CN103395809B - One kind is using solvent displacement/azeotropic point distillation seasoning synthesis nanometer γ Al2O3Method and its application - Google Patents
One kind is using solvent displacement/azeotropic point distillation seasoning synthesis nanometer γ Al2O3Method and its application Download PDFInfo
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- CN103395809B CN103395809B CN201310310408.4A CN201310310408A CN103395809B CN 103395809 B CN103395809 B CN 103395809B CN 201310310408 A CN201310310408 A CN 201310310408A CN 103395809 B CN103395809 B CN 103395809B
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Abstract
The invention discloses a kind of synthesize nanometer γ Al using solvent displacement/azeotropic point distillation seasoning2O3Method, AlCl3The concentration of solution is 0.7mol L‑1, the molar concentration ratio of dispersant is Al3+：Dispersant=250：1, stir after adding solvent, 580 DEG C of furnace temperature, with cheap AlCl3Replacing expensive aluminium alcoholates with n-butyl alcohol is raw material, controls Al by adding surfactant3+Hydrolysis rate and granule size, seasoning is distilled using solvent displacement/azeotropic point and effectively eliminates the hard aggregation of presoma gel aluminum hydroxide, prepared nanometer γ Al2O3Specific surface area is high, even particle distribution, and particle size is between 30nm to 70nm.Nanometer γ Al by preparation2O3Add in aluminium polychlorid, after being sufficiently mixed, prepared nano modification aluminium polychlorid.The coagulating waste water effect of settling of aluminium polychlorid can effectively be lifted.
Description
Technical field
The present invention relates to the technical field of materials chemistry preparation, particularly to nanometer γ-Al2O3Preparation method, especially
One kind is using solvent displacement/azeotropic point distillation seasoning synthesis nanometer γ-Al2O3Method and its application.
Background technology
With the quickening developing rapidly with Development of China's Urbanization of China's industrial and agricultural production, mass production and sanitary sewage produce
Amount increases severely.Especially since pursuing the restriction of economic interests and technical conditions, many sewage are unprocessed to be just directly discharged into ring
In border, lead to increasing water body to be contaminated, cause a series of society and environmental problem.Therefore, new and effective water
Treatment agent is the basic industry given priority in water process environmental protection industry technical field all the time, is also that water and wastewater industry is controlled with water pollution
The basic industry of science and engineering journey technological innovation development.
Flocculation technique be commonly used to both at home and abroad at present to increase water quality treatment effect a kind of not only facilitated but also economic water at
Reason technology, key issue therein is the selection of flocculant.According to the difference of composition, flocculant can be divided into inorganic flocculating agent, have
Machine flocculant and microbial flocculant.
The inorganic flocculating agent of tradition application is low molecular aluminium salt and iron salt.Aluminium salt mainly has aluminum sulfate, Alumen, sodium aluminate
Deng.Iron salt mainly has ferric chloride, ferrous sulfate and iron sulfate etc..But the molecular weight of inorganic flocculating agent is not high enough, aggregation
Adsorption bridging ability is not strong, especially poor many than organic polymer to the adsorption bridging ability of colloidal substance, and exists
The shortcomings of dosage is more, sludge quantity that is producing is larger, post processing is difficult.And, low molecule inorganic salt corrosivity are strong, decolouring,
The effect of turbidity removal is undesirable, and added amount of chemical is big, and residual quantity is also big, gradually by inorganic polymer flocculant and organic polymer
Flocculant is replaced.
Organic polymer coargulator mainly includes synthetic class and natural polymer two kinds of class of modification.With inorganic polymer
Flocculant ratio, organic polymer coargulator has that consumption is few, flocculation rate fast, by salt coexists, pH value affected little, generate mud
Less and disposable the advantages of, but there is toxic and expensive problem in it.
Narrowly, microbial flocculant falls within natural polymer Organic substance, is that people utilize biotechnology in recent years
The class developed is by the microorganism product with flocculation activity that growth metabolism to certain phase produces under Incubation Condition
Thing.It is to utilize biotechnology, extracted by fermentable, refined obtained from a kind of new, efficient, cheap water process
Agent.So far find the microorganism with flocculability more than 17 kinds, including mycete, antibacterial, actinomycetes and yeast etc., but flocculation
The condition of culture of agent producing strains, extraction, purifying complex, industrialized production difficulty is big.How to find at a kind of efficient, economic water
Reason method is one of water treatment field problem demanding prompt solution.
