Composite adsorbing material and preparation method thereof
Technical field
The present invention relates to water process field of environment protection, and in particular to a kind of to be with coal dust ash, ultra-fine analcime and active carbonaceous
Organic and inorganic fossil water treatment and purification material of primary raw material and preparation method thereof.
Background technology
With the development of petrochemical industry and related industry, organic wastewater has become one of main pollution source of water body.Have
Machine waste component is complicated, and content of organics is big, and most of deposited in the form of the aromatic groups such as benzene, naphthalene, anthracene, quinone is parents
Have the characteristics that coloration depth, strong toxicity, difficult to degrade, the threat of getting worse is constituted to water environment.In addition, with industry
Rapid development and waste water unreasonable discharge, the pollution of Heavy Metals in Waters is also increasingly severe, heavy metal wastewater thereby mainly come
From industries such as mining, smelting, electronics, plating, pesticide, pigment manufactures, usually based on one or two kinds of heavy metal contaminants,
A variety of inorganic and organic pollution coexists.The toxicity of heavy metal pollution is big, be not easy to be metabolized in the environment, easy biological concentration, Yi Tong
It crosses food chain and enters human body, seriously endanger human health.In certain special water bodys, also contain excessive F-, also to human body
Health threatens.
It is more that it is directed to above-mentioned organic and heavy metal polluted waste water processing method at present, including oxidizing process, photocatalytic method, mixed
Solidifying method, membrane separation process and absorption method etc..It in the above processing method, cuts both ways, absorption method therein is easy to operate, using more
Extensively.
CN201310733073. 7 provide it is a kind of processing methylene blue dye wastewater method, with diatomite, etc. for original
Material prepares sorbent-loaded yeast and handles dyestuff organic wastewater.The mullite that is used in this method, analcime, the absorption of diatom great soil group
Agent specific surface area is relatively low, limited to each organic molecular species pollutant energy-absorbing power.Meanwhile used yeast is to inorganic metal ion
Degradation cannot be played.A kind of modified walnut shell active carbon adsorbent of CN201510688988.X offers and preparation method thereof, it is main
It is used for the adsorbing and removing of heavy metal ion, it is limited for the pollutant effect of organic.
The sorbing material that existing absorption method processing trade effluent uses generally has the disadvantages that:Different sorbing materials
Saturated adsorption capacity is different, and is limited by the pore structure and surface texture of adsorbent, and the sorbing material of single mass is difficult reality
Handle the organic and inorganic pollution that type in water body is various, distinct to existing broad spectrum activity.Therefore, exploitation it is a kind of simple and
Organic and inorganic wastewater the sorbing material of processing can be efficiently cooperateed with to have great importance.
Invention content
For existing deficiency, the present invention provides a kind of composite adsorbing materials, can with broad spectrum activity adsorb and exist in waste water
Various organic pollutions, heavy metal ion and other harmful ions.
The composite adsorbing material of the present invention, on the basis of composite adsorbing material weight, including 5%-50% coal dust ash, 10%-
50% activated carbon and the nanometer analcime of 5%-60%;Wherein it is connected by activated carbon between flyash and analcime;It is compound
The specific surface area of sorbing material is 300-1500m2/ g, Kong Rongwei 0.3-1.5cm3/ g, mechanical strength 5-25N/mm.
In the composite adsorbing material of the present invention, coal dust ash granularity is -1000 mesh of 100 mesh, -800 mesh of preferably 300 mesh;Coal
Powder ash aperture is 1-200 μm, preferably 10-100 μm.
In the composite adsorbing material of the present invention, nanometer analcime crystal grain is nearly spherical, a diameter of 10-200nm, preferably
20-100nm。
The preparation method of the composite adsorbing material of the present invention, including following content:
(1) preparation of nanometer analcime
(1)Silicon source, alkali source, N- crassitudes and water are uniformly mixed, after closed hydro-thermal process, material is cooled to room temperature,
Then silicon source is added to again in the material after hydro-thermal process, is uniformly mixed;
(2)By step(1)Material through aging, crystallization, washing, drying and roasting, obtain a nanometer analcime.
Step(1)The alkali source is alkali metal hydroxide, preferably sodium hydroxide.
Step(1)The silicon source is Ludox, silica gel, white carbon, waterglass, silester -28, silester -32
Or one kind in silester -40, diatomite and silicon alkoxide or combinations thereof object, preferably Ludox, white carbon, silester -
28, one or more of silester -32 or silester -40.
Step(1)The silicon source be selected from sodium metaaluminate, aluminum nitrate, aluminium chloride, aluminum sulfate, aluminium oxide and aluminium hydroxide and
One or more of one kind in organo-aluminium alcoholate or combinations thereof object, preferably sodium metaaluminate, aluminium isopropoxide and aluminium secondary butylate.
Step(1)The hybrid mode is mechanical agitation, magnetic agitation or the either type of oscillation.
