CN103395809A - Method for synthesizing nanometer gama-Al2O3 by adopting solvent replacement/azeotropic distillation drying method and applications thereof - Google Patents

Method for synthesizing nanometer gama-Al2O3 by adopting solvent replacement/azeotropic distillation drying method and applications thereof Download PDF

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CN103395809A
CN103395809A CN2013103104084A CN201310310408A CN103395809A CN 103395809 A CN103395809 A CN 103395809A CN 2013103104084 A CN2013103104084 A CN 2013103104084A CN 201310310408 A CN201310310408 A CN 201310310408A CN 103395809 A CN103395809 A CN 103395809A
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solvent exchange
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CN103395809B (en
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王趁义
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The east of a river, Ningbo Sheng Chuan Design of Industrial Product Co., Ltd
Zhejiang Wan Li University
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Zhejiang Wanli College
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Abstract

The invention discloses a method for synthesizing nanometer gama-Al2O3 by adopting a solvent replacement/azeotropic distillation drying method. The method is characterized in that the concentration of a AlCl3 solution is 0.7mol.L<-1>, the molar concentration ratio of Al<3+> to a dispersing agent is 250:1, adding a solvent is added and then agitating is carried out, the furnace temperature is 580DEG C, low-cost AlCl3 and n-butyl alcohol replace expensive alcohol aluminum as raw materials, the hydrolysis rate of Al<3+> and the particle size are controlled through adding a surfactant, the hard agglomerate of a precursor aluminium hydroxide gel can be effectively eliminated by adopting the solvent replacement/azeotropic distillation drying method, the prepared nanometer gama-Al2O3 is high in specific area and even in particle distribution, and the particle sizes range from 30nm to 70nm. The prepared nanometer gama-Al2O3 is added in polymeric aluminium chloride and fully mixed to prepare the nanometer modified polymeric aluminium chloride. The waste water coagulating sedimentation effect of the polymeric aluminium chloride can be effectively promoted.

Description

A kind of employing solvent exchange/azeotropic point distillation desiccating method synthesis of nano γ-Al 2O 3Method and application thereof
Technical field
The present invention relates to technical field prepared by materials chemistry, particularly nanometer γ-Al 2O 3The preparation method, especially a kind of employing solvent exchange/azeotropic point distillation desiccating method synthesis of nano γ-Al 2O 3Method and application thereof.
Background technology
Along with the quickening with Development of China's Urbanization that develops rapidly of China's industrial and agricultural production, there is a sharp increase in output for mass production and sanitary sewage.Particularly, due to the restriction of pursuing economic interests and technical qualification, much sewage is unprocessed just directly to be entered in environment, causes increasing water body to be polluted, and has caused a series of society and environmental problem.Therefore, new and effective water treatment agent is the basic industry of giving priority in water treatment environmental protection industry technical field all the time, is also the basic industry of water and wastewater industry and water pollution control engineering innovation and development.
Flocculation technique is generally to be used at present both at home and abroad increasing water quality a kind of not only convenient but also economic water technology for the treatment of effect, and key issue wherein is the selection of flocculation agent.According to the difference that forms, flocculation agent can be divided into inorganic flocculating agent, organic floculant and microbial flocculant.
The inorganic flocculating agent of tradition application is low molecular aluminium salt and molysite.Aluminium salt mainly contains Tai-Ace S 150, alum, sodium aluminate etc.Molysite mainly contains iron trichloride, ferrous sulfate and ferric sulfate etc.But the molecular weight of inorganic flocculating agent is not high enough, and the adsorption bridging ability of aggregate is strong not, and is especially poor many to the adsorption bridging energy force rate organic polymer of colloidalmaterial, and has the shortcomings such as dosage sludge quantity more, that produce is large, aftertreatment is difficult.And low molecule inorganic salt corrodibility is strong, and the effect of decolouring, turbidity removal is undesirable, and added amount of chemical is large, and residual quantity is also large, by inorganic polymer flocculant and organic polymer coargulator, is replaced gradually.