Nano material is new material that a class has a extensive future it is considered to be the new material of 21 century.Its development,
Provide a kind of possible approach for solving water pollution problems.The size range of nanoparticle between 1nm-100nm, due to it
Size is little, and specific surface is big, shows small-size effect, skin effect, quantum effect and macro quanta tunnel effect of uniqueness etc.,
Its physics, chemical property is made also accordingly to there occurs huge changing and many " anomalism " occurs：Excellent mechanical property, spy
Different magnetic property, high conductivity and diffusibility, high reactivity, adsorptivity and catalytic performance etc., cause countries in the world
Scientific and technological circle and the extensive concern of industrial circle.Therefore as 21 century, there is one of functional material and the structural material of development prospect
The nano alumina powder jointed focus being also always nano materials research field in recent years.
γ-Al2O3Belong to cubic system, spinel structure, wherein oxygen atom are in face-centered cubic packing, aluminium atom is filled in sky
In gap.From prepared nanoscale Al such as the mid-80 Gleiter2O3Since powder, people are continuous to the understanding of this new high-tech material
Deepen and find many of which characteristic, the such as characteristic such as high intensity, high rigidity, anticorrosive, high temperature resistant, non-oxidizability is extensive
For conventional industries (light industry, chemical industry, building materials etc.) and the high-tech area such as new material, microelectronics, aerospace industry, application prospect
Very wide.And because its specific surface area is big, particle surface has abundant mismatch key and oxygen debt key, superficiality activity is high, absorption
Ability is strong, is widely used as adsorbent, it has good adsorption to inorganic matters, Organic substance and heavy metal ion, can again
For the purified treatment of waste water, the enrichment of trace metal and recovery.
Although applied research in environmental conservation for the nanotechnology is started late.But quickly grow, have a extensive future, present
Scene of flourishing life.At present, had both at home and abroad and be much used for sewage disposal, sterilizing, purify sky with regard to nano material
The reports such as gas, control noise.
Up to the present, it has been found that a variety of methods preparing all kinds of nanoparticles.But there is no definite at present
Scientific classification standard.According to the initial condition classification of material, corresponding preparation method is broadly divided into：Vapor phase method, solid phase method,
Liquid-phase chemical reaction method etc..
Vapor phase method is directly to utilize gas or by the side such as plasma, laser evaporation, electron beam heating, electric arc heated
Material is become gas by formula, is allowed to issue biological reason or chemical reaction in gaseous state, finally condenses in cooling procedure and grow up
Form micropowder.Its easily-controlled reaction conditions, product are easily refined, as long as controlling reacting gas and the rarefied content of gas can obtain
To few nano powder reunited or do not reunite, particle dispersion is good, particle diameter is little, narrowly distributing, but this method high cost, output capacity are low, difficult
To realize industrialized production.
Solid phase method is to be calcined aluminium salt or aluminium oxide after grinding, ultra-fine by occurring solid state reaction to be directly obtained
Low-level oxidation aluminium powder, gained particle diameter is the α-Al of 20 to 60nm2O3Or γ-the Al of 4 to 20nm2O3.This method can be divided into pyrolysismethod, combustion
Burning method and Amorphous Crystallization method, wherein aluminium powder combustion method are methods the most classical, but equipment is complicated, and have dangerous, and powder is collected
Also difficult, application prospect is little.
The method of liquid phase method has many kinds, wherein sol-gel process because simple to operate, technological process is short, production cost phase
To relatively low, each constituent content is accurately controlled, and can achieve the uniform mixing on molecule/atomic level, prepared narrow particle size distribution,
Activity is high, be shaped as spherical nanometer Al2O3Granule, and become current preparation nanometer Al2O3Main stream approach, but this method
The price of raw materials used aluminium alcoholates is high, the more difficult control of gelation of colloidal sol, and various process conditions are complicated, easily reunites, to operation
Bring very big difficulty.For obtaining preferable nanometer spherical powder, many scholars try every means to control hydrolysising condition, its
Middle drying is a crucial step in liquid phase method, from colloidal sol preparation, be aged drying, calcining each stage all may lead to
Particle growth or reunion, wherein drying process condition have a significant impact to the performance of powder body.In recent years, someone was dry using freezing
Dry method, high-pressure drying method and Supercritical Drying Technology reduce and prevent the reunion in particle drying procedures, but technique and equipment are relatively
For complexity.
