CN107244723B - A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance - Google Patents

A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance Download PDF

Info

Publication number
CN107244723B
CN107244723B CN201710500797.5A CN201710500797A CN107244723B CN 107244723 B CN107244723 B CN 107244723B CN 201710500797 A CN201710500797 A CN 201710500797A CN 107244723 B CN107244723 B CN 107244723B
Authority
CN
China
Prior art keywords
purifying agent
water
photocatalysis
polluted water
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710500797.5A
Other languages
Chinese (zh)
Other versions
CN107244723A (en
Inventor
陈彪
肖艳春
黄婧
魏云华
钱庆荣
张燕青
林香信
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences
Original Assignee
Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences filed Critical Institute of Agricultural Engineering Technology of Fujian Academy of Agricultural Sciences
Priority to CN201710500797.5A priority Critical patent/CN107244723B/en
Publication of CN107244723A publication Critical patent/CN107244723A/en
Application granted granted Critical
Publication of CN107244723B publication Critical patent/CN107244723B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/22—Nature of the water, waste water, sewage or sludge to be treated from the processing of animals, e.g. poultry, fish, or parts thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention belongs to environment-friendly materials technical fields, and in particular to a kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance.Titanium dioxide powder is prepared by butyl titanate hydrolysis, then it is compound with di-iron trioxide, finally by nanometer Fe2O3‑TiO2Composite material and polysilicon acid solution, aluminium chloride and iron chloride chelate the purifying agent for polluted water that modifying titanium dioxide chelating poly aluminium iron silicate is prepared jointly.There is the purifying agent for polluted water that the present invention is prepared coagulation performance to have high-efficiency photocatalysis oxidization performance again, be capable of the organic matter, ammonia nitrogen waste water and heavy metal classes sewage of photocatalytic degradation high concentration, have good practical application prospect.