Organic polymer coargulator mainly comprises two kinds of synthetic class and natural polymer modification classes.With the inorganic polymer flocculant ratio, organic polymer coargulator has that consumption is few, flocculation rate is fast, and the salt that coexisted, pH value affect little, generate the few and easy advantage such as processing of mud, but it has toxicity and expensive problem.
Strict microbial flocculant also belongs to the natural polymer organism in fact, is that people utilize a class that biotechnology develops by the microorganism product with flocculation activity that growth metabolism produces to certain phase under Incubation Condition in recent years.It is to utilize biotechnology, by microorganism fermented extracted, refining a kind of novel, efficient, the cheap water conditioner that obtains.So far find that the microorganism with flocculence surpasses 17 kinds, comprise mould, bacterium, actinomycetes and yeast etc., but the culture condition of bacterium for producing flocculant, extraction, purifying complex, the suitability for industrialized production difficulty is large.How finding a kind of efficient, economic water treatment method is one of water treatment field problem demanding prompt solution.
Nano material is the type material that a class has a extensive future, and is considered to the novel material of 21 century.Its development, provide a kind of possible approach for solving water pollution problems.The size range of nanoparticle is between 1nm-100nm, because its size is little, specific surface is large, show unique small-size effect, surface effects, quantum effect and macro quanta tunnel effect etc., make that its physics, chemical property are also corresponding huge variation have been occurred and many " abnormal phenomenas " occurred: good mechanical property, special magnetic property, high electric conductivity and diffusivity, high reactive behavior, adsorptivity and catalytic performance etc., caused the extensive concern of countries in the world scientific and technological circle and industrial community.Therefore as 21 century have one of the functional materials of development prospect and structured material nano alumina powder jointed be also the focus in nano materials research field in recent years always.
γ-Al 2O 3Belong to isometric system, spinel structure, wherein Sauerstoffatom is face-centered cubic packing, and the aluminium atom is filled in space.From the mid-80 Gleiter etc., make nano level Al 2O 3Since powder, people constantly deepen the understanding of this new high-tech material and find wherein to have numerous characteristics, as characteristics such as high strength, high rigidity, anticorrosive, high temperature resistant, oxidation-resistances, be widely used in the high-tech areas such as conventional industries (light industry, chemical industry, building materials etc.) and novel material, microelectronics, aerospace industry, application prospect is very wide.And because its specific surface area is large, particle surface has abundant mismatch key and oxygen debt key, the superficiality activity is high, high adsorption capacity, be widely used as again sorbent material, it has good adsorption to inorganics, organism and heavy metal ion, can be used for the purifying treatment of waste water, the enrichment of trace-metal and recovery.
Although the applied research of nanotechnology in environment protection started late.But development rapidly, has a extensive future, and presents scene of flourishing life.At present, had much about nano material for sewage disposal, sterilization and disinfection both at home and abroad, purified air, controlled the reports such as noise.
Up to the present, it has been found that the method for all kinds of nanoparticles of a variety of preparations.But there is no at present definite scientific classification standard.According to the virgin state classification of material, corresponding preparation method is broadly divided into: vapor phase process, solid phase method, liquid-phase chemical reaction method etc.
Vapor phase process is directly to utilize gas or by modes such as plasma body, laser evaporation, electron beam heating, electric-arc heating, material is become to gas, make it to issue biological reason or chemical reaction at gaseous phase, finally in process of cooling, condense the formation ultrafine powder of growing up.Its easily-controlled reaction conditions, product are easily refining, as long as control the nano powder that the rarefied content of reactant gases and gas just can obtain few reunion or not reunite, particle dispersion is good, particle diameter is little, narrowly distributing, but this method cost is high, output capacity is low, is difficult to realize suitability for industrialized production.
Solid phase method is that aluminium salt or aluminum oxide are calcined after grinding, and by solid state reaction occurs, directly makes the superfine aluminum oxide powder, and the gained particle diameter is α-Al of 20 to 60nm 2O 3Or γ-Al of 4 to 20nm 2O 3.This method can be divided into pyrolysis method, combustion method and Amorphous Crystallization method, and wherein the aluminium powder combustion method is the most classical method, but the equipment complexity, and tool danger, powder collection is also difficult, and application prospect is little.