Content of the invention
The technical problem to be solved is the shortcoming that the nano-powder for sol-gel process preparation is easily reunited,
There is provided one kind using solvent displacement/azeotropic point distillation seasoning synthesis nanometer γ-Al2O3Method and its application, with cheap
AlCl3Replacing expensive aluminium alcoholates with n-butyl alcohol is raw material, controls Al by adding surfactant3+Hydrolysis rate and
The size of grain, this method effectively eliminates the hard aggregation of presoma gel aluminum hydroxide, prepared nanometer γ-Al2O3Specific surface area
High, even particle distribution, particle size is between 30nm to 70nm.With nanometer γ-Al2O3Modified polyaluminium chloride, can effectively carry
Rise the coagulant precipitation effect of aluminium polychlorid.
The present invention solves the technical scheme that adopted of above-mentioned technical problem：
One kind is using solvent displacement/azeotropic point distillation seasoning synthesis nanometer γ-Al2O3Method, it is characterized in that：Including
Following steps：
Step one, concentration is taken to be 0.6mol L-1To 0.8mol L-1AlCl3Solution 30mL, Al in molar ratio3+：Point
Powder is 250：1 consumption adds dispersant, and mixed liquor is uniformly dispersed using supersonic oscillations；
Step 2, dispersion are rapidly added 1 after terminating:1 ammonia 15.5mL, control ph between 7 to 9, and by mixed liquor
There is precipitation from homogeneous solution reaction in microwave chemical reactor；
Step 3, by precipitate centrifugation and wash；
Step 4, precipitate is aged certain time, then puts it in the n-butyl alcohol of 50mL ultrasonic disperse uniformly,
Carry out solvent displacement azeotropic point distillation under normal pressure, obtain light yellow gel predecessor；
Step 5, at 60 DEG C, light yellow gel predecessor is vacuum dried 2 hours, then calcination 2 hours after being ground,
Obtain white nanometer γ-Al2O3.
The Optimized Measures taken also include：
AlCl in above-mentioned step one3Solution concentration is 0.7mol L-1
Above-mentioned dispersant is polyvinyl alcohol or Polyethylene Glycol or acrylic acid or starch derivatives.
In above-mentioned step 2, the pH value of mixed liquor is 8.
In above-mentioned step 3 by the speed of precipitate centrifugation be 4000r min-1.
In above-mentioned step 4, the azeotropic point of solvent displacement is 92 DEG C.
In above-mentioned step 5, the calcination temperature of light yellow gel predecessor is 580 DEG C.
It is additionally provided with Cl between above-mentioned step 3 and step 4-Detecting step：Use 0.1mol L-1AgNO3Solution is checked
Precipitate after washing, until inspection is less than Cl-Exist, then precipitate is aged.
Nanometer γ-the Al being obtained in above-mentioned step 52O3Particle size is between 30nm to 70nm.
A kind of nanometer γ-Al2O3Application：By nanometer γ-Al2O3Add in aluminium polychlorid, after being sufficiently mixed, be obtained
Nano modification aluminium polychlorid.
Compared with prior art, the azeotropic distillation drying that the present invention adopts is a kind of important organic solvent displacement side
Formula, forms two component azeotropic mixture systems by adding the water in the boiling point organic solvent and gel low higher than water, surface tension, adopts
N-butyl alcohol, as solvent, takes away the water in gel in the way of azeotropic to greatest extent, and the hydroxyl of particle surface is taken by butoxy
In generation, thus preventing the formation of Al-O-Al key between granule, the hard aggregation producing when being dried can be inherently eliminated, substantially improve
Nanometer γ-Al2O3The dispersive property of powder, and the distinctive cavitation of ultrasound wave can make the generating rate raising of nucleus several
The order of magnitude, thus reducing grain diameter, suppressing the coalescence of nucleus and growing up, stoping the formation of granule hard aggregation, so that being obtained
γ-the Al obtaining2O3Specific surface area is big, and pore structure is excellent, even particle size distribution, and with transmission electron microscope (TEM) and X-ray diffraction
(XRD) nanometer Al to gained for the means such as2O3Characterized, obtained specific surface area height, even particle distribution, particle size is existed
Nanometer γ-Al between 30nm to 70nm2O3.