Description

A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance
Technical field
The invention belongs to environment-friendly materials technical fields, and in particular to a kind of with photocatalytic degradation and coagulation composite performance Purifying agent for polluted water and its application.
Background technique
Since 20th century, economic rapid development and industrialized production bring huge negative effect-earth ecology Worsening.National governments have had appreciated that the seriousness of environmental problem at present, the depollution of environment and energy development etc. one Series of problems promotes the height to the relationship country survival and development to treat, thus the research and technology of this respect is developed by generation The concern of people.
In the industrial production, the pollution of food industrial wastewater merits attention, typical as candied food processing waste water is dirty Dye.These food are in production process, especially pickling process, can generate the organic wastewater of a large amount of high concentration and highly concentrated The bittern of degree.Contain the pollutants such as a large amount of carbohydrate, pectin, pomace, organic acid, mineral salt, COD in these sewageCrUp to 5000mg/L or more, there are also the salt of high concentration to belong to treating high-concentration saline organic wastewater, if not being subject at concentrations up to 20g/100mL Processing, direct emission will cause surrounding body seriously to pollute, and adverse condition is detrimental to health.For another example roast eel processing is useless Water, mainly contains large amount of organic in waste water, such as protein, fat, microbial cells and ammonia nitrogen, total phosphorus concentration compared with Height, after being directly discharged into water body, due to its good biodegradability and organic loading is high, and serious rich battalion can be caused to water ecological setting Feedingization.It currently, produce waste water for preserved fruit waste water and roast eel, is handled using bioanalysis, but it is simple Bioprocess technology treated that discharge standard is not achieved in waste water, need to handle with other method group technologies by bioanalysis this kind of Food processing wastewater.
And in urban life, the pollution of landfill leachate and river sewage is especially serious, conventionally employed river sewage It is long that processing technique generally administers the time, and input cost is high, has been unable to meet the needs of the modern life, and some effects are preferably dirty Method for treating water, and large scale equipment, a huge sum of money are needed, medium-sized and small enterprises are generally difficult to undertake.And landfill leachate is in health A kind of organic wastewater for being difficult to directly degrade formed during landfill, have coloration is big, organic concentration is high and type is complicated, All higher etc. characteristics of the content of ammonia nitrogen and heavy metal.More mature in now current refuse leachate treatment technology is MBR, From " the 2009 advanced prevention and cure of pollution exemplary teachings register of country ".But the MBR water outlet after anaerobism+nitration denitrification COD is much higher than direct emission standard still between 400mg/L~800mg/L.Because this part of COD does not have substantially Condition that can be directly biochemical, so present further treatment technique only continues plus NF and RO.But these physical treatment methods Such as in the presence of many technology barriers that can not go beyond: the pollution problem of film, the lost of life problem of film, the disposition for separating dope are asked Topic, treatment effeciency problem, energy consumption problem etc..
In addition, because use bath mode cleans place, there is large amount of sewage discharge daily in Animal husbandry production, these There are a large amount of organic matter, disinfectant, cause of disease bacteria microorganism and parasitic ovum etc. in sewage, affect the existence of aquatile and leads Cause serious water eutrophication.There are also higher concentration terramycin, sulphadiazine in breeding wastewater, some researches show that, for a long time compared with The residual that the antibiotic medicine discharge of high concentration may cause such drug in the environment receptor such as farm's surrounding water, soil is tired Product, to bring potential hazard to ecological environment and human health, current cleanser or precipitating medicament remove antibiotic Except there is no furtheing investigate, especially there are certain difficulty for decomposition substance of this kind.
Currently, mainly have an absorption method to the processing method of hardly degraded organic substance waste water, absorption method mainly use exchange adsorption, Pollutant is adsorbed on adsorbent, to achieve the purpose that removal by the modes such as physical absorption or chemisorption from waste water.Absorption effect Fruit is influenced by factors such as the structure and property of sorbent structure, property and pollutant and operating procedures, common to adsorb The active charcoal of agent, resin, activated carbon fibre, diatomite etc..The advantages of method is that equipment investment is few, high treating effect, land occupation face Product is small.But since the adsorption capacity of adsorbent is limited, often energy consumption is very big for the regeneration after absorption, and discharge easily causes secondary after discarding Pollution.In recent years, Photocatalytic Oxidation With Semiconductors technology is most study, a most widely used high-level oxidation technology, is not only dropped It is fast to solve rate, does not generate secondary pollution, and reaction condition is mild, can solve conventional physico-chemical process, biochemical method is difficult to remove has Machine pollutant problem, if can be by catalysis material in conjunction with inorganic high molecular purifying agent, this will greatly improve answering for cleanser With efficiency and range.Titanium