The method of liquid phase method has a variety of, wherein sol-gel method because of simple to operate, technical process is short, production cost is relatively low, each component concentration can accurately be controlled, and can realize the even mixing on molecule/atomic level, make narrow particle size distribution, active high, be shaped as spherical nanometer Al 2O 3Particle, and become present preparation nanometer Al 2O 3Main stream approach, but the price of the raw materials used aluminium alcoholates of this method is high, the more difficult control of the gelation of colloidal sol, various processing condition impacts are complicated, easily reunite, and to operation, bring very large difficulty.For obtaining desirable nanometer spherical powder, many scholars try every means the controlled hydrolysis condition, wherein drying is the step of a key in liquid phase method, from colloidal sol preparation, ageing, to every one-phase dry, calcining, all may cause particle grow up or reunite, wherein the drying process condition has remarkably influenced to the performance of powder.In recent years, someone utilized freeze-drying, high-pressure drying method and Supercritical Drying Technology reduce and prevent the reunion in the particle drying process, but technology and equipment is comparatively complicated.
Summary of the invention
Technical problem to be solved by this invention is the shortcoming of easily reuniting for nano-powder prepared by sol-gel method, and a kind of employing solvent exchange/azeotropic point distillation desiccating method synthesis of nano γ-Al is provided 2O 3Method and application thereof, with the AlCl of cheapness 3With propyl carbinol, replacing the more expensive aluminium alcoholates of price is raw material, by adding tensio-active agent, controls Al 3+Hydrolysis rate and the size of particle, this method has been eliminated the hard aggregation of presoma aluminum hydroxide gel, the nanometer γ that makes-Al effectively 2O 3Specific surface area is high, even particle distribution, and particle size is between 30nm to 70nm.With nanometer γ-Al 2O 3Modified polyaluminium chloride, can effectively promote the coagulant precipitation effect of polymerize aluminum chloride.
The present invention solves the problems of the technologies described above the technical scheme that adopts:
A kind of employing solvent exchange/azeotropic point distillation desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: comprise the following steps:
Step 1, to get concentration be 0.6molL -1To 0.8molL -1AlCl 3Solution 30mL, Al in molar ratio 3+: dispersion agent is that the consumption of 250:1 adds dispersion agent, adopts ultra-sonic oscillation to be uniformly dispersed mixed solution;
Step 2, dispersion add rapidly 1:1 ammoniacal liquor 15.5mL after finishing, and control the pH value between 7 to 9, and mixed solution is occurred in microwave chemical reactor to for the precipitation from homogeneous solution (PFHS) reaction;
Step 3, by the throw out centrifugation and the washing;
Step 4, by throw out ageing certain hour, then put it into ultrasonic being uniformly dispersed in the propyl carbinol of 50mL, under normal pressure, carry out the distillation of solvent exchange azeotropic point, obtain the light yellow gel precursor;
Step 5, under 60 ℃ to light yellow gel precursor vacuum-drying 2 hours, then calcination 2 hours after it is ground, obtain white nanometer γ-Al 2O 3.
The optimized Measures of taking also comprises:
AlCl in above-mentioned step 1 3Strength of solution is 0.7molL -1
Above-mentioned dispersion agent is polyvinyl alcohol or polyoxyethylene glycol or vinylformic acid or starch derivative.
In above-mentioned step 2, the pH value of mixed solution is 8.
In above-mentioned step 3, by the speed of throw out centrifugation, be 4000rmin -1.
In above-mentioned step 4, the azeotropic point of solvent exchange is 92 ℃.
In above-mentioned step 5, the calcination temperature of light yellow gel precursor is 580 ℃.
Between above-mentioned step 3 and step 4, also be provided with Cl -Detecting step: use 0.1molL -1AgNO 3Throw out after solution check washing, until check is less than Cl -Exist, then by the throw out ageing.