Nanometer γ-the Al that the present invention is obtained2O3Add in commercially available aluminium polychlorid (PAC), be sufficiently mixed and obtain nanometer
Modified coagulant, had both given the extremely strong characterization of adsorption of its nano material, had reduced the content of residual Al again, expanded answering of PAC
With scope, further improve the coagulation effect of PAC, its characteristic and advantage also illustrate one extensively for the development of water technology
Wealthy prospect.For the water treatment experiment of ultra, result shows a nanometer γ-Al2O3Modified aluminium polychlorid is to high concentrtion
The sedimentation velocity of water improves 22.7%, and coagulation effect has reached 68.6%, improves 11.4% than single aluminium polychlorid,
Significantly improve the coagulation effect of aluminium polychlorid.γ-the Al being produced using this law2O3Purity can reach more than 99.9%, grain
Footpath can control in below 40nm.
Brief description
Fig. 1 is γ-Al2O3The X-ray diffractogram of powder；
Fig. 2 is the γ-Al of sol-gel process preparation2O3γ-Al with present invention preparation2O3Comparison diagram, left side be colloidal sol-
γ-the Al of gel method preparation2O3,Right side is the γ-Al of present invention preparation2O3；
Fig. 3 is γ-Al after calcining under 853K2O3The transmission electron microscope figure of sample, wherein a curve are sol-gel
γ-the Al of method preparation2O3, the γ-Al that b curve is prepared for the present invention2O3.
Specific embodiment
Following examples are described in further detail to the present invention.
The present invention to tell about γ-Al by experiment2O3Preparation and its application：
Reagent and instrument：
Strong aqua ammonia, crystal aluminum chloride, NaOH, HCl, n-butyl alcohol, commercially available aluminium polychlorid, organic polymeric dispersants are (poly-
Ethylene glycol HO (CH2CH2O)nH (Polyethylene Glycol, PEG MP：600 to 800 and 5000), silver nitrate solution
(0.1mol·L-1), be analysis pure, experimental water be redistilled water.
500mL distilling flask, spherical condensation tube, crucible, electric-heated thermostatic water bath H.H.S11-2K, far infrared rapid draing
Device 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 oscillators, 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
Ultramicroscope, SXZ-2-5-10 chamber type electric resistance furnace.
Nanometer γ-Al2O3Preparation：
Concentration is taken to be 0.7mol L-1AlCl3Solution 30mL, Al in molar ratio3+:Dispersant=250:1 consumption, adds suitable
Amount dispersant Polyethylene Glycol, supersonic oscillations are uniformly dispersed, and are then rapidly added 1:1 ammonia 15.5mL, control ph is left 8.0
Right.There is precipitation from homogeneous solution reaction, centrifugation (4000r min in microwave chemical reactor-1) and wash precipitation, until using
0.1mol·L-1AgNO3Solution is checked less than Cl-Till, it is aged certain time, then make in the n-butyl alcohol be deposited in 50mL
Ultrasonic disperse uniformly, carries out (92 DEG C) distillation certain time (t of solvent displacement azeotropic point at ambient pressure>40min) obtain showing slightly yellow
The gel predecessor of color, 60 DEG C are continued vacuum drying 2h, then are ground calcination 2h at 580 DEG C, obtain final product the nanometer of white
γ-Al2O3.
Main chemical reaction is as follows：
1.Al (H2O)6 3+→Al(H2O)5OH2+→Al(H2O)4(OH)2 +→Al(H2O)3(OH)3；
2.Al (OH)nCl3-n(6-n)H2O+(3-n)NH3·H2O→Al(H2O)3(OH)3+(3-n)NH4Cl+(3-n)H2O；
3.Al (H2O)3(OH)3+3ROH→Al(OR)3+6H2O；
4.2Al (OR)3+6H2O→Al2O3·3H2O+6ROH (R is alkyl)；
5.Al2O3·3H2O80℃γ-Al2O3+3H2O.
Nanometer γ-Al2O3Sign：
Test the diffraction curve of nanotube sample with x-ray powder diffraction instrument, compare with X-ray standard diagram, sample is entered
Row thing phase and crystalline structure analysis；By transmission electron microscope observing nanometer Al2O3The particle diameter of crystal grain, pattern and reunion situation etc..