dioxide is semiconductor light-catalyst of greatest concern so far, and not only activity is high, thermal stability It is good, and chemical property is stable, anti-photooxidation is strong, but spectral response range is limited to ultraviolet region, in practical applications There is a situation where that quantum low efficiency, the efficiency of light energy utilization be not high, it is low to the utilization rate of visible light.It is carried to reduce titanium dioxide photoproduction The recombination rate of son is flowed, light excitation wavelength is increased, titanium dioxide and other narrow band gaps can be used to sun light utilization efficiency in raising The method of semiconductors coupling.In numerous metal-oxide semiconductor (MOS)s, iron oxide series is because its band gap is relatively narrow and possesses n-type Structure, nanometer Fe2O3Band gap is narrow, generally 2.2 eV, and a length of 560 nm of maximum absorption wave can be used as the load of titanium dioxide Body expands the optical response range of catalysis material if titanium dioxide and its recombination energy to be reduced to the forbidden bandwidth of catalysis material Exhibition improves the utilization rate in light-catalyzed reaction to light to visible light.
Therefore, the present invention passes through modified TiO obtained2The purifying agent for polluted water for chelating poly aluminium iron silicate, both plays coagulation Effect, and play photochemical catalytic oxidation function, in visible-range can responsible photocatalytic degradation technique, the reaction skill Art can carry out at normal temperatures and pressures, can thoroughly destroy organic matter and ammonia nitrogen substance, and decomposition rate is very fast, without secondary pollution, It is applied to the processing of preserved foods processing waste water, the processing of roast eel processing waste water, landfill leachate, river sewage and breeding wastewater There is very big effect in processing, there is good practical application meaning.
Summary of the invention
The purpose of the present invention is to provide a kind of purifying agent for polluted water with photocatalysis and coagulation composite performance and its applications. The present invention prepares titanium dioxide powder by butyl titanate hydrolysis, then it is composite modified with di-iron trioxide, finally by nanometer Fe2O3-TiO2Composite material and polysilicon acid solution, aluminium chloride and iron chloride chelate jointly is prepared modifying titanium dioxide chelating The purifying agent for polluted water of poly aluminium iron silicate has high efficiency photocatalysis performance with coagulation performance again.
To achieve the above object, the present invention adopts the following technical scheme:
The composite type purifying agent is a kind of nano-TiO2/Fe2O3Compound polysilicate aluminum ferric sulfate cleanser；Wherein it is based on Polysilicate aluminum ferric sulfate poidometer, TiO2Weight fraction is 7.71%, Fe2O3Weight fraction is 2.95%.
The preparation method of the cleanser, the specific steps are as follows:
(1) 20wt% sodium silicate solution 0.1mol/L dilute sulfuric acid is adjusted into pH to 3, then stops stirring, it is quiet at 40 DEG C Polymerization is set, polymerization time is 1 ~ 2h, obtains activation polysilicon acid solution；
(2) at room temperature, 8.5 mL butyl titanates are measured to mix with 20 mL dehydrated alcohols, is denoted as solution A, measure 20 mL The solution mixing of dehydrated alcohol, 5 mL glacial acetic acid and 2.5 mL deionized waters composition, is denoted as solution B, solution A is added dropwise to In solution B, it is stirred continuously to being added dropwise, stands 0.5 h, form the colloidal sol of homogeneous transparent；Colloidal sol is ground after standing and air-drying At powder, dry 2 h at 150 DEG C, obtained dry gel powder, which is put into Muffle furnace at 500 DEG C, is heat-treated 3 h, grinding It is sieved up to nano-TiO2Powder；
(3) 7.27 g, nine water ferric nitrate is added in 30 mL dehydrated alcohols, adds nanometer made from 1.5 g steps (2) Titanium dioxide；At room temperature, magnetic agitation and each 30 min of water bath sonicator are successively carried out, 6 h are stirred for, then, by mixed liquor Under the conditions of centrifuge is 6000 r-6500 r, 7 min are centrifuged, supernatant is removed, being placed in temperature is 50 DEG C of baking oven drying, directly It volatilizees completely to dehydrated alcohol；Then product is calcined to 10 h to be cleaned multiple times with ethyl alcohol again at 300 DEG C, dries；Finally sample Nanometer Fe can be obtained in 300 DEG C of 10 h of roasting in product2O3-TiO2Composite material；
(4) 25 are configuredwtThe sulfuric acid solution of %, chlorine is added under the mixing speed of 350 r/min in 70 DEG C of water-bath Change aluminium and iron chloride, control pH value is 1 ~ 2, and then this mixed solution is added in step (1) activation polysilicon acid solution and is stirred (Fe/Al/Si molar ratio is 1:2:3), while adding the nanometer Fe that 5 wt % steps (3) obtain2O3-TiO2Composite material and 1wt% CaCO3(nucleating agent effect) chelates under conditions of temperature is 40-60 DEG C and mixing speed is 200~400r/min After 30min, curing 1h is stood at a temperature of 55 DEG C, gel is formed, then gel is placed in 100 DEG C of drying boxes and is dried to perseverance Weight, then washing 2 times is carried out, alcohol is washed 2 times, is placed into 80 DEG C of drying boxes and is dried, and grinding obtains powdered modified titanium dioxide chelating The purifying agent for polluted water of poly aluminium iron silicate.
Purifying agent for polluted water with photocatalysis and coagulation composite performance of the invention is applied to: preserved foods processing waste water is net Change processing, the processing of roast eel processing waste water purified treatment, waste leachate purification, river sewage purified treatment, livestock breeding wastewater Processing.
Remarkable advantage of the invention is:
(1) present invention preparation has the purifying agent for polluted water of photochemical catalytic oxidation and coagulation composite performance, is not only only capable of in room temperature Organic matter is thoroughly destroyed under normal pressure, including simple and complicated alkane, acid, alkene and aromatic hydrocarbon halides and its derivative, And with toxicity Polychlorinated biphenyls difficult to degrade, chlorophenol, antibiotics, pesticide etc., finally all it is broken down into H2O、CO2With Inorganic ions, decomposition rate is very fast, without secondary pollution, and can degradation of ammonia nitrogen waste water, due in aqueous solution, TiO2Surface High active substance (OH etc.) can be generated, they are from TiO2Surface desorption enters solution and oxidation reaction occurs for ammonia nitrogen class solute, Therefore solute is degraded the reaction was continued for generation intermediate product, ultimately produces stable H2O、CO2And NO3 -With inorganic ions etc., this is just Overcome conventional process organic matter and high ammonia nitrogen class waste water using the method for microbial degradation and more group technologies of electric flocculation, originally The cleanser application method of invention is simple, settles at one go, is not necessarily to multiple programs combination purification, purification efficiency is highly efficient, therefore Especially suitable for the food processing wastewater processing containing high concentration organic contaminant and ammonia nitrogen, it is also applied for the eutrophication of high ammonia nitrogen The river sewage of type is handled, suitable for the livestock breeding wastewater processing containing antibiotic medicine.
(2) compound purifying agent for sewage of the invention is for the garbage filter containing high concentration heavy metal and organic pollutant Liquid has efficient clean-up effect, this is because the metal ion as electron acceptor is given with as electronics in terms of catalytic mechanism The organic matter of body coexists certainly will be all advantageous to two processes.When pollution species (such as organic matter or metal ion) is adsorbed onto semiconductor TiO2When surface, electronics or hole will be respectively obtained, is occurred corresponding
Redox reaction, to achieve the purpose that eliminate pollutant, it can be said that of the invention have photocatalysis The cleanser of degradation can simultaneously heavy-metal ion removal and degradation of organic substances, overcome tradition administer in step by step carry out or film mistake Filter the trouble of processing.
(3) inorganic high molecular purifying agent produced by the present invention, coagulation sedimentation can cannot be completely removed in waste water has Machine harmful components non-selectivity photocatalytic degradation be carbon dioxide and water, and pass through both titanium dioxide and di-iron trioxide Compound action make the optical response range of catalysis material extend to visible light, overcome simple optically catalytic TiO 2 only in purple The drawbacks of area Wai Guang responds greatly improves the utilization rate in light-catalyzed reaction to light, improves photocatalysis treatment of waste water efficiency；
(4) the composite type inorganic polymer cleanser prepared by the present invention with photochemical catalytic oxidation and coagulation double action, Be by di-iron trioxide modifying titanium dioxide, then simultaneously with polysilicon acid solution, aluminium chloride and iron chloride jointly polymerize generate change Property TiO2Chelate poly aluminium iron silicate cleanser, the inorganic high molecular purifying agent can not only photocatalytic degradation of organic matter, can also will The effects of incomplete macromolecule organic pollutant of photochemical catalytic oxidation is caught, electrically neutralized by adsorption bridging, cohesion net is further It is removed, it is organic to high concentration difficult to degrade useless to further compensate for photocatalysis using oxidation, the complementarity of coagulation and synergistic effect The catalysis deficiency problem of water solves the problems, such as that photochemical catalyst inactivation and degradation effect are bad.
Detailed description of the invention
Fig. 1 is the modified TiO of the present invention2Chelate the different amplification scanning electron microscope (SEM) photograph of poly aluminium iron silicate cleanser；
Fig. 2 is the modified TiO of the present invention2Chelate the different amplification transmission electron microscope picture of poly aluminium iron silicate cleanser.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
The preparation of the composite type purifying agent with Photocatalytic Degradation Property:
(1) 20wt% sodium silicate solution 0.1mol/L dilute sulfuric acid is adjusted into pH to 3, then stops stirring, it is quiet at 40 DEG C Polymerization is set, polymerization time 1h obtains activation polysilicon acid solution；
(2) at room temperature, 8.5 mL butyl titanates are measured to mix with 20 mL dehydrated alcohols, is denoted as solution A, measure 20 mL The solution mixing of dehydrated alcohol, 5 mL glacial acetic acid and 2.5 mL deionized waters composition, is denoted as solution B, solution A is added dropwise to In solution B, it is stirred continuously to being added dropwise, stands 0.5 h, form the colloidal sol of homogeneous transparent；Colloidal sol is ground after standing and air-drying At powder, dry 2 h at 150 DEG C, obtained dry gel powder, which is put into Muffle furnace at 500 DEG C, is heat-treated 3 h, grinding It is sieved up to nano-TiO2Powder；
(3) 7.27 g, nine water ferric nitrate is added in 30 mL dehydrated alcohols, adds nanometer made from 1.5 g steps (2) Titanium dioxide；At room temperature, magnetic agitation and each 30 min of water bath sonicator are successively carried out, 6 h are stirred for, then, by mixed liquor Under the conditions of centrifuge is 6000 r-6500 r, 7 min are centrifuged, supernatant is removed, being placed in temperature is 50 DEG C of baking oven drying, directly It volatilizees completely to dehydrated alcohol；Then product is calcined to 10 h to be cleaned multiple times with ethyl alcohol again at 300 DEG C, dries；Finally sample Nano-titanium dioxide/ferric oxide composite material can be obtained in 300 DEG C of 10 h of roasting in product；
