacrylate, poly-2-acrylamide-2-methylpropanesulfonic acid, polystyrene b-poly-4-vinylpyrrolidone, polystyrene-b-polymethyl methacrylate, polystyrene-b-polyethylene oxide, polystyrene-b poly-2-vinylpyrrolidone, polystyrene-g-polyacrylic acid, poly-2-vinylpyrrolidone-b-polybutadiene, poly-2-vinylpyrrolidone-b-polyvinylpyrrolidone, poly-2-vinylpyrrolidone, Any one of polyvinylpyrrolidone-b-polyethylene oxide, polyethylene glycol-b-polymethyl methacrylate, polyacrylic acid-b-polyacrylamide, polyacrylic acid-b-polyhydroxyethyl acrylate, polyethylene oxide-b-polyethyleneimine, branched polyethylene oxide-b-polyethyleneimine and polymethyl methacrylate-g-polyacrylic acid, polydiallyldimethylammonium chloride, poly 2-hydroxy-3-methacrylate trimethyl ammonium chloride, polyacrylamide, chitosan and polyaniline.

16. The supported composite modified nano TiO of any one of claims 4 to 9₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the composite modified nano TiO is₂Sol is semiconductor coupled TiO₂The composite material sol is obtained by the following method:

step (201), nanometer TiO is added₂Ultrasonically dispersing in absolute ethyl alcohol according to the proportion of 20g/L-200g/L to obtain a mixed solution C;

step (202), dropwise adding the prepared metal salt solution into the mixed solution C to obtain a mixture D, then slowly dropwise adding a sodium salt solution and a potassium salt solution which can react with the metal salt and then are roasted to form the metal oxide or sulfide or selenide into the mixed solution D, stirring for reaction, and homogenizing to obtain the semiconductor modified TiO₂And (3) composite material sol.

17. The supported composite modified nano TiO of claim 16₂The preparation method of the wastewater and waste gas pollutant treatment ball is characterized in that the metal in the metal salt solution is any one of Zn, Cd, W, Sn, Cd, Pb or Fe; the metal oxide formed by roasting is ZnO and WO₃、SnO₂、PbS、Fe₂0₃The sulfide is CdS, and the selenide is CdSe.

18. The supported composite modified nano TiO of any one of claims 4 to 9₂The preparation method of the wastewater and waste gas pollutant treating ball is characterized in that the step (4) specifically comprises the following steps:

carrying out composite modification on the nano TiO prepared in the step (3)₂Soaking the hollow spheres in plant extract photosensitizer at a ratio of 50g/L to 100g/L for 20-30 hours, and vacuum drying to obtain load composite modified nano TiO₂The wastewater and waste gas pollutant treatment ball;

19. The supported composite modified nano TiO of any one of claims 4 to 9₂The preparation method of the waste water and gas pollutant treating ball is characterized in that,

step (3) soaking the active microporous ball in the sol for 5-50h, taking out, drying at 60-80 ℃ for 2-4h, finally heating to 300-600 ℃ at the speed of 10 ℃/min in the air atmosphere, and keeping the temperature for 4h to obtain the load composite modified nano TiO₂The hollow ball.