Nanometer γ-Al2O3With PAC complication experiment：
A certain amount of nanometer of γ-Al is added in aluminium polychlorid2O3, at room temperature supersonic oscillations be uniformly dispersed, ripe
Change, obtain final product modified polyaluminium chloride flocculating agent.
Experimental technique flow process：
Crystal aluminum chloride → dissolving → dispersant → vibration → ammonia → centrifugation → washing → solvent → distillation → calcination →
Self assembly is combined → modified polyaluminium chloride
Nanometer γ-Al2O3Identification：
γ-the Al of the preparation method preparation through the present invention2O3Purity can reach more than 99.9%, particle diameter can control
Below 40nm.Measure its crystalline structure with X-ray diffractometer, compare with the X-ray diffraction standard diagram of standard, be accredited as γ-
Al2O3, as shown in Figure 1.
Microstructure analysis with compare：
The γ that in Fig. 2, a and b is respectively prepared using sol-gel process and solvent displacement/azeotropic point distillation seasoning-
Al2O3The transmission electron microscope photo of powder body.γ-the Al of seasoning preparation knowable to figure compares, is distilled by solvent displacement/azeotropic point2O3
Granule dispersion is more uniform, and particle size distribution is narrower, the profile of crystal grain trend towards spherical, particle size 30nm to 70nm it
Between, method by asking statistical average, mensure particle diameter is 40nm, can improve the single dispersing performance of powder well.
This is because before it is dried, gel particles surface adsorption has substantial amounts of moisture and free hydroxyl, due to the surface of water
Tension force is very big, gel when being dried, volume-diminished, Distance Shortened between adjacent micelle, hydrone pass through hydrogen bond act on adjacent
Bridge between granule.If directly the generation of chemical bonding between granule will be led to, thus forming hard aggregation by calcined dehydration.And adopt
When being dried with the distillation of solvent displacement/azeotropic point, the moisture of gel particles surface adsorption has removed substantially, when the water quilt of particle surface
N-butyl alcohol replaces, and n-butyl alcohol polar hydroxyl groups form hydrogen bond with the free hydroxyl on micelle surface；It is coated on the n-butyl alcohol of gel surface
Nonpolar alkoxyl mix and infiltrate with the n-butyl alcohol in medium, it is to avoid form hydrogen bond action between particle；Again due to positive fourth
Alcohol surface tension is little and sterically hindered effect, and total effect makes interparticle force be lowered.In calcining, prevent adjacent grain
The formation of Al-O-Al key between son, thus overcome the generation of hard agglomeration.
AlCl3The concentration of solution selects：
The change of concentration is very big to the particle size influences of end product.Because concentration is high, aggregation velocity is fast, gives birth to during precipitation
The nucleus quantity becoming is many, obtains a large amount of amorphous sediments.Conversely, concentration is low, nucleation rate is slow, and the radius of granule is big.Experiment is sent out
Existing, when concentration is high, such as 1.0mol L-1When, due to Al3+Concentration is higher, and the particle surface energy being formed is big, and grain spacing is short,
, under surface force (Van der Waals force, surface electrostatic power, hydrogen bond force etc.) effect, gather together formation soft aggregate for granule and granule.
But these soft aggregates are difficult in time separately, to reform into hard aggregation through subsequent treatment, the powder granule size prepared is little,
But reunite seriously it is desirable to higher mechanical lapping just can reach requirement.And concentration is too low, then it is difficult nucleation, plus surface
The effect of power, mutually exclusive between granule, form stable state, thus affecting last yield rate.Control AlCl3The concentration of solution
In 0.7mol L-1, make the speed of nucleation and easily scatter and do not reunite.
The selection of dispersant：
The selection principle of dispersant is exactly can to dispose in subsequent treatment, does not affect product property.With liquid phase method
When preparing inorganic nanometer oxide, in system, add polyvinyl alcohol (PVA), Polyethylene Glycol (PEG), acrylic acid and starch derivatives
Make dispersant Deng Organic substance or polymer, the agglomeration traits of particle can be obviously improved.Wherein, Polyethylene Glycol, be a kind of non-from
Sub- surfactant, its good water solubility, there are excellent stability and lubricity, product is nontoxic and nonirritant.This project is preferential
Make dispersant from Polyethylene Glycol (PEG).