(4) 25 are configuredwtThe sulfuric acid solution of %, chlorine is added under the mixing speed of 350 r/min in 70 DEG C of water-bath Change aluminium and iron chloride (Fe/Al molar ratio is 1:2), control pH value is 1 ~ 2, and it is living that this mixed solution is then added to step (1) Change stirring in polysilicon acid solution (Fe/Al/Si molar ratio is 1:2:3), while adding the nanometer that 5 wt % steps (3) obtain Fe2O3-TiO2Composite material and 1 wt% CaCO3(nucleus is conducive to coagulation) is 40-60 DEG C and mixing speed in temperature After chelating 30min under conditions of 200~400r/min, curing 1h is stood at a temperature of 55 DEG C, gel is formed, then by gel It is placed in 100 DEG C of drying boxes that drying to constant weight, then carries out washing 2 times, alcohol is washed 2 times, is placed into 80 DEG C of drying boxes and is dried, and is ground Obtain the purifying agent for polluted water of powdered modified titanium dioxide chelating poly aluminium iron silicate.
Comparative example
(1) 20wt% sodium silicate solution 0.1mol/L dilute sulfuric acid is adjusted into pH to 3, then stops stirring, it is quiet at 40 DEG C Polymerization is set, polymerization time 2h obtains activation polysilicon acid solution；
(2) aluminium chloride and iron chloride (Fe/Al molar ratio is 1:2) are weighed, the concentrated sulfuric acid and water is added, is then added to step (1) stirring in polysilicon acid solution (Fe/Al/Si molar ratio is 1:2:3), control reaction temperature is 40 ~ 60 DEG C, is then allowed to stand ageing 1h obtains poly aluminium iron silicate colloid.
Application example: (the applicable pH value model of the purifying agent for polluted water of modifying titanium dioxide chelating poly aluminium iron silicate of the invention It encloses for 5-9, wherein comparative example uses the cleanser without photo-catalysis function of above-mentioned preparation.)
(1) preserved foods class processing waste water: the sewage that the present invention uses for the haline water of Yongtai County preserved fruit processing factory and The high mixed sewage of syrup, water quality main indicator are as follows: pH 4.5, ClOneFor 5443.5 mg/L, CODCrFor 4356.5mg/ L, NH3- N is 172.8mg/L, and TP is 10.1 mg/L.
Application method: firstly, adjusting pH value is 5 or so.Then, add cleanser in proportion, turn on agitator with 600r.min−1After 30 min are sufficiently stirred, then in 200 r.min−1Under mix slowly 60 min.Finally, allowing its natural subsidence 60min is separated, indices in a certain amount of supernatant analysis waste water are drawn.
Clean-up effect: sewage per ton uses 0.10 kilogram of cleanser of the present invention, by the purification of 150min, ClOneRemoval rate Up to 78.2%, COD removal rate is up to 97.8%, NH3- N removal rate is up to 91.8%, TP removal rate and is up to 95.2%.This is because The coagulation property of poly aluminium iron silicate can remove part ClOne, reduce influence of the salinity to photocatalysis performance, while passing through photocatalysis Efficient degradation organic sugar pollutant is aoxidized, water outlet meets " integrated wastewater discharge standard GB 8978- so that treated 1996 " first discharge standard in.
Comparative example application effect: it is handled using the poly aluminium iron silicate cleanser without photocatalysis effect of comparative example preparation, only Change effect: sewage per ton uses 0.15 kilogram of cleanser, by the purification of 150min, ClOneRemoval rate is 28.1%, COD removal rate Up to 62.5%, NH3- N removal rate is up to 41.8%, TP removal rate and is up to 55.2%.
(2) roast eel processing waste water: company is dirty according to production technology characteristic using sea eel as the food processing factory of primary raw material Dye source is mainly the organic wastewater generated during killing eel and roast eel and roast eel mechanical cleaning water etc..The suspended matter of waste water, animal Grease type and high protein material concentration are high, and ammonia nitrogen and phosphorus are higher, and water temperature is low, and biodegradation rate is slow.Roast eel processing waste water Water quality indicator are as follows: pH 7.2, CODCrIt is 305.9 mg/L, NH for 2549.1mg/L, SS3- N is 178.2mg/L.
Application method: firstly, removing 95% or more molecular state oils using oily water separation technique；Using built-in grille, Remove the sediments such as fish pomace, fish-bone.Then, cleanser is added in proportion, and turn on agitator is first with 600r.min−1It is sufficiently stirred After 30 min, then in 200 r.min−1Under mix slowly 30 min.Finally, its natural subsidence is allowed to separate 30min, draw certain Measure indices in supernatant analysis waste water.
Clean-up effect: sewage per ton uses 0.08 kilogram of cleanser of the present invention, by the purification of 90min time, COD removal Rate is up to 96.2%, SS removal rate and is up to 90.0%, NH3- N removal rate is up to 92.8%, and water outlet meets " integrated wastewater row after processing Put standard GB 8978-1996 " in first discharge standard.
Comparative example application effect: it is handled using the poly aluminium iron silicate cleanser without photocatalysis effect of comparative example preparation, only Change effect: sewage per ton uses 0.15 kilogram of cleanser, and by the purification of 90min time, COD removal rate is 56.2%, SS removal Rate is 68.5%, NH3- N removal rate is 51.8%.
(3) landfill leachate: water-soluble containing the more height of humic acid material and type difficult to degrade in landfill leachate Property small molecule hardly degraded organic substance.Bioanalysis is easy to scale since its process is simple, and removes and imitate to biodegradable material Fruit is good, is widely used in the pretreatment of percolate, percolate can be made to reach stabilization of state.But because it not can be removed object difficult to degrade Matter, so that the coloration of landfill leachate bio-chemical effluent and COD are still higher, rest COD is generally in 500-1300 mgL−1It Between, it can not qualified discharge.The landfill leachate that the present invention is directed to is refuse landfill water outlet after pretreatment, physics and chemistry Matter: pH 8.1, coloration are 2500.8 degree, turbidity 146.2NTU, COD 1019.1mg/L, NH3- N is 138.8 mg/L, weight Metal concentration is respectively Cu 1.1mg/L, Zn1.1mg/L, Fe23.6mg/L, Cd1.8mg/L, Pb0.9mg/L.