The nanometer γ that makes in above-mentioned step 5-Al 2O 3Particle size is between 30nm to 70nm.
A kind of nanometer γ-Al 2O 3Application: by nanometer γ-Al 2O 3Add in polymerize aluminum chloride, after fully mixing, make the nano modification polymerize aluminum chloride.
Compared with prior art, the azeotropic distillation drying that the present invention adopts is a kind of important organic solvent substitute mode, by adding boiling point to form two component azeotropic systems higher than the low organic solvent of water, surface tension and the water in gel, adopt propyl carbinol as solvent, mode with azeotropic is taken away the water in gel to greatest extent, the hydroxyl of particle surface is replaced by butoxy, thereby prevented the formation of Al-O-Al key between particle, the hard aggregation that produces in the time of can fundamentally eliminating drying, improved nanometer γ-Al greatly 2O 3The dispersing property of powder, and the distinctive cavatition of ultrasonic wave can make the generating rate of nucleus improve several orders of magnitude, thus reduce grain diameter, suppress the coalescent of nucleus and grow up, stop the formation of particle hard aggregation, thereby make the γ-Al that obtains 2O 3Specific surface area is large, and pore structure is good, and size distribution is even, and with the nanometer Al of the means such as transmission electron microscope (TEM) and X-ray diffraction (XRD) to gained 2O 3Characterize, obtain that specific surface area is high, even particle distribution, the nanometer γ of particle size between 30nm to 70nm-Al 2O 3.
The nanometer γ that the present invention is made-Al 2O 3Add in commercially available polymerize aluminum chloride (PAC), fully be mixed to get the nano modification coagulating agent, both given the extremely strong characterization of adsorption of its nano material, reduced again the content of residual Al, enlarged the range of application of PAC, further improved the coagulation effect of PAC, its characteristic and advantage have also been showed a wide prospect for the development of water technology.For ultra's water treatment experiment, result shows nanometer γ-Al 2O 3The polymerize aluminum chloride of modification has improved 22.7% to ultra's settling velocity, and coagulation effect has reached 68.6%, than single polymerize aluminum chloride, has improved 11.4%, has obviously improved the coagulation effect of polymerize aluminum chloride.γ-the Al that adopts this law to produce 2O 3Purity can reach more than 99.9%, and particle diameter can be controlled at below 40nm.
The accompanying drawing explanation
Fig. 1 is γ-Al 2O 3The X-ray diffractogram of powder;
Fig. 2 is γ-Al prepared by sol-gel method 2O 3γ-the Al for preparing with the present invention 2O 3Comparison diagram, left side are γ-Al prepared by sol-gel method 2O 3,Right side is γ-Al prepared by the present invention 2O 3
Fig. 3 is the rear γ-Al of calcining under 853K 2O 3The transmission electron microscope figure of sample, wherein a curve is γ-Al prepared by sol-gel method 2O 3, the b curve is γ-Al prepared by the present invention 2O 3.
Embodiment
Following examples are described in further detail the present invention.
The present invention tells about γ-Al by experiment 2O 3Preparation and application thereof:
Reagent and instrument:
Strong aqua, crystal aluminum chloride, NaOH, HCl, propyl carbinol, commercially available polymerize aluminum chloride, organic polymer dispersion agent (polyoxyethylene glycol HO (CH 2CH 2O) nH (Polyethylene Glycol, PEG MP:600 to 800 and 5000), silver nitrate solution (0.1molL -1), being analytical pure, experimental water is redistilled water.
The 500mL distilling flask, spherical condensation tube, crucible, electric-heated thermostatic water bath H.H.S11-2K, far infrared flash dryer 766-3, electromagnetic centrifugal machine LXJ-64-01, contact voltage regulator TDGCZ-1KVA, X ray microcosmic layer scanning technology XMT-8000, SB-3200 type ultrasonic oscillator, be equipped with the LWMC-205 power-adjustable microwave chemical reactor of return-flow system, DZF6050 type vacuum drying oven, Rigaku Rigaku D/max-γ A type x-ray powder diffraction instrument, JEM-200CX type transmission electron microscope, SXZ-2-5-10 chamber type electric resistance furnace.
Nanometer γ-Al 2O 3Preparation:
Getting concentration is 0.7molL -1AlCl 3Solution 30mL, Al in molar ratio 3+: the consumption of dispersion agent=250:1, add appropriate dispersion agent polyoxyethylene glycol, ultra-sonic oscillation are uniformly dispersed, and then add rapidly 1:1 ammoniacal liquor 15.5mL, control the pH value in 8.0 left and right.The precipitation from homogeneous solution (PFHS) reaction occurs in microwave chemical reactor, centrifugation (4000rmin -1) and washing precipitation, until use 0.1molL -1AgNO 3The solution check is less than Cl -Till, the ageing certain hour, then make to be deposited in ultrasonic being uniformly dispersed in the propyl carbinol of 50mL, under normal pressure, carry out solvent exchange azeotropic point (92 ℃) distillation certain hour (t>40min) and obtain the slightly gel precursor of displaing yellow, 60 ℃ are continued vacuum-drying 2h, after again it being ground, in 580 ℃ of lower calcination 2h, obtain white nanometer γ-Al 2O 3.
Main chemical reaction is as follows:
1．Al(H 2O) 6 3+→Al(H 2O) 5OH 2+→Al(H 2O) 4(OH) 2 +→Al(H 2O) 3(OH) 3；
2．Al(OH) nCl 3-n(6-n)H 2O+(3-n)NH 3·H 2O→Al(H 2O) 3(OH) 3+(3-n)NH 4Cl+(3-n)H 2O；
3．Al(H 2O) 3(OH) 3+3ROH→Al(OR) 3+6H 2O；
4.2Al (OR) 3+ 6H 2O → Al 2O 33H 2O+6ROH (R is alkyl);
Figure 412686DEST_PATH_IMAGE002
5．Al 2O 3·3H 2O 80℃ γ-Al 2O 3+3H 2O。
Nanometer γ-Al 2O 3Sign:
Diffraction curve with x-ray powder diffraction instrument test nanotube sample, contrast with the X ray standard diagram, and sample is carried out to phase and crystalline structure analysis; By transmission electron microscope observing nanometer Al 2O 3The particle diameter of crystal grain, pattern and reunion situation etc.
Nanometer γ-Al 2O 3With the PAC complication experiment:
In polymerize aluminum chloride, add a certain amount of nanometer γ-Al 2O 3, at room temperature ultra-sonic oscillation are uniformly dispersed, and slaking obtains modified polyaluminium chloride flocculating agent.
The experimental technique flow process:
Crystal aluminum chloride → dissolving → dispersion agent → vibration → ammoniacal liquor → centrifugal → washing → solvent → distillation → calcination → self-assembly is compound → modified polyaluminium chloride
Nanometer γ-Al 2O 3Evaluation:
γ-the Al for preparing through preparation method of the present invention 2O 3Purity can reach more than 99.9%, particle diameter can be controlled at below 40nm.With X-ray diffractometer, measure its crystalline structure, with the X-ray diffraction standard diagram of standard, contrast, be accredited as γ-Al 2O 3, as shown in Figure 1.
Microstructure analysis and comparison:
In Fig. 2, a and b are respectively and adopt sol-gel method and solvent exchange/azeotropic point to distill γ-Al prepared by desiccating method 2O 3The transmission electron microscope photo of powder.More as can be known from figure, by γ-Al that solvent exchange/prepared by azeotropic point distillation desiccating method 2O 3Particle disperses comparatively even, and particle size distribution is narrower, and the profile of crystal grain trends towards spherical, and particle size is between 30nm to 70nm, and by asking the method for statistical average, the mensuration particle diameter is 40nm, can improve well the monodispersity energy of powder.