The selection of solvent：
Solvent should be dissolved each other with water section or immiscible, and boiling point is higher than water, is preferably formed with OH group, the OH of such colloid surface
Group can progressively be substituted by another group of solvent, and plays certain sterically hindered effect, so that the dispersibility of colloid is shown
Write and improve.Its reaction equation is as follows：
Al-OH+HO-R→Al-O-R+H2O
It is filled with hydrone, during convection drying, colloidal solid is mutual under capillary force action between aqueous precursor gel particle
Mutually close, easily form hard aggregation.And adopt solvent displacement/azeotropic point to distill the generation that seasoning can suppress hard aggregation, well
Azeotropic solvent should meet following condition：(1) azeotropic mixture can be formed with water；(2) water in steam phase under azeotropic conditions
Content is big；(3) boiling point of azeotropic solvent itself is relatively low.Learn that the water content in azeotropic mixture is bigger by experiment, neat solvent
The boiling point of itself is lower, more favourable to separating, and relatively after several alcohols, finds that selection n-butyl alcohol does azeotropic solvent best.Under
Table is the water content in the boiling point of several frequently seen alcohols and azeotropic mixture.
Water content in the boiling point of common azeotropic solvent and azeotropic mixture：
| Material | Pure material boiling point/DEG C | Azeotropic mixture boiling point/DEG C | Azeotropic mixture water content/% |
| N-butyl alcohol | 117.17 | 92.0 | 44.5 |
| Isobutanol | 108.4 | 89.7 | 30.0 |
| Sec-butyl alcohol | 99.5 | 88.5 | 32.0 |
| N-amyl alcohol | 138.0 | 95.4 | 55.0 |
| Benzene | 80.2 | 69.3 | 8.9 |
| Propanoic acid | 141.1 | 100.0 | 82.3 |
The selection of furnace temperature：
Due to being aluminium alcoholates through prepare after distillation, it is in xerogel state.Easily produce when temperature is too high α-
Al2O3Although granule may be also smaller, but it does not have γ-Al2O3Chemism high.In addition in order to ensure Organic substance calcination
Totally, temperature should not be too low, and experimental temperature controls best when 580 DEG C.
Furnace temperature and particle diameter relation：
| Furnace temperature/DEG C | 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-Al2O3Optimum proportioning with aluminium polychlorid：
Quantitative aluminium polychlorid (0.1g) is taken to add different amounts of γ-Al respectively2O3, then carry out grouping experiment, identical
The graduated cylinder of specification takes the coal slurry water (1,10g/100mL) of 40mL and the clay (2,10g/100mL) of 40mL to carry out contrast experiment.Number
According to as follows：
Modified post-polymerization aluminum chloride coagulation experiment coal slurry (1) and clay water slurry (2) coagulation experiment：
| Aluminium polychlorid:Al2O3Ratio 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 discovery, aluminium polychlorid and γ-Al2O3When from different material coagulation, effect is different, the polymerization of same amount
Aluminum chloride, different amounts of γ-Al2O3Coagulation effect is different.γ-Al2O3The impurity coagulation effect little to turbidity, granule is little is relatively
Good, and γ-Al2O3The micelle of institute's coagulation is thinner, but settling velocity very fast, thoroughly and water body transparency high, subsequent treatment ratio
It is easier to.And the coagulation effect that aluminium polychlorid is big to turbidity, granule is big is preferably, but comparatively speaking sedimented particle is larger,
Water transparency after process does not have γ-Al2O3Modified height.This experiment determine proportioning be：For suspension precipitation process,
Optimum proportioning clay water slurry 1:4, coal slurry is 1:3.And the sedimentation velocity of nano modification polymeric aluminum is than single aluminium polychlorid
Improve 22.7%.
Nano modification aluminium polychlorid is compared with single aluminium polychlorid flocculating effect：
Raw water quality：5 DEG C of turbidity of pH value=7.8 T=I=265.7NTU COD=399.3mg/L.