Application method: after adding cleanser in proportion, turn on agitator is first with 600r.min−110 min are sufficiently stirred Afterwards, then in 200 r.min−1Under mix slowly 20 min.Later, it allows its natural subsidence to separate 30min, draws a certain amount of supernatant Liquid analyzes indices in waste water.
Clean-up effect: sewage per ton uses 0.05 kilogram of cleanser of the present invention, by the purification of 60min, chroma removal rate Up to 98.2%, turbidity removal rate is up to 95.1%, COD removal rate and is up to 91.5%, NH3- N removal rate is 92.3%, and heavy metal is gone Except rate is respectively Cu 88.4%, Zn 96.0%, Fe 86.0%, Cd 84.2%, Pb 92.6%.Landfill leachate is through of the invention net After agent processing, water outlet meets first discharge standard in " integrated wastewater discharge standard GB 8978-1996 ".
Comparative example application effect: it is handled using the poly aluminium iron silicate cleanser without photocatalysis effect of comparative example preparation, only Change effect: sewage per ton uses 0.10 kilogram of cleanser, and by the purification of 60min, chroma removal rate is up to 46.5%, and turbidity is gone 78.5%, NH is up to except rate is up to 76.1%, COD removal rate3- N removal rate is 58.8%, and heavy metal removing rate is respectively Cu 46.4%、Zn 58.5%、Fe 62.1%、Cd 51.6%、Pb 60.8%。
(4) river sewage: processing Foochow city river sewage, which is urban life area river, is mainly lived Sewage mixing.The four seasons spring, summer, autumn and winter water quality indicator of river sewage is different, and wherein the breeding wastewater in dry season in winter is every The equal highest of index.Dry season in winter water quality main indicator are as follows: SS is 154.5 mg/L, COD 180.4mg/L, NH3- N is 28.3 Mg/L, TP 5.1.
Application method: after adding cleanser in proportion, turn on agitator is first with 600r.min−110 min are sufficiently stirred Afterwards, then in 200 r.min−1Under mix slowly 20 min.Later, it allows its natural subsidence to separate 30min, draws a certain amount of supernatant Liquid analyzes indices in waste water.
Clean-up effect: sewage per ton uses 0.03 kilogram of cleanser of the present invention, and by the purification of 60min, SS removal rate is high 91.2%, NH is up to up to 94.0%, COD removal rate3- N removal rate is that 88.3%, TP removal rate is 85.3%, and water outlet reaches The level-one A standard of " urban wastewater treatment firm pollutant emission standard " (GB 18918-2002).
Comparative example application effect: it is handled using the poly aluminium iron silicate cleanser without photocatalysis effect of comparative example preparation, only Change effect: sewage per ton uses 0.05 kilogram of cleanser, and by the purification of 60min, SS removal rate is up to 64.9%, COD removal rate Up to 52.7%, NH3- N removal rate is that 36.8%, TP removal rate is 45.3%.
(5) livestock breeding wastewater: the sewage that the present invention uses is the large and medium-sized pig farm in Fuzhou City (scraping cleaning up excrement technique) Breeding wastewater, the four seasons spring, summer, autumn and winter concentration of breeding wastewater is different, wherein the breeding wastewater indices in dry season in winter Equal highest.Sampled measurement, breeding wastewater (winter) items physical and chemical index are as follows: pH 8.2, SS are 1411.5 mg/L, and COD is 2117.1mg/L NH3- N is 850.8 mg/L, and TP is 38.8 mg/L, and the average content of As, Cd, Cr, Hg and Pb are respectively 0.3,0.2,1.6,0.3 and 0.9 mg/L, antibiotic mass concentration are 2.1 mg/L.
Application method: after adding cleanser in proportion, turn on agitator is first with 600r.min−130 min are sufficiently stirred Afterwards, then in 200 r.min−1Under mix slowly 30 min.Later, it allows its natural subsidence to separate 60min, draws a certain amount of supernatant Liquid analyzes indices in waste water.
Clean-up effect: sewage per ton uses 0.07 kilogram of cleanser of the present invention, and by the purification of 120min, SS removal rate is high 88.2%, NH is up to up to 90.9%, COD removal rate3- N removal rate is up to 92.0%, TP removal rate and is up to 85.9%, heavy metals removal Rate is respectively As 89.2%, Cd 86.0%, Cr 86.8%, Hg 94.2%, Pb 94.1%, and antibiotic removal rate reaches 95.9% More than, reach livestock and poultry breeding industry pollutant emission standard (GB 18596--2001).
Comparative example application effect: it is handled using the poly aluminium iron silicate cleanser without photocatalysis effect of comparative example preparation, only Change effect: sewage per ton uses 0.10 kilogram of cleanser, and by the purification of 120min, SS removal rate is 44.6%, COD removal rate For 38.5%, NH3- N removal rate is that 39.8%, TP removal rate is 31.8%, and heavy metal removing rate is respectively As 62.7%, Cd 71.1%, Cr 58.2%, Hg 46.3%, Pb 68.9%, antibiotic removal rate are 10.8%.
Application example the result shows that, for different quality index, pass through and increase pretreatment, adjust purification dosage or control The technological means such as clarification time realize processing up to standard.Purifying agent for polluted water prepared by the present invention processes food processing wastewater, roast eel Waste water, landfill leachate, 5 kinds of waste water of river sewage and livestock breeding wastewater purification indices achieve good effect Fruit, treated, and sewage can qualified discharge.The application effect of embodiment and comparative example further illustrates modified TiO2Chelating is poly- The cleanser of aluminium iron silicate has powerful photochemical catalytic oxidation and coagulation composite performance, and the two synergy reaches purification sewage Purpose.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (7)