Step(1)Described in alkali source, silicon source, water, silicon source, N- crassitudes in terms of following substance, proportionate relationship
Meet:
SiO2/Al2O3Molar ratio is 5-80
N- crassitudes/SiO2Molar ratio is 0.05-0.25
H2O/SiO2Molar ratio is 20-100
OH-/SiO2Molar ratio is 0.5-0.9
Step(1)The closed hydrothermal conditions are:It is hydro-thermal process 1-24 hours closed at 90-120 DEG C.
Step(2)The aging condition is:30 ~ 80 DEG C of aging temperature, ageing time are 0.5 ~ 10 hour, preferably 1-6
Hour, more preferably 2-5 hour, carry out under agitation, further preferably ultrasonic disperse and stir collective effect under into
Row aging;The wherein described ultrasound condition is:The energy density of ultrasonic disperse is 0.2-4kW/L, the time of ultrasound and stirring action
It is 2-5 hours;The mode of the stirring includes mechanical agitation and/or magnetic agitation.
Step(2)The crystallization process carries out in a kettle, and crystallization condition is:Crystallization temperature is 140-200 DEG C, excellent
160-190 DEG C is selected, crystallization 5-250 hours, preferably 72-170 hours, pressure was the self-generated pressure of reaction kettle.
Product washing described in the method for the present invention, dry and roasting process are this field conventional process, and the present invention takes
Treatment conditions be:Reaction product is washed to neutrality using distilled water, then 5-24 hours dry at 80-150 DEG C, roasting temperature
Degree is 500-800 DEG C, and roasting time is 2-10 hours.
(2) coal dust ash, nanometer analcime are uniformly mixed, then add phenol resin solution kneading at viscous group, so
Aftershaping, molding high temperature cabonization, obtains composite adsorbing material.
Carbonization Conditions:Under inert gas shielding, it is warming up to 600-1000 DEG C, heating rate is 0.1-20 DEG C/min, carbonization
Time is 3-12 hours.Composite adsorbing material of the present invention is obtained after cooling.
The coal dust ash itself that the compound adsorbent of the present invention includes has natural multistage pore structure, and it is useless to be conducive to filtering
The large scales component such as colloid, larger molecular organics in water, the carbonaceous material hole formed after phenolic resin carbonized in adsorbent
Structure is flourishing, can be used for the absorption of small organic molecule and metal ion, and ultra-fine analcime belongs to nanoscale little crystallite size,
Outer surface prosperity can further depth absorption small organic molecule and metal ion, the special pore size distribution size that analcime has,
The range of adsorbable molecule can further be expanded.Therefore the compound material for water treatment of multi-stage porous of the present invention can be with broad spectrum activity same
Organic and inorganic pollution effective adsorbing and removing various to type in industrial wastewater, distinct Shi Shixian, method is simple,
It is easily operated.
Description of the drawings
Fig. 1 is the X-ray diffraction spectrum for the nano level superfine analcime that the embodiment of the present invention 1 synthesizes.
Fig. 2 is the scanning electron microscope image for the nano level superfine analcime that the embodiment of the present invention 1 synthesizes.
Specific implementation mode
The method of the present invention is described in detail below by embodiment.The crystal form of analcime uses X-ray diffraction table
Sign, pattern and size carry out observation and dimensional measurement using scanning electron microscope.Specific surface area uses low temperature nitrogen absorption method
It measures.Mechanical strength measurement is measured using QCY-602 type catalyst strength analyzers according to HG/T 2782-1996 standards.
Embodiment 1
At room temperature, water, sodium hydroxide, Ludox, N- crassitudes are mixed according to a certain percentage, then 90 DEG C of closed hydro-thermals
24 hours, it is cooled to room temperature, then spare sodium metaaluminate powder is added in above-mentioned solution, and stir evenly.Final material
Proportioning meets:Al2O3/SiO2=30, N- crassitude/SiO2=0.15, OH-/SiO2=0.75, H2O/SiO2=40.It later will be upper
Mixture is stated at 40 DEG C, ultrasound(1.0KW/L)And magnetic agitation 3 hours, it is then charged into reaction kettle in 175 DEG C of crystallization 120
Hour.Products therefrom is washed with distilled water, and after 120 DEG C of dryings, is roasted 5 hours through 550 DEG C.Analcime is turned out to be through XRD detections,
Scanned electron microscope observation is spherical-like morphology, and crystallite dimension is about 30nm, belongs to ultrafine nanometer range, specific surface area
270m2/g.By the coal dust ash of 200 mesh(Containing 10-100 μm of macropore and super big hole)It is uniformly mixed with ultra-fine analcime(Coal dust ash
With the mass ratio 1 of analcime:1), then fully infiltrated with 20% phenol resin solution, then reconciled again, kneading is at viscous group, then
It is extruded as the cylinder of 2mm diameters using former, after dry, be carbonized 6 hours for 800 DEG C under nitrogen protection, obtain coal dust ash-
The trielement composite material of analcime-carbonaceous.Coal dust ash content is 30% to composite material by weight, and analcime content is 30%,
Remaining group is divided into carbonaceous.The specific surface area of composite material is 629 m2/ g, Kong Rongwei 0.51cm3/ g, mechanical strength 11N/mm.Absorption
Performance is shown in Table 1.
Embodiment 2
At room temperature, water, sodium hydroxide, Ludox, N- crassitudes are mixed according to a certain percentage, then 100 DEG C of closed water
Heat 24 hours, is cooled to room temperature, then spare sodium metaaluminate powder is added in above-mentioned solution, and stir evenly.Final thing
Material proportioning meets:Al2O3/SiO2=40, N- crassitude/SiO2=0.20, OH-/SiO2=0.8, H2O/SiO2=60.Later will
Said mixture is at 60 DEG C, ultrasound(0.5KW/L)And stir 3 hours, it is then charged into reaction kettle small in 180 DEG C of crystallization 140
When.Products therefrom is washed with distilled water, and after 120 DEG C of dryings, is roasted 5 hours through 550 DEG C.Product detects the side's of turning out to be boiling through XRD
Stone, scanned electron microscope observation are spherical-like morphology, and crystallite dimension is about 35nm, belongs to nano-scale range, specific surface area
212m2/g.By the coal dust ash of 500 mesh(Containing 10-100 μm of macropore and super big hole)It is uniformly mixed with ultra-fine analcime(Coal dust ash
With the mass ratio 1 of analcime:1), reconciliation, kneading are at viscous group after adding 20% phenol resin solution mixing fully wetting, so
It uses former to be extruded as the cylinder of 2mm diameters afterwards, after dry, be carbonized 6 hours for 900 DEG C under nitrogen protection, obtain coal dust
The trielement composite material of ash-analcime-carbonaceous.Coal dust ash content is 35% to composite material by weight, and analcime content is 35%,
Remaining group is divided into carbonaceous.The specific surface area of composite material is 1056 m2/ g, Kong Rongwei 0.67cm3/ g, mechanical strength 14N/mm.It inhales
Attached performance is shown in Table 1.
Embodiment 3
At room temperature, water, sodium hydroxide, Ludox, N- crassitudes are mixed according to a certain percentage, then 120 DEG C of closed water
Heat 6 hours, is cooled to room temperature, then aluminium isopropoxide powder is added in above-mentioned solution, and stir evenly.Final material proportioning is full
Foot:Al2O3/SiO2=60, N- crassitude/SiO2=0.25, OH-/SiO2=0.9, H2O/SiO2=80.Later by above-mentioned mixing
Object is at 50 DEG C, ultrasound(2.0KW/L)And magnetic agitation 3 hours, it is then charged into reaction kettle in 180 DEG C of crystallization 140 hours.Institute
It obtains product to be washed with distilled water, after 120 DEG C of dryings, be roasted 5 hours through 550 DEG C.Product turns out to be analcime through XRD detections, passes through
Scanning electron microscope is observed, and is spherical-like morphology, crystallite dimension is about 18nm, belongs to superfine nano range, specific surface area
380m2/g.By the coal dust ash of 500 mesh(Containing 10-100 μm of macropore and super big hole)It is uniformly mixed with ultra-fine analcime(Coal dust ash
With the mass ratio 1 of analcime:2), then with 20% phenol resin solution mixing fully wetting, then through reconcile, kneading at viscous group, so
It uses former to be extruded as the cylinder of 2mm diameters afterwards, after dry, be carbonized 6 hours for 900 DEG C under nitrogen protection, obtain coal dust
The trielement composite material of ash-analcime-carbonaceous.Coal dust ash content is 20% to composite material by weight, and analcime content is 40%,
Remaining group is divided into carbonaceous.The specific surface area of composite material is 1347 m2/ g, Kong Rongwei 0.78cm3/ g, mechanical strength 15N/mm.
Absorption property is shown in Table 1.
Comparative example 1
Sorbing material is prepared in the method for embodiment 1 in CN201310733073. 7.Absorption property is shown in Table 1.
Comparative example 2
Sorbing material is prepared in the method for embodiment in CN201510688988.X 1.Absorption property is shown in Table 1.
Comparative example 3
The carbonaceous material that the phenolic resin of flyash, ultra-fine analcime and same deal that embodiment 1 is used is formed is through simple
Mechanical mixture adsorbent is made.Absorption property is shown in Table 1.
1 sorbing material of table compares the absorption property for simulating trade effluent
Simulate trade effluent composition:Methylene blue concentration 2000mg/L, mercury chloride concentration 200mg/L, nitric acid lead concentration 200mg/
L, concentration of sodium fluoride 10mg/l.The mass ratio of adsorbent and simulation sewage is 1:250, adsorption temp, 25 DEG C of room temperature, adsorption treatment
Time is 30 minutes.