Nano modification aluminium polychlorid is compared with single aluminium polychlorid flocculating effect：
| Flocculant species | Dosage (mg/L) | Water outlet COD | COD clearance (%) | Sludge volume (mL) |
| Nano modification aluminium polychlorid | 100 | 125.4 | 68..6 | 13.4 |
| Aluminium polychlorid | 100 | 170.9 | 57.2 | 18.2 |
Can show that nano modification aluminium polychlorid removes COD and reached 68.6% by this table, carry than single aluminium polychlorid
High by 11.4%.Meanwhile, sludge volume greatly reduces, and is reduced into 13.4mL, reduces when processing than single aluminium polychlorid
26.4%, improve the coagulation effect of aluminium polychlorid.
Have been found through experimentation that the present invention has advantages below：
1. with cheap AlCl3·6H2O and n-butyl alcohol replace expensive aluminium alcoholates for raw material, prepare high-purity nm oxidation
Aluminum, then is modified being combined with aluminium polychlorid, increased the coagulation effect of aluminium polychlorid, has good economic benefit
And social benefit.Start the new technology producing water treatment agent with high-purity nm modified polyaluminium chloride.
2. can effectively remove the moisture in gel precursors using n-butyl alcohol azeotropic distillation, the hydroxyl of particle surface is by butoxy
Replace, thus preventing the formation of Al-O-Al key between granule, eliminating hard aggregation, substantially improving a nanometer γ-Al2O3Powder
Dispersive property.
3. nanometer γ-Al2O3Solvent displacement/azeotropic distillation method produce γ-Al2O3Purity can reach 99.9% with
On, particle diameter can control in below 40nm.
4. use nanometer γ-Al2O3Modified polymeric aluminum processes waste water, and optimum proportioning clay water slurry is 1:4, coal slurry is 1:3.
And nanometer γ-Al2O3The sedimentation velocity of modified poly aluminum improves 22.7% than single aluminium polychlorid；Remove COD to reach
68.6%, improve 11.4% than single aluminium polychlorid.Meanwhile, sludge volume greatly reduces, than single aluminium polychlorid
During process, sludge volume reduces 26.4%, improves the coagulation effect of aluminium polychlorid, is that the development of water technology is shown
One wide prospect.
Claims (1)
1. one kind is using solvent displacement/azeotropic point distillation seasoning synthesis nanometer γ-Al2O3Application, it is characterized in that：Described
Nanometer γ-Al2O3It is 0.7mol L that synthesis inclusion takes concentration-1AlCl3Solution 30mL, Al in molar ratio3+:Dispersant is 250:1
Consumption, add dispersant Polyethylene Glycol, mixed liquor is uniformly dispersed using supersonic oscillations, dispersion terminate after be rapidly added 1:
1 ammonia 15.5mL, control ph is 8.0；And mixed liquor is occurred in microwave chemical reactor precipitation from homogeneous solution react, will precipitate
Thing is in centrifuge speeds 4000r min-1Lower centrifugation is simultaneously washed, and uses 0.1mol L-1AgNO3After solution inspection washing
Precipitate, until inspection less than Cl-Exist, then precipitate is aged；Precipitate is aged certain time, then puts it into
In the n-butyl alcohol of 50mL, ultrasonic disperse uniformly, carries out solvent displacement azeotropic point distillation, azeotropic point is 92 DEG C, during distillation at ambient pressure
Between be more than 40min, obtain light yellow gel predecessor, at 60 DEG C to light yellow gel predecessor be vacuum dried 2 hours, then will
It grinds calcination 2h at 580 DEG C, obtains final product the nanometer γ-Al of white2O3, nanometer γ-Al2O3Purity reach 99.9%, particle diameter
In below 40nm；A certain amount of nanometer of γ-Al is added in aluminium polychlorid2O3, at room temperature supersonic oscillations be uniformly dispersed,
Ripening, obtains final product nano modification aluminium polychlorid；Process waste water, aluminium polychlorid during clay water slurry with nano modification aluminium polychlorid
With nanometer γ-Al2O3Ratio be 1:4, aluminium polychlorid and nanometer γ-Al during coal slurry2O3Ratio be 1:3, nano modification gathers
The sedimentation velocity closing aluminum chloride improves 22.7% than single aluminium polychlorid；Remove COD and reach 68.6%, more poly- than single
Close aluminum chloride and improve 11.4%；Meanwhile, sludge volume greatly reduces, and when processing than single aluminium polychlorid, sludge volume reduces
26.4%, improve the coagulation effect of aluminium polychlorid.
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| 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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