1. a kind of preparation method of the purifying agent for polluted water with photocatalysis and coagulation composite performance, it is characterised in that: the purification Agent is a kind of nano-TiO2-Fe2O3Chelate polysilicate aluminum ferric sulfate cleanser；It is wherein based on polysilicate aluminum ferric sulfate poidometer, TiO2Weight fraction is 7.71%, Fe2O3Weight fraction is 2.95%；Preparation method: specific step is as follows:
(1) 20wt% sodium silicate solution 0.1mol/L dilute sulfuric acid is adjusted into pH to 3, then stops stirring, stood at 40 DEG C poly- It closes, polymerization time is 1 ~ 2h, obtains activation polysilicon acid solution；
(2) at room temperature, 8.5 mL butyl titanates are measured to mix with 20 mL dehydrated alcohols, is denoted as solution A, it is anhydrous to measure 20 mL The solution mixing of ethyl alcohol, 5 mL glacial acetic acid and 2.5 mL deionized waters composition, is denoted as solution B, solution A is added dropwise to solution In B, it is stirred continuously to being added dropwise, stands 0.5 h, form the colloidal sol of homogeneous transparent；Colloidal sol is pulverized after standing and air-drying End, dry 2 h at 150 DEG C, obtained dry gel powder, which is put into Muffle furnace at 500 DEG C, is heat-treated 3 h, is ground up, sieved Up to nano-TiO2Powder；
(3) 7.27 g, nine water ferric nitrate is added in 30 mL dehydrated alcohols, adds nano-TiO made from 1.5 g steps (2)2； At room temperature, magnetic agitation and each 30 min of water bath sonicator are successively carried out, 6 h is stirred for, then, is in centrifuge by mixed liquor Under the conditions of 6000 rpm -6500 rpm, 7 min are centrifuged, supernatant is removed, being placed in temperature is 50 DEG C of baking oven drying, until nothing Water-ethanol volatilizees completely；Then product is calcined to 10 h to be cleaned multiple times with ethyl alcohol again at 300 DEG C, dries；Finally sample is existed 300 DEG C of 10 h of roasting, can be obtained nanometer Fe2O3-TiO2Composite material；
(4) 25 are configuredwtThe sulfuric acid solution of %, aluminium chloride is added under the mixing speed of 350 r/min in 70 DEG C of water-bath And iron chloride, control pH value are 1 ~ 2, and then this mixed solution is added in step (1) activation polysilicon acid solution and is stirred, simultaneously Add the nanometer Fe that 5 wt % steps (3) obtain2O3-TiO2Composite material and 1 wt% CaCO3, temperature be 40-60 DEG C and After mixing speed chelates 30min under conditions of being 200~400r/min, curing 1h is stood at a temperature of 55 DEG C, forms gel, so Gel is placed in 100 DEG C of drying boxes to drying to constant weight afterwards, then carries out washing 2 times, alcohol is washed 2 times, is placed into 80 DEG C of drying boxes Drying, grinding obtain the purifying agent for polluted water of powdered modified titanium dioxide chelating poly aluminium iron silicate.
2. preparation method according to claim 1, it is characterised in that: Fe element and chlorination in step (4) in iron chloride The molar ratio of Si element is 1:2:3 in Al element and activation polysilicon acid in aluminium.
3. the purifying agent for polluted water with photocatalysis and coagulation composite performance being prepared method according to claim 1 with In the application administered on roast eel production waste water.
4. the purifying agent for polluted water with photocatalysis and coagulation composite performance being prepared method according to claim 1 with In the application administered on preserved fruit processing waste water.
5. the purifying agent for polluted water with photocatalysis and coagulation composite performance being prepared method according to claim 1 with In the application administered on river sewage.
6. the purifying agent for polluted water with photocatalysis and coagulation composite performance being prepared method according to claim 1 with In the application administered on landfill leachate.
7. the purifying agent for polluted water with photocatalysis and coagulation composite performance being prepared method according to claim 1 with In the application administered on livestock breeding wastewater.
CN201710500797.5A 2017-06-27 2017-06-27 A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance Active CN107244723B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710500797.5A CN107244723B (en) 2017-06-27 2017-06-27 A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710500797.5A CN107244723B (en) 2017-06-27 2017-06-27 A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance

Publications (2)

Publication Number Publication Date
CN107244723A CN107244723A (en) 2017-10-13
CN107244723B true CN107244723B (en) 2019-09-27

Family

ID=60014738

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710500797.5A Active CN107244723B (en) 2017-06-27 2017-06-27 A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance

Country Status (1)

Country Link
CN (1) CN107244723B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019066764A1 (en) * 2017-09-29 2019-04-04 Mykytiuk Oleksandr Yuriiovych Active substance for sewage treatment and dewatering of solid domestic wastes landfills
CN111204824A (en) * 2020-01-17 2020-05-29 广东东日环保股份有限公司 River surge sewage treatment agent and preparation method thereof
CN111841659B (en) * 2020-07-28 2023-03-28 福建省农业科学院农业工程技术研究所 Preparation of magnetic suspended 3D microspheres and application thereof in catalyzing ozone to mineralize refractory organic matters
CN112174279B (en) * 2020-11-13 2022-08-02 陕西科技大学 Polymeric aluminosilicate inorganic flocculant and preparation method and application thereof
CN116462378B (en) * 2023-06-14 2023-09-01 河北旺效环保工程有限公司 Combined treatment method for antibiotic production wastewater

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1493394A (en) * 2002-10-31 2004-05-05 中国科学院广州能源研究所 Iron oxide enveloped titanium dioxide photocatalyst and its preparation method and use
CN104117360A (en) * 2014-07-10 2014-10-29 青岛润国生态科技发展有限公司 Preparation method of flocculation-photocatalysis composite powder
CN105983399A (en) * 2015-01-28 2016-10-05 青岛润国生态科技研究院 Preparation method of modified bentonite sewage treatment material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1493394A (en) * 2002-10-31 2004-05-05 中国科学院广州能源研究所 Iron oxide enveloped titanium dioxide photocatalyst and its preparation method and use
CN104117360A (en) * 2014-07-10 2014-10-29 青岛润国生态科技发展有限公司 Preparation method of flocculation-photocatalysis composite powder
CN105983399A (en) * 2015-01-28 2016-10-05 青岛润国生态科技研究院 Preparation method of modified bentonite sewage treatment material

Also Published As

Publication number Publication date
CN107244723A (en) 2017-10-13

Similar Documents

Publication Publication Date Title
CN107244723B (en) A kind of purifying agent for polluted water and its application with photocatalysis and coagulation composite performance
Oladoye et al. Methylene blue dye: Toxicity and potential elimination technology from wastewater
Ali Removal of Mn (II) from water using chemically modified banana peels as efficient adsorbent
Elleuch et al. A new insight into highly contaminated landfill leachate treatment using Kefir grains pre-treatment combined with Ag-doped TiO2 photocatalytic process
Ilinoiu et al. Photocatalytic activity of a nitrogen-doped TiO2 modified zeolite in the degradation of Reactive Yellow 125 azo dye
Peighambardoust et al. Sono-photocatalytic activity of sea sediment@ 400/ZnO catalyst to remove cationic dyes from wastewater
CN109734228A (en) A kind of compound sewage processing method
CN101891274B (en) Method for coprocessing crystal violet polluted sewage by outdoor natural light-hydrogen peroxide
CN108502943A (en) A kind of printing and dying industry wastewater flocculating agent and preparation method thereof
Zuo et al. The formation of alpha-FeOOH onto hydrothermal biochar through H2O2 and its photocatalytic disinfection
Moosa et al. Removal of zinc ions from aqueous solution by bioadsorbents and CNTs
Shahraki et al. Papaya peel waste carbon dots/reduced graphene oxide nanocomposite: from photocatalytic decomposition of methylene blue to antimicrobial activity
Das et al. ZrO2@ chitosan composite for simultaneous photodegradation of three emerging contaminants and antibacterial application
CN101337705B (en) Montmorillonite complexes for removing blue algaes and method for preparing same
Hanoon et al. Adsorption of methyl orange from wastewater by using biochar
CN110946147A (en) Safe and environment-friendly sewage disinfection powder and preparation method and application thereof
Chakhtouna et al. Photocatalytic and bactericidal behaviors of Ag/TiO2 doped biochar through Ball–milling approach
CN110038528A (en) A kind of preparation method of Cellulose/Chitosan composite antibacterial adsorbent
CN110776079B (en) Method for promoting phenol pollutants to be efficiently photo-catalytically oxidized in situ by utilizing organic arsenic pollutants
CN102276012B (en) Method for purifying perfluorooctane sulfonate in water by photocatalysis in simulated sunlight
CN111115729A (en) Composite material for industrial wastewater treatment tubular membrane filter layer
CN101113028A (en) Method for preparing demulsification clarifier
CN103071399B (en) Composite flat membrane with regeneration capacity and preparation method thereof
CN107235531B (en) A kind of purifying agent for polluted water of modifying titanium dioxide chelating poly aluminium iron silicate
Huo et al. Effect of trace Ag+ adsorption on degradation of organic dye wastes

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant