CN107915293A - A kind of Novel sewage processing composite flocculation agent and preparation method thereof - Google Patents

A kind of Novel sewage processing composite flocculation agent and preparation method thereof Download PDF

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Publication number
CN107915293A
CN107915293A CN201711328884.3A CN201711328884A CN107915293A CN 107915293 A CN107915293 A CN 107915293A CN 201711328884 A CN201711328884 A CN 201711328884A CN 107915293 A CN107915293 A CN 107915293A
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solution
flocculation agent
oxide
composite flocculation
matrix
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何梦婷
付亚冰
刘洋
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Jiangxi Zi Xuan Science And Technology Co Ltd
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Jiangxi Zi Xuan Science And Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention discloses a kind of Novel sewage to handle composite flocculation agent, and the composite flocculation agent is combined by oxide and chitosan, and the oxide includes Fe2O3Matrix and TiO2‑IrO2Active site position, the TiO2‑IrO2Active site bit distribution is in Fe2O3In the surface and hole of matrix.The present invention, which has synthesized, contains TiO2‑IrO2The Fe of active site position2O3The flocculant that matrix oxide is compounded to form with chitosan, the flocculant of preparation is compared to existing chitosan flocculant, COD removal rates, turbidity removal rate and Pb2+Concentration rate of descent is respectively provided with significant raising, and the sedimentation time shortens than chitosan flocculant, and wastewater purifying efficiency significantly optimizes.

Description

A kind of Novel sewage processing composite flocculation agent and preparation method thereof
Technical field
The invention belongs to technology of waste water control field, more particularly to a kind of Novel sewage processing composite flocculation agent and its preparation Method.
Background technology
The material that every solute that can make in solution, colloid or suspended particle produce flocculent deposit is all called flocculation Agent.In a kind of solution, the referred to as composite flocculation agent of impurity deposition is made using two or more material.The wadding of flocculant Solidifying effect is sufficiently complex physics, chemical process, and present most people thinks that the mechanism of flocculation is flocculation and cohesion two The process of kind effect.Coacervation process is colloidal solid unstability and forms the process of small agglomerate；Flocculation process is institute's shape Into small agglomerate flocculant effect under produce large volume flocculate process.
The species of flocculant mainly has inorganic, organic, microorganism and compound four major class.Inorganic flocculating agent is also referred to as solidifying Poly- agent, is mainly used in processing of drinking water, the purified treatment of industrial wastewater and underground water etc..Molysite system and aluminium salt system are nothings The two main major classes of machine flocculant, can be divided into hydrochloric acid system and sulfuric acid system, according to relative molecular weight according to the component of anion Two major class of low molecule and Polymer Systems can be divided into again.Organic polymer coargulator is to start the last century 60's progressively to make Second generation flocculant.With inorganic polymer flocculant Comparatively speaking, organic polymer coargulator has dosage few, flocculates It hurry up, influenced the advantages of small by salt, the pH value of accessing pending water and temperature coexists.But organic and inorganic polymer flocculant work It is not quite similar with mechanism, inorganic polymer flocculant is mainly by the charge effect between colloidal particle in flocculant and water body Decline N current potentials, colloidal particle is reunited, but micelle is mainly adsorbed onto wadding by organic polymer coargulator by suction-operated On solidifying agent molecule chain, so as to form floccule body.Microbiocidal flocculant is that one kind is nontoxic, efficient, use scope is wide, can voluntarily drop Solution, the flocculant of new generation of non-secondary pollution.The mechanism of action of microbial flocculant mainly has three kinds：Neutralization, bridging are made With with the volume effect of sweeping.
Recent study personnel research with flocculant process is complicated, waste water of the dispersion stablized when, find compound Type flocculant process effect is better than single flocculant, has pH value accommodation big, to low concentration or high-concentration waste water, Duo Zhonggong The advantages that industry waste water, colorful wastewater have good treatment effect, and dehydration property is good.Composite flocculant it is cleaned Journey is generally attracted on the surface of inorganic flocculating agent using compounding mechanism, one side sewage impurity or ion, and charge neutrality occurs Act on and agglomerate impurity；On the other hand by high molecular bridging effect, impurity absorption is made on high molecular active group, Together sink so as to capture other impurity particles.But now widely used composite flocculant is to dirty water pollutant Remove single, selectivity is stronger, it is difficult to the comprehensive numerous type dopants removed in sewage；Manufacturing process is complicated, to product effect Disturbing factor it is more, adsorption effect be difficult control；It is higher to manufacture cost, is unfavorable for large-scale industrialization promotion.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of Novel sewage to handle composite flocculation agent, described multiple Close flocculant to be combined by oxide and chitosan, the oxide includes Fe2O3Matrix and TiO2-IrO2Active site position, institute State TiO2-IrO2Active site bit distribution is in Fe2O3In the surface and hole of matrix.
Further, the preparation method of the oxide comprises the following steps：
(1) Fe2O3The synthesis of matrix：Take a certain amount of FeCl3Or FeCl3·6H2O is soluble in water to be configured to FeCl3Solution, so Backward FeCl3L-phenylalanine, polyethylene glycol and hydrogen peroxide are added in solution, solution is sufficiently stirred, then is added dropwise into solution Ammonium hydroxide is more than 11 until solution pH value, and solution is transferred in water heating kettle, and sealing autoclave body carries out hydro-thermal reaction, hydrothermal temperature >=200 DEG C, the reaction time is more than 15h, and solution is cooled to room temperature simultaneously separation of solid and liquid, solid phase deionized water after the completion of reaction Fully washing, drying, the solid after drying calcine 2~3h at 450~500 DEG C, that is, obtain Fe2O3Matrix powder；
(2) TiO2-IrO2The formation of active site position：The mixed of butyl titanate, chloro-iridic acid, ethylene glycol and ethanol is prepared in a reservoir Solution is closed, mixed solution stirs, then by the Fe2O3Matrix powder is dispersed in mixed solution, sealing container, Air pressure in container is evacuated to less than 0.05 atmospheric pressure, more than pressurize 30min, carries out ultrasound in pressure maintaining period to mixed solution Ripple shakes, equalizing reservoir inner and outer air pressure after the completion of ultrasonic vibration, by mixed solution separation of solid and liquid, solid phase drying and processing, after drying 1~2h of calcining at 400~500 DEG C is placed in, that is, obtains and contains TiO2-IrO2The Fe of active site position2O3Matrix oxide.
Further, the step of oxide passes through modification, the modification be：
1) glacial acetic acid and iron chloride are dissolved in water and are configured to modification liquid, the mass percent of acetic acid is in the modification liquid 10%~20%, the concentration of the iron chloride is 0.1~0.3mol/L；
2) oxide is immersed in the modification liquid, carrying out heating to modified solution boils, boiling time for 10~ 15min；
3) heating cools down modification liquid after boiling, separation of solid and liquid, collects solid phase and is washed with deionized 3~4 times, then by solid phase It is dry, that is, obtain the oxide after modification.
Further, the quality of the modification liquid is more than 4 times of the oxide mass.
Further, the FeCl3Fe in solution3+Molar concentration be 0.1~0.3mol/L, addition L-phenylalanine, The amount of polyethylene glycol and hydrogen peroxide is in mass ratio：
FeCl3Solution:L-phenylalanine:Polyethylene glycol:Hydrogen peroxide=10:1~2:0.1~0.5:0.03~0.08,
Hydrogen peroxide mass fraction >=35% in the hydrogen peroxide.
Further, in the step (2), butyl titanate, chloro-iridic acid, ethylene glycol and ethanol mixed solution in, each group Divide and be respectively by weight：10~30 parts of butyl titanate, 5~8 parts of chloro-iridic acid, 20~30 parts of ethylene glycol, 100 parts of ethanol, it is described The quality of mixed solution is Fe2O3More than 2 times of matrix powder quality.
The invention also discloses the preparation method of the composite flocculation agent, contains TiO by described2-IrO2Active site position Fe2O3Matrix oxide ultrasonic wave is dispersed in the aqueous solution of citric acid, methylcellulose and sodium pyrophosphate, in dispersion process not It is disconnected to stir, the acetic acid solution of chitosan is added in whipping process into solution, sodium hydroxide is added dropwise solution is in neutrality, then Acrylamide water bath with thermostatic control reaction is added into solution, separation of solid and liquid obtains cotton-shaped filtrate after the completion of reaction, and filtrate is existed Less than 70 DEG C drying, that is, obtain composite flocculation agent of the present invention.
Further, in the aqueous solution of the citric acid, methylcellulose and sodium pyrophosphate, the mass fraction of citric acid is 5%~8%；The mass fraction of methylcellulose is 12%~20%；The mass fraction of sodium pyrophosphate is 1%~5%, citric acid, methyl The quality of the aqueous solution of cellulose and sodium pyrophosphate is 10~20 times of the oxide mass.
Further, the concentration of chitosan is 0.4~0.9g/mL in the acetic acid solution of the chitosan, chitosan acetic acid The addition of solution for citric acid, methylcellulose and sodium pyrophosphate aqueous solution 1~1.6 times of volume, the acrylamide The molal quantity of addition is more than the molal quantity of chitosan in solution.
Further, the water-bath temperature is 55~60 DEG C, and the reaction time is more than 4h.
As can be seen from the above technical solutions, it is an advantage of the invention that：
1. the present invention, which has synthesized, contains TiO2-IrO2The Fe of active site position2O3The wadding that matrix oxide is compounded to form with chitosan Solidifying agent, the flocculant of preparation is compared to existing chitosan flocculant, COD removal rates, turbidity removal rate and Pb2+Concentration rate of descent Significant raising is respectively provided with, and the sedimentation time shortens than chitosan flocculant, wastewater purifying efficiency significantly optimizes；
2. experiment is found, sewage purification adsorption effect of the modification processing method of the present invention to the oxide, which has, to be promoted Into effect, modified oxide is used for preparing synthesis composite flocculation agent, can further improve the water purification of composite flocculation agent Ability.This is probably since modification liquid causes the TiO of some passivation states2-IrO2Active site position is activated, and modified-reaction pair Fe2O3There is matrix certain etching and opening up hole to act on so that the active surface area of oxide significantly improves, and shows as to sewage The raising of middle granular absorption performance；
3. present invention optimizes the technique that chitosan prepares flocculant, by introducing methylcellulose and sodium pyrophosphate so that oxygen Compound is disperseed evenly in flocculant, and flocculant synthesis is more abundant, and flocculating effect is more preferable.
Embodiment
Technical scheme is described in detail with reference to embodiment：
Embodiment 1
A kind of Novel sewage handles composite flocculation agent, and the composite flocculation agent is combined by oxide and chitosan, the oxygen Compound includes Fe2O3Matrix and TiO2-IrO2Active site position, the TiO2-IrO2Active site bit distribution is in Fe2O3The surface of matrix In hole.
The preparation method of the oxide comprises the following steps：
(1) Fe2O3The synthesis of matrix：Take a certain amount of FeCl3Or FeCl3·6H2O is soluble in water to be configured to FeCl3Solution, FeCl3Fe in solution3+Molar concentration be 0.1mol/L.Then to FeCl3In solution add L-phenylalanine, polyethylene glycol and Hydrogen peroxide mass fraction is 35% hydrogen peroxide, and the amount of addition L-phenylalanine, polyethylene glycol and hydrogen peroxide is in mass ratio：
FeCl3Solution:L-phenylalanine:Polyethylene glycol:Hydrogen peroxide=10:1:0.1:0.03,
Solution is sufficiently stirred, then into solution be added dropwise ammonium hydroxide until solution pH value be more than 11, solution is transferred in water heating kettle, Seal autoclave body and carry out hydro-thermal reaction, hydrothermal temperature is 200 DEG C, and solution, is cooled to by reaction time 16h after the completion of reaction Room temperature and separation of solid and liquid, solid phase are fully washed with deionized water, dried, and the solid after drying calcines 2h at 450 DEG C, that is, obtains Fe2O3Matrix powder；
(2) TiO2-IrO2The formation of active site position：By butyl titanate 100g, chloro-iridic acid 50g, ethylene glycol 200g, ethanol 1000g Mixed solution is configured in a reservoir, and mixed solution stirs, then by 500gFe2O3Matrix powder is dispersed in mixing In solution, sealing container, less than 0.05 atmospheric pressure is evacuated to by the air pressure in container, pressurize 50min, to mixing in pressure maintaining period Solution carries out ultrasonic oscillation, equalizing reservoir inner and outer air pressure after the completion of ultrasonic vibration, by mixed solution separation of solid and liquid, solid phase drying Processing, drying, which is placed at 400 DEG C, calcines 1h, that is, obtains and contain TiO2-IrO2The Fe of active site position2O3Matrix oxide.
The preparation method of above-mentioned composite flocculation agent is：
By the TiO of the above-mentioned synthesis of 100g2-IrO2The Fe of active site position2O3Matrix oxide ultrasonic wave be dispersed in 1.5kg citric acids, In the aqueous solution of methylcellulose and sodium pyrophosphate, the mass fraction of citric acid is 5% in solution；The quality of methylcellulose point Number is 12%；The mass fraction of sodium pyrophosphate is 1%.It is stirred continuously in dispersion process, adding shell into solution in whipping process gathers Sugared concentration be 0.4g/mL chitosan acetic acid solution, the addition volume and citric acid of chitosan acetic acid solution, methylcellulose It is equal with the volume of the aqueous solution of sodium pyrophosphate.Sodium hydroxide, which is added dropwise, causes solution to be in neutrality, and propylene is then added into solution Acid amides water bath with thermostatic control is reacted, and the molal quantity of acrylamide addition is more than the molal quantity of chitosan in solution, water-bath Temperature is 55~60 DEG C, reaction time 5h.Separation of solid and liquid obtains cotton-shaped filtrate after the completion of reaction, by filtrate 70 DEG C with Lower drying, that is, obtain composite flocculation agent of the present invention.
Embodiment 2
A kind of Novel sewage handles composite flocculation agent, and the composite flocculation agent is combined by oxide and chitosan, the oxygen Compound includes Fe2O3Matrix and TiO2-IrO2Active site position, the TiO2-IrO2Active site bit distribution is in Fe2O3The surface of matrix In hole.
The preparation method of the oxide comprises the following steps：
(1) Fe2O3The synthesis of matrix：Take a certain amount of FeCl3Or FeCl3·6H2O is soluble in water to be configured to FeCl3Solution, FeCl3Fe in solution3+Molar concentration be 0.2mol/L.Then to FeCl3In solution add L-phenylalanine, polyethylene glycol and Hydrogen peroxide mass fraction is 35% hydrogen peroxide, and the amount of addition L-phenylalanine, polyethylene glycol and hydrogen peroxide is in mass ratio：
FeCl3Solution:L-phenylalanine:Polyethylene glycol:Hydrogen peroxide=10:1.3:0.5:0.06,
Solution is sufficiently stirred, then into solution be added dropwise ammonium hydroxide until solution pH value be more than 11, solution is transferred in water heating kettle, Seal autoclave body and carry out hydro-thermal reaction, hydrothermal temperature is 230 DEG C, and solution, is cooled to by reaction time 16h after the completion of reaction Room temperature and separation of solid and liquid, solid phase are fully washed with deionized water, dried, and the solid after drying calcines 2h at 450 DEG C, that is, obtains Fe2O3Matrix powder；
(2) TiO2-IrO2The formation of active site position：By butyl titanate 150g, chloro-iridic acid 66g, ethylene glycol 240g, ethanol 1000g Mixed solution is configured in a reservoir, and mixed solution stirs, then by 600gFe2O3Matrix powder is dispersed in mixing In solution, sealing container, less than 0.05 atmospheric pressure is evacuated to by the air pressure in container, pressurize 50min, to mixing in pressure maintaining period Solution carries out ultrasonic oscillation, equalizing reservoir inner and outer air pressure after the completion of ultrasonic vibration, by mixed solution separation of solid and liquid, solid phase drying Processing, drying, which is placed at 420 DEG C, calcines 1h, that is, obtains and contain TiO2-IrO2The Fe of active site position2O3Matrix oxide.
The preparation method of above-mentioned composite flocculation agent is：
The above-mentioned synthesis of 100g is contained into TiO2-IrO2The Fe of active site position2O3Matrix oxide ultrasonic wave is dispersed in 1.8kg lemons In the aqueous solution of lemon acid, methylcellulose and sodium pyrophosphate, the mass fraction of citric acid is 6% in solution；The matter of methylcellulose It is 14% to measure fraction；The mass fraction of sodium pyrophosphate is 2%.It is stirred continuously in dispersion process, is added in whipping process into solution Chitosan concentration is the acetic acid solution of the chitosan of 0.7g/mL, and the addition of chitosan acetic acid solution is citric acid, Methyl cellulose 1.2 times of the volume of the aqueous solution of element and sodium pyrophosphate.Sodium hydroxide, which is added dropwise, causes solution to be in neutrality, and third is then added into solution Acrylamide water bath with thermostatic control is reacted, and the molal quantity of acrylamide addition is more than the molal quantity of chitosan in solution, and water-bath is anti- It is 55~60 DEG C to answer temperature, reaction time 5h.Separation of solid and liquid obtains cotton-shaped filtrate after the completion of reaction, by filtrate at 70 DEG C Dry below, that is, obtain composite flocculation agent of the present invention.
Embodiment 3
A kind of Novel sewage handles composite flocculation agent, and the composite flocculation agent is combined by oxide and chitosan, the oxygen Compound includes Fe2O3Matrix and TiO2-IrO2Active site position, the TiO2-IrO2Active site bit distribution is in Fe2O3The surface of matrix In hole.
The preparation method of the oxide comprises the following steps：
(1) Fe2O3The synthesis of matrix：Take a certain amount of FeCl3Or FeCl3·6H2O is soluble in water to be configured to FeCl3Solution, FeCl3Fe in solution3+Molar concentration be 0.2mol/L.Then to FeCl3In solution add L-phenylalanine, polyethylene glycol and Hydrogen peroxide mass fraction is 35% hydrogen peroxide, and the amount of addition L-phenylalanine, polyethylene glycol and hydrogen peroxide is in mass ratio：
FeCl3Solution:L-phenylalanine:Polyethylene glycol:Hydrogen peroxide=10:1.6:0.2:0.05,
Solution is sufficiently stirred, then into solution be added dropwise ammonium hydroxide until solution pH value be more than 11, solution is transferred in water heating kettle, Seal autoclave body and carry out hydro-thermal reaction, hydrothermal temperature is 200 DEG C, and solution, is cooled to by reaction time 17h after the completion of reaction Room temperature and separation of solid and liquid, solid phase are fully washed with deionized water, dried, and the solid after drying calcines 3h at 480 DEG C, that is, obtains Fe2O3Matrix powder；
(2) TiO2-IrO2The formation of active site position：By butyl titanate 240g, chloro-iridic acid 74g, ethylene glycol 250g, ethanol 1000g Mixed solution is configured in a reservoir, and mixed solution stirs, then by 500gFe2O3Matrix powder is dispersed in mixing In solution, sealing container, less than 0.05 atmospheric pressure is evacuated to by the air pressure in container, pressurize 50min, to mixing in pressure maintaining period Solution carries out ultrasonic oscillation, equalizing reservoir inner and outer air pressure after the completion of ultrasonic vibration, by mixed solution separation of solid and liquid, solid phase drying Processing, drying, which is placed at 480 DEG C, calcines 2h, that is, obtains and contain TiO2-IrO2The Fe of active site position2O3Matrix oxide.
The preparation method of above-mentioned composite flocculation agent is：
The above-mentioned synthesis of 100g is contained into TiO2-IrO2The Fe of active site position2O3Matrix oxide ultrasonic wave is dispersed in 1.8kg lemons In the aqueous solution of lemon acid, methylcellulose and sodium pyrophosphate, the mass fraction of citric acid is 8% in solution；The matter of methylcellulose It is 17% to measure fraction；The mass fraction of sodium pyrophosphate is 4.2%.It is stirred continuously in dispersion process, adds in whipping process into solution Enter the acetic acid solution for the chitosan that chitosan concentration is 0.8g/mL, the addition of chitosan acetic acid solution is citric acid, methyl fibre 1.3 times of the volume of the aqueous solution of dimension element and sodium pyrophosphate.Sodium hydroxide, which is added dropwise, causes solution to be in neutrality, and is then added into solution Acrylamide water bath with thermostatic control is reacted, and the molal quantity of acrylamide addition is more than the molal quantity of chitosan in solution, water-bath Reaction temperature is 55~60 DEG C, reaction time 5h.Separation of solid and liquid obtains cotton-shaped filtrate after the completion of reaction, by filtrate 70 Dried below DEG C, that is, obtain composite flocculation agent of the present invention.
Embodiment 4
A kind of Novel sewage handles composite flocculation agent, and the composite flocculation agent is combined by oxide and chitosan, the oxygen Compound includes Fe2O3Matrix and TiO2-IrO2Active site position, the TiO2-IrO2Active site bit distribution is in Fe2O3The surface of matrix In hole.
The preparation method of the oxide comprises the following steps：
(1) Fe2O3The synthesis of matrix：Take a certain amount of FeCl3Or FeCl3·6H2O is soluble in water to be configured to FeCl3Solution, FeCl3Fe in solution3+Molar concentration be 0.3mol/L.Then to FeCl3In solution add L-phenylalanine, polyethylene glycol and Hydrogen peroxide mass fraction is 35% hydrogen peroxide, and the amount of addition L-phenylalanine, polyethylene glycol and hydrogen peroxide is in mass ratio：
FeCl3Solution:L-phenylalanine:Polyethylene glycol:Hydrogen peroxide=10:2:0.3:0.08,
Solution is sufficiently stirred, then into solution be added dropwise ammonium hydroxide until solution pH value be more than 11, solution is transferred in water heating kettle, Seal autoclave body and carry out hydro-thermal reaction, hydrothermal temperature is 250 DEG C, and solution, is cooled to by reaction time 15h after the completion of reaction Room temperature and separation of solid and liquid, solid phase are fully washed with deionized water, dried, and the solid after drying calcines 2h at 500 DEG C, that is, obtains Fe2O3Matrix powder；
(2) TiO2-IrO2The formation of active site position：By butyl titanate 300g, chloro-iridic acid 80g, ethylene glycol 280g, ethanol 1000g Mixed solution is configured in a reservoir, and mixed solution stirs, then by 500gFe2O3Matrix powder is dispersed in mixing In solution, sealing container, less than 0.05 atmospheric pressure is evacuated to by the air pressure in container, pressurize 50min, to mixing in pressure maintaining period Solution carries out ultrasonic oscillation, equalizing reservoir inner and outer air pressure after the completion of ultrasonic vibration, by mixed solution separation of solid and liquid, solid phase drying Processing, drying, which is placed at 500 DEG C, calcines 1h, that is, obtains and contain TiO2-IrO2The Fe of active site position2O3Matrix oxide.
The preparation method of above-mentioned composite flocculation agent is：
The above-mentioned synthesis of 100g is contained into TiO2-IrO2The Fe of active site position2O3Matrix oxide ultrasonic wave is dispersed in 2kg lemons In the aqueous solution of acid, methylcellulose and sodium pyrophosphate, the mass fraction of citric acid is 6% in solution；The quality of methylcellulose Fraction is 20%；The mass fraction of sodium pyrophosphate is 5%.It is stirred continuously in dispersion process, adds shell in whipping process into solution Glycan concentration is the acetic acid solution of the chitosan of 0.9g/mL, and the addition of chitosan acetic acid solution is citric acid, methylcellulose With 1.2 times of the volume of the aqueous solution of sodium pyrophosphate.Sodium hydroxide, which is added dropwise, causes solution to be in neutrality, and propylene is then added into solution Acid amides water bath with thermostatic control is reacted, and the molal quantity of acrylamide addition is more than the molal quantity of chitosan in solution, water-bath Temperature is 55~60 DEG C, reaction time 5h.Separation of solid and liquid obtains cotton-shaped filtrate after the completion of reaction, by filtrate 70 DEG C with Lower drying, that is, obtain composite flocculation agent of the present invention.
Comparative example 1
A kind of sewage disposal composite flocculation agent, the composite flocculation agent is by Fe2O3It is combined with chitosan, composite flocculation agent Preparation method and embodiment 3 are identical, differ only in：This comparative example is using Fe2O3It is compound with chitosan, Fe used2O3 The Fe synthesized for step (1) in embodiment 32O3Matrix powder, Fe2O3Matrix powder is without synthesis TiO2-IrO2Active site position It is directly used in (i.e. not comprising step (2)) compound with chitosan.Other processes and synthesis step are same as Example 3, system Obtain 1 sewage disposal composite flocculation agent of comparative example.
Comparative example 2
A kind of sewage disposal composite flocculation agent, and embodiment 3 are identical, and composite flocculation agent described in this comparative example is also by oxide and shell Glycan is combined, and oxide includes Fe2O3Matrix and TiO2-IrO2Active site position, the synthetic method of oxide also with embodiment 3 is identical.This comparative example and embodiment 3 difference lies in：Oxide passes through modification, and the oxide after modification uses again The step of method same as Example 3 and chitosan be compound to prepare composite flocculation agent, the modification is：
1) glacial acetic acid and iron chloride being dissolved in water and is configured to modification liquid, the mass percent of acetic acid is 16% in modification liquid, The concentration of the iron chloride is 0.27mol/L；
2) 200g oxides are immersed in modification liquid described in 860g, carrying out heating to modified solution boils, and boiling time is 10min；
3) heating cools down modification liquid after boiling, separation of solid and liquid, collects solid phase and is washed with deionized 3~4 times, then by solid phase It is dry, that is, obtain the oxide after modification.
Modified oxide 100g is taken, composite flocculation agent is synthesized according to 3 the method for embodiment, it is dirty to obtain comparative example 2 Water treatment composite flocculant.
Comparative example 3
A kind of sewage disposal composite flocculation agent, composite flocculation agent described in this comparative example are also combined by oxide and chitosan, Wherein the preparation method of oxide is identical with 3 the method for embodiment, preparation method and the institute of embodiment 3 of composite flocculation agent Difference is stated, it is differed only in, and the 100g of this comparative example synthesis contains TiO2-IrO2The Fe of active site position2O3Matrix oxide Ultrasonic wave is dispersed in 1.8kg aqueous citric acid solutions, and the mass fraction of citric acid is 8% in solution, without addition methyl in solution Cellulose and sodium pyrophosphate.Other step parameters, method and materials etc. are identical with embodiment 3, are made at 3 sewage of comparative example Manage composite flocculation agent.
Embodiment 5
The sewage of certain farm discharge of Jiangxi Poyang Lake Ecological Economic Region is selected as research object.With of the present invention multiple Before closing flocculant process, COD, turbidity and ammonia nitrogen concentration value in farm's waste discharge are first measured, then takes the row of the farm Put waste water and be divided into 24 parts, every part of 1L waste water.Plumbi nitras powder is added into every part of waste water so that Pb in waste water2+Ion concentration is 5mmol/L.Every 3 parts of waste water is divided into one group, totally eight groups of test groups, and above-described embodiment 1~4, comparative example 1~3 and common shell are gathered Sugared flocculant is separately added into the waste water of eight groups of test groups, and same group of waste water is purified using same flocculant, quiet under room temperature Sedimentation 2h is put, the addition of flocculant is 42mg flocculants/every liter of waste water.Taken after the completion of flocculating setting below liquid level at 3~5cm Liquid measure Pb2+Ion concentration, COD, turbidity and ammonia nitrogen concentration value, calculate Pb2+The removal rate of ion concentration, Pb2+Ion is gone Except rate=(Pb in raw wastewater2+Pb in solution after ion concentration-sedimentation2+Ion concentration) Pb in ÷ raw wastewaters2+Ion concentration × 100%, same group of measured value is averaged the purification result value as corresponding flocculant, and the results are shown in Table 1.
Table 1
As shown in table 1, comparative example 1~3 and common chitosan flocculant are understood, in process of the present invention and parameter The composite flocculation agent purifying water effect prepared under scope will be far superior to common chitosan flocculant, to wastewater COD removal rate, turbid Spend removal rate, ammonia nitrogen concentration rate of descent and Pb2+Concentration rate of descent is respectively provided with significant raising effect, and waste water can reach after handling 2h To the discharge standard of national regulation.Knowable to comparative example 3 and comparative example 1, Fe2O3The TiO of matrix surface synthesis2-IrO2Activity Point position has purification of waste water significant facilitation, there is TiO2-IrO2The Fe of active site position2O3Flocculant ratio made from matrix There is no the flocculant of active site position in COD removal rates, turbidity removal rate, ammonia nitrogen concentration rate of descent and Pb2+Concentration rate of descent each side Face is respectively provided with very big difference.Comparative example 3 and comparative example 2 understand that modification processing method of the present invention is to the oxidation The sewage purification adsorption effect of thing has facilitation, and modified oxide is used for preparing synthesis composite flocculation agent, Neng Goujin Improve to one step the water purification ability of composite flocculation agent.This is probably since modification liquid causes the TiO of some passivation states2-IrO2Activity Point position is activated, and modified-reaction is to Fe2O3There is matrix certain etching and opening up hole to act on so that the active table of oxide Area significantly improves, and shows as the raising to granular absorption performance in sewage.Comparative example 3 and comparative example 3 are understood, compound Methylcellulose and sodium pyrophosphate are introduced in the preparation of flocculant, the sewage disposal energy of flocculant can be improved to a certain extent Power.
Technical solution provided by the present invention is described in detail above, for those of ordinary skill in the art, According to the thought of the embodiment of the present invention, there will be changes in specific embodiments and applications, in conclusion this theory Bright book content should not be construed as limiting the invention.

Claims (10)

1. a kind of Novel sewage handles composite flocculation agent, it is characterised in that the composite flocculation agent is answered by oxide and chitosan Conjunction forms, and the oxide includes Fe2O3Matrix and TiO2-IrO2Active site position, the TiO2-IrO2Active site bit distribution exists Fe2O3In the surface and hole of matrix.
A kind of 2. Novel sewage processing composite flocculation agent according to claim 1, it is characterised in that the system of the oxide Preparation Method comprises the following steps：
(1) Fe2O3The synthesis of matrix：Take a certain amount of FeCl3Or FeCl3·6H2O is soluble in water to be configured to FeCl3Solution, so Backward FeCl3L-phenylalanine, polyethylene glycol and hydrogen peroxide are added in solution, solution is sufficiently stirred, then is added dropwise into solution Ammonium hydroxide is more than 11 until solution pH value, and solution is transferred in water heating kettle, and sealing autoclave body carries out hydro-thermal reaction, hydrothermal temperature >=200 DEG C, the reaction time is more than 15h, and solution is cooled to room temperature simultaneously separation of solid and liquid, solid phase deionized water after the completion of reaction Fully washing, drying, the solid after drying calcine 2~3h at 450~500 DEG C, that is, obtain Fe2O3Matrix powder；
(2) TiO2-IrO2The formation of active site position：The mixing of butyl titanate, chloro-iridic acid, ethylene glycol and ethanol is prepared in a reservoir Solution, mixed solution stir, then by the Fe2O3Matrix powder is dispersed in mixed solution, sealing container, will Air pressure in container is evacuated to less than 0.05 atmospheric pressure, more than pressurize 30min, and ultrasonic wave is carried out to mixed solution in pressure maintaining period Shake, equalizing reservoir inner and outer air pressure after the completion of ultrasonic vibration, by mixed solution separation of solid and liquid, solid phase drying and processing, dries postposition 1~2h is calcined at 400~500 DEG C, that is, obtains and contains TiO2-IrO2The Fe of active site position2O3Matrix oxide.
3. a kind of Novel sewage processing composite flocculation agent according to claim 2, it is characterised in that the oxide passes through The step of modification, the modification is：
1) glacial acetic acid and iron chloride are dissolved in water and are configured to modification liquid, the mass percent of acetic acid is in the modification liquid 10%~20%, the concentration of the iron chloride is 0.1~0.3mol/L；
2) oxide is immersed in the modification liquid, carrying out heating to modified solution boils, boiling time for 10~ 15min；
3) heating cools down modification liquid after boiling, separation of solid and liquid, collects solid phase and is washed with deionized 3~4 times, then by solid phase It is dry, that is, obtain the oxide after modification.
A kind of 4. Novel sewage processing composite flocculation agent according to claim 3, it is characterised in that the matter of the modification liquid Measure as more than 4 times of the oxide mass.
5. composite flocculation agent is handled according to a kind of Novel sewage of claim 2~4 any one of them, it is characterised in that described FeCl3Fe in solution3+Molar concentration be 0.1~0.3mol/L, addition L-phenylalanine, the amount of polyethylene glycol and hydrogen peroxide are pressed Mass ratio：
FeCl3Solution:L-phenylalanine:Polyethylene glycol:Hydrogen peroxide=10:1~2:0.1~0.5:0.03~0.08,
Hydrogen peroxide mass fraction >=35% in the hydrogen peroxide.
6. composite flocculation agent is handled according to a kind of Novel sewage of claim 2~4 any one of them, it is characterised in that described In step (2), butyl titanate, chloro-iridic acid, ethylene glycol and ethanol mixed solution in, each component is respectively by weight：Metatitanic acid 10~30 parts of butyl ester, 5~8 parts of chloro-iridic acid, 20~30 parts of ethylene glycol, 100 parts of ethanol, the quality of the mixed solution is Fe2O3Base More than 2 times of body powder quality.
7. the preparation method of composite flocculation agent as described in any one of claim 1~6, it is characterised in that contain TiO by described2- IrO2The Fe of active site position2O3Matrix oxide ultrasonic wave is dispersed in the aqueous solution of citric acid, methylcellulose and sodium pyrophosphate In, it is stirred continuously in dispersion process, adds the acetic acid solution of chitosan in whipping process into solution, sodium hydroxide is added dropwise and causes Solution is in neutrality, and acrylamide water bath with thermostatic control reaction is then added into solution, separation of solid and liquid obtains cotton-shaped mistake after the completion of reaction Screening, filtrate is dried below 70 DEG C, that is, obtains composite flocculation agent of the present invention.
8. the preparation method of a kind of composite flocculation agent according to claim 7, it is characterised in that the citric acid, methyl In the aqueous solution of cellulose and sodium pyrophosphate, the mass fraction of citric acid is 5%~8%；The mass fraction of methylcellulose is 12% ~20%；The mass fraction of sodium pyrophosphate is 1%~5%, and the quality of the aqueous solution of citric acid, methylcellulose and sodium pyrophosphate is 10~20 times of the oxide mass.
A kind of 9. preparation method of composite flocculation agent according to claim 7, it is characterised in that the acetic acid of the chitosan The concentration of chitosan is 0.4~0.9g/mL in solution, the addition of chitosan acetic acid solution is citric acid, methylcellulose and 1~1.6 times of the volume of the aqueous solution of sodium pyrophosphate, the molal quantity of the acrylamide addition are more than rubbing for chitosan in solution That number.
A kind of 10. preparation method of composite flocculation agent according to claim 7, it is characterised in that the water-bath temperature Spend for 55~60 DEG C, the reaction time is more than 4h.
CN201711328884.3A 2017-12-13 2017-12-13 A kind of Novel sewage processing composite flocculation agent and preparation method thereof Withdrawn CN107915293A (en)

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