This is because before drying, and the gel particles surface adsorption has a large amount of moisture and free hydroxyl, because the surface tension of water is very large, gel when drying, volume-diminished, adjacent micelle spacing shortens, water molecules is by the bridge joint between adjacent particle that acts on of hydrogen bond.If directly by calcined dehydration, will cause the generation of chemical bonding between particle, thereby form hard aggregation.Solvent exchange/when azeotropic point distillation was dry, the moisture of gel particles surface adsorption had removed substantially and adopt, when the water of particle surface is replaced by propyl carbinol, and the free hydroxyl formation hydrogen bond on propyl carbinol polarity hydroxyl and micelle surface; Be coated on the nonpolar alkoxyl group of propyl carbinol of gel surface and the propyl carbinol in medium and mix and infiltrate, avoided between particle forming hydrogen bond action; And sterically hindered effect little due to the propyl carbinol surface tension again, total effect is lowered interparticle force.When calcining, stoped the formation of Al-O-Al key between adjacent particles, thereby overcome the generation of hard agglomeration.
AlCl 3The concentration of solution is selected:
The variation of concentration is very large to the particle size influences of final product.Because concentration is high, aggregation velocity is fast, and the nucleus quantity that generates during precipitin reaction is many, obtains a large amount of amorphous sediments.Otherwise concentration is low, and nucleation rate is slow, and the radius of particle is large.Experiment is found, when concentration is high, as 1.0molL -1The time, due to Al 3+Concentration is higher, and formed particle surface energy is large, and grain spacing is short, and particle and particle are under surface force (Van der Waals force, surface electrostatic power, hydrogen bond force etc.) effect, and the formation soft aggregate gathers together.But these soft aggregates are difficult in time separately, through subsequent disposal, just become hard aggregation, and the powder granule size of preparing is little, but it is serious to reunite, and the mechanical mill of having relatively high expectations just can reach requirement.And concentration is too low, is difficult for nucleation, is adding the effect of surface force, between particle, mutually repels, and forms stable state, thereby affects last yield rate.Control AlCl 3The concentration of solution is at 0.7molL -1, make the speed of nucleation and easily scatter and do not reunite.
The selection of dispersion agent:
The selection principle of dispersion agent can be disposed exactly in subsequent disposal, do not affect product property.With the Liquid preparation methods inorganic nanometer oxide time, in system, add the organism such as polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), vinylformic acid and starch derivative or polymkeric substance to make dispersion agent, can obviously improve the agglomeration traits of particle.Wherein, polyoxyethylene glycol, be a kind of nonionogenic tenside, and its good water solubility, have good stability and oilness, the nontoxic and nonirritant of product.This project preferentially selects polyoxyethylene glycol (PEG) to make dispersion agent.
The selection of solvent:
Solvent should dissolve each other or not dissolve each other with water section, and boiling point is higher than water, and the OH group is preferably arranged, and the OH group of colloid surface can progressively be substituted by another group of solvent like this, and plays certain sterically hindered effect, and the dispersiveness of colloid is significantly improved.Its reaction equation is as follows:
Al-OH+HO-R→Al-O-R+H 2O
Between the aqueous precursor gel particle, be full of water molecules, during convection drying, colloidal solid is adjacent to each other under capillary force action, easily forms hard aggregation.And adopting solvent exchange/azeotropic point distillation desiccating method can suppress the generation of hard aggregation, good azeotropic solvent should meet following condition: (1) can form azeotropic mixture with water; (2) under azeotropic conditions in vapor phase water-content large; (3) boiling point of azeotropic solvent itself is lower.Learn that by experiment the water content in azeotropic mixture is larger, the boiling point of neat solvent itself is lower, and is more favourable to separating, and after more several alcohols, finds to select propyl carbinol to do azeotropic solvent best.Following table is the boiling point of several frequently seen alcohols and the water content in azeotropic mixture.
The boiling point of common azeotropic solvent and the water content in azeotropic mixture:
Material The pure substance boiling point/℃ The azeotrope boiling point/℃ Azeotrope water content/%
Propyl carbinol 117.17 92.0 44.5
Isopropylcarbinol 108.4 89.7 30.0
Sec-butyl alcohol 99.5 88.5 32.0
Pentyl alcohol 138.0 95.4 55.0
Benzene 80.2 69.3 8.9
Propionic acid 141.1 100.0 82.3
The selection of furnace temperature:
Due to what after distillation, prepare, be aluminium alcoholates, be in the xerogel state.During excess Temperature, easily produce α-Al 2O 3Although particle may be also smaller, it does not have γ-Al 2O 3Chemically reactive high.Clean in order to guarantee the organism calcination in addition, temperature should not be too low, and is best when experimental temperature is controlled at 580 ℃.
Furnace temperature and particle diameter relation:
Furnace temperature/℃ 540 560 580 590 700
Time/min 40 40 30 30 30
Particle size/mm <0.10 <0.10 <0.10 0.15 0.15
Nanometer γ-Al 2O 3Best proportioning with polymerize aluminum chloride:
Get respectively γ-Al that quantitative polymerize aluminum chloride (0.1g) adds different amounts 2O 3, then carry out grouping experiment, the graduated cylinder of same size get 40mL coal slurry water (1,10g/100mL) and the clay of 40mL (2,10g/100mL) carry out the contrast experiment.Data are as follows:
Modification post polymerization aluminum chloride coagulation experiment coal slurry (1) and clay water slurry (2) coagulation experiment:
Polymerize aluminum chloride: Al 2O 3Ratio 1:0 1:2 1:3 1:4 1:5 1:6
Consumption/g 0.01 0.01 0.01 0.01 0.01 0.01
Average settling time 1/S 220 175 170 195 280 350
Average settling time 2/S 215 170 165 160 250 300
Research is found, polymerize aluminum chloride and γ-Al 2O 3Effect is different from the different substances coagulation time, the polymerize aluminum chloride of same amount, the γ-Al of different amounts 2O 3The coagulation effect difference.γ-Al 2O 3The impurity coagulation effect little to opacity, that particle is little is better, and γ-Al 2O 3The micelle of institute's coagulation is thinner, but sedimentation speed is very fast, thorough and transparency water body is high, and the subsequent disposal ratio is easier to.And the coagulation effect that polymerize aluminum chloride is large to opacity, particle is large is better, but comparatively speaking sedimented particle is larger, and the water transparency after processing does not have γ-Al 2O 3The height of modification.The proportioning that this experiment is determined is: for the suspension liquid precipitation process, and best proportioning clay water slurry 1:4, coal slurry is 1:3.And the settling velocity of nano modification polymeric aluminum has improved 22.7% than single polymerize aluminum chloride.
Nano modification polymerize aluminum chloride and single polymerize aluminum chloride flocculating effect compare:
Raw water quality: pH value=5 ℃ of turbidity of 7.8 T=I=265.7NTU COD=399.3mg/L.
Nano modification polymerize aluminum chloride and single polymerize aluminum chloride flocculating effect compare:
The flocculation agent kind Dosage (mg/L) Water outlet COD COD clearance (%) Sludge volume (mL)
The nano modification polymerize aluminum chloride 100 125.4 68..6 13.4
Polymerize aluminum chloride 100 170.9 57.2 18.2
Table can show that nano modification polymerize aluminum chloride removal COD has reached 68.6%, has improved 11.4% than single polymerize aluminum chloride thus.Simultaneously, sludge volume greatly reduces, and is reduced into 13.4mL, while than single polymerize aluminum chloride, processing, has reduced 26.4%, has improved the coagulation effect of polymerize aluminum chloride.
Can show that by experiment the present invention has the following advantages:
1. with the AlCl of cheapness 36H 2It is raw material that O and propyl carbinol replace the more expensive aluminium alcoholates of price, prepares high purity nanometer alumina, and then to carry out modification compound with polymerize aluminum chloride, has increased the coagulation effect of polymerize aluminum chloride, has good economic benefit and social benefit.Started the novel process of producing water treatment agent with the high-purity nm modified polyaluminium chloride.
2. adopt the moisture in propyl carbinol component distillation energy effective elimination gel precursor, the hydroxyl of particle surface is replaced by butoxy, thereby has prevented the formation of Al-O-Al key between particle, has eliminated hard aggregation, has greatly improved nanometer γ-Al 2O 3The dispersing property of powder.
3. nanometer γ-Al 2O 3γ-Al of producing of solvent exchange/azeotropic distn 2O 3Purity can reach more than 99.9%, particle diameter can be controlled at below 40nm.
4. with nanometer γ-Al 2O 3The polymeric aluminum of modification is processed waste water, and best proportioning clay water slurry is 1:4, and coal slurry is 1:3.And nanometer γ-Al 2O 3The settling velocity of modified poly aluminium has improved 22.7% than single polymerize aluminum chloride; Remove COD and reached 68.6%, than single polymerize aluminum chloride, improved 11.4%.Simultaneously, sludge volume greatly reduces, and while than single polymerize aluminum chloride, processing, sludge volume has reduced 26.4%, has improved the coagulation effect of polymerize aluminum chloride, for a wide prospect has been showed in the development of water technology.

Claims (10)

1. one kind is adopted solvent exchange/azeotropic point distillation desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: comprise the following steps:
Step 1, to get concentration be 0.6molL -1To 0.8molL -1AlCl 3Solution 30mL, Al in molar ratio 3+: dispersion agent is the consumption of 250:1, adds dispersion agent, adopts ultra-sonic oscillation to be uniformly dispersed mixed solution,
Step 2, dispersion add rapidly 1:1 ammoniacal liquor 15.5mL after finishing, and control the pH value between 7 to 9, and mixed solution is occurred in microwave chemical reactor to for the precipitation from homogeneous solution (PFHS) reaction;
Step 3, by the throw out centrifugation and the washing;
Step 4, by throw out ageing certain hour, then put it into ultrasonic being uniformly dispersed in the propyl carbinol of 50mL, under normal pressure, carry out the distillation of solvent exchange azeotropic point, obtain the light yellow gel precursor;
Step 5, under 60 ℃ to light yellow gel precursor vacuum-drying 2 hours, then calcination 2 hours after it is ground, obtain white nanometer γ-Al 2O 3.
2. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: AlCl in described step 1 3Strength of solution is 0.7molL -1.
3. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: described dispersion agent is polyvinyl alcohol or polyoxyethylene glycol or vinylformic acid or starch derivative.
4. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: in described step 2, the pH value of mixed solution is 8.
5. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: in described step 3, by the speed of throw out centrifugation, be 4000rmin -1.
6. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: in described step 4, the azeotropic point of solvent exchange is 92 ℃.
7. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: in described step 5, the calcination temperature of light yellow gel precursor is 580 ℃.
8. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: between described step 3 and step 4, also be provided with Cl -Detecting step: use 0.1molL -1AgNO 3Throw out after solution check washing, until check is less than Cl -Exist, then by the throw out ageing.
9. a kind of employing solvent exchange according to claim 1/azeotropic point is distilled desiccating method synthesis of nano γ-Al 2O 3Method, it is characterized in that: the nanometer γ that makes in described step 5-Al 2O 3Particle size is between 30nm to 70nm.
10. the nanometer γ for preparing by the described method of claim 1-Al 2O 3Application, it is characterized in that: by nanometer γ-Al 2O 3Add in polymerize aluminum chloride, after fully mixing, make the nano modification polymerize aluminum chloride.
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CN1752007A (en) * 2005-05-24 2006-03-29 武汉大学 Preparation method of active nano-aluminium oxide for coating
CN1986409A (en) * 2006-12-22 2007-06-27 武汉大学 Preparing process of nano gamma-alumina powder with intraparticle mesoporous structure

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CN107001040A (en) * 2014-10-08 2017-08-01 莱姆泰克株式会社 The method for manufacturing metal oxide powder
CN104817192A (en) * 2015-05-14 2015-08-05 余守德 Mixed biochemical water purifying agent and application thereof in sewage treatment
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