CN103920459A - Method for preparing efficient adsorption composite material by taking silicate clay and rice husk as raw materials - Google Patents
Method for preparing efficient adsorption composite material by taking silicate clay and rice husk as raw materials Download PDFInfo
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Abstract
The invention discloses a method for preparing an efficient adsorption composite material by taking silicate clay and rice husk as raw materials. The method comprises: adding a NaOH solution with a concentration of 1.5-4 mol/L into a mixture of silicate clay and rice husk with a mass ratio of 0.2-3:1, placing in a high-pressure reaction kettle, raising the temperature to 150-250 DEG C, and keeping warm for 10-24 h, wherein the mass ratio of the sum of silicate clay and rice husk to NaOH is 0.4-1.2:1; adding a NaAlO2 solution into the mixed slurry, under the condition of stirring, raising the temperature to 30-95 DEG C, and keeping warm for 4-25 h, wherein the mass ratio of the NaAlO2 solution to the silicate clay/rice husk active carbon composite material prepared in the step 2 is 8-25:1, and the NaAlO2 solution is prepared from NaAlO2 and deionized water according to a mass ratio of 3:10; and performing filtering, washing and drying on the crystallized substance, at nitrogen atmosphere, raising the temperature to 430-580 DEG C, and sintering for 2-16 h to prepare the efficient adsorption composite material. The efficient adsorption composite material prepared by taking silicate clay and rice husk as the raw materials is verified to have excellent adsorption performance.
Description
Technical field
The present invention relates to a kind ofly take silicate clay and rice husk and prepare the preparation method of efficient adsorption composite as raw material, belong to the preparing technical field of adsorbent.
Background technology
In the past few decades, along with the acceleration of industrial high speed development and Process of Urbanization Construction, the drinking water source of various places is subject to day by day serious pollution.In drinking water, the quantity of chemical composition is in continuous increase, and the various pathogenic microorganism factors constantly occur.Some epidemiologists' of Britain, the U.S. and Holland investigation proves, long-term drinking is containing the resident of lot of trace organic matter (especially carcinogenic, teratogenesis, mutagenic pollution) water, and its gastral cancer mortality is apparently higher than the control group resident of drinking purified.151 surface water source regions of China have 65.4% population to drink the water that does not meet water quality standard for drinking water, wherein approximately 200,000,000 people drink the water that coliform exceeds standard, 1.64 hundred million people drink the serious water of organic contamination, the disease relevant with pollution of waterhead nearly more than 50 planted, and the incidence of disease of malignant tumour and hepatitis is the trend of obvious rising.Therefore, remove the top priority that these trace contaminants in drinking water have become water purification.What the most of water factory of China was used is all for the conventional water treatment process of clean source water, mainly coagulation-precipitation-filtration-disinfection unit, consists of.This technique is better to the removal effect of the particles such as bacterium and turbidity, and not ideal to the removal effect of " three cause " pollutant existing with solubilised state, the microbial contamination in addition causing in water transfer pipe network, causes the security of drinking water can not be guaranteed.
At present, the Advanced Drinking Water Purification Technology adopting has: the technology such as film separation, ozone (O3) oxidation, Photocatalytic Oxidation With Semiconductors (as nano-titanium oxide), absorption.Membrane separation technique mainly contains ultrafiltration, nanofiltration, counter-infiltration etc., have efficient, can be in harmonious proportion the excellent features such as simple process.But because membrane aperture is very little, the ion in water (comprising the trace unit useful to human body) is almost removed, and the water that long-term drinking is this is harmful to people's health.In addition, the deficiency that the cost of film is high, contamination resistance is poor, operating pressure is large, energy consumption is higher limits its large-scale application.Ozone is a kind of very strong oxidant and disinfectant, although it can react with organic matter in most of water, uses separately ozone oxidation, limited to purification of water quality treatment effect.There are some researches show, ozone oxidation is to almost not removal effect of the chloroform having formed in water, to not removal effect of the heavy metal ion in water.Therefore, ozone is used seldom separately in water depth treatment process.On this basis, ozone and active carbon GC-MS grow up gradually and are widely used.Ozone can be little molecular state larger molecular organics oxidation Decomposition in water, thereby has improved the possibility that organic matter enters activated carbon capillary inside, takes full advantage of the absorption surface of active carbon, has extended life cycle.Have result of study to find, after ozone Oxidation Treatment, in water, biodegradable organic matter (BDOC) increases by 30%, then after biological activated carbon is processed, the organic clearance of bio-degradable is significantly improved.Photocatalysis oxidation technique is a kind of emerging modern water technology, its principle is to utilize energy to be equal to or greater than the irradiation semi-conducting material of semi-conducting material energy gap, electronics (e-) in its valence band is excited and transits to conduction band, in valence band, produce corresponding hole (h+).Photo-induced hole (h+) has the extremely strong electronic capability that obtains, by the OH-of its adsorption and H
2o is oxidized to hydroxyl radical free radical (OH).The standard oxidizing potential of OH reaches 2.8eV, is oxidant the strongest except element fluorine, can be without selectively most organic matter exhaustive oxidations being become to CO
2, H
2o and other inorganic matter.In light-catalyzed reaction numerous semiconductor catalysts used, the advantage such as catalytic activity is high owing to having for nano titania particle, stable in properties, nontoxic, anti-chemistry and photoetch becomes the first-selection of numerous researchers.For many years, people are in the modification of nano titania particle preparation, photocatalytic activity raising, light-catalyzed reaction mechanism, nano-titanium oxide (doping, compound, noble metal loading, dye sensitization) and make nano-titanium oxide absorption spectrum Einstein shift improve the aspects such as visible ray utilization ratio to have carried out further investigation, obtained a lot of achievements.Because nano-titanium oxide particle diameter is little, easily run off, the separation of later stage catalyst and recovery difficulty, make it be difficult to extensive use in drink water purifying is processed.Research work mostly rests on laboratory stage, and the application in water treatment Practical Project seldom.Absorption method is to utilize the surface nature of sorbing material, with bigger serface, water pollutant is carried out to enrichment with separated, has advantages of that convenient operation and management and energy consumption are low, is the focus that people study always.The effect of adsorption method for purifying water quality depends on sorbing material performance, and the economy of adsorption method for purifying water quality mainly depends on sorbing material price.Conventional sorbing material has active carbon, expanded graphite, clay mineral, zeolite, hydrotalcite, metal oxide, metal phosphate and flyash etc.Sorbing material has the feature of selective absorption to water pollutant, active carbon and expanded graphite are fine to Adsorption of Organic effect in water, but not good enough to heavy metal ion adsorbed effect in water; The inorganic material such as clay mineral and zeolite is high to removal of heavy metal ions rate in water, and to some organic matter in water, possibility absorption property is poor.Therefore, in the urgent need to developing, a kind of organic pollutants and inorganic pollution are all had to excellent absorption property and cheap Novel water-purifying material.
Summary of the invention
The object of the invention is to be to solve the aforementioned disadvantages that prior art exists, provide that a kind of technique is simple, cost is low and there is the efficient adsorption composite of excellent absorption property.
The principle that realizes the technical scheme of the object of the invention is: first silicate clay is mixed and made silicate clay and rice husk composite granule by mechanical agitation with rice husk, with H
3pO
4for activator at high temperature activates silicate clay and rice husk composite granule, so both can activate rice husk and make rice hull active carbon, can carry out surface active to silicate clay again; Then under hydrothermal condition, pass through NaOH simultaneously by the silicon stripping in silicate clay and rice hull active carbon, then add NaAlO
2solution carries out crystallization, synthesizes molecular sieve, filters, and a kind of efficient adsorption composite is prepared in final high temperature roasting.Certainly, machinery step compound and activation can be omitted, and also can make efficient adsorption composite, and just adsorptivity is slightly poor.
The method that silicate clay and rice husk prepare efficient adsorption composite as raw material of take specifically comprises following four schemes:
Scheme one comprises the following steps:
Step 1: the NaOH solution that adds 1.5-4mol/L in the silicate clay that is 0.2 ~ 3:1 to mass ratio and rice husk, wherein the gross weight of silicate clay and rice husk and the mass ratio of NaOH are 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 2: add NaAlO in the mixed serum of step 1 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 3: by the crystallization thing of step 2 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
Scheme two comprises the following steps:
Step 1: composition silicate clay and rice husk: be that 0.2 ~ 3:1 carries out mechanical agitation and mixes in mass ratio by silicate clay and rice husk, stir 5 ~ 35 hours, through 50 ~ 300 object filter mesh sieves, make silicate clay and rice husk composite granule;
Step 2: to the NaOH solution that adds 1.5-4mol/L in the silicate clay of step 1 gained and the compound split of rice hull active carbon, wherein the mass ratio of composite and NaOH is 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 3: add NaAlO in the mixed serum of step 2 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 4: by the crystallization thing of step 3 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
Scheme three comprises the following steps:
Step 1: the silicate clay that is 0.2 ~ 3:1 to mass ratio and rice husk in to add mass percentage concentration be 20% ~ 75% H
3pO
4solution, stirs, wherein composite granule and pure H
3pO
4mass ratio be 0.6 ~ 1:1, flood after 8 ~ 72 hours, macerate is placed under nitrogen atmosphere, is warming up to 250 ~ 620 ℃, activate 0.5 ~ 7 hour, naturally cool to room temperature, by the activation products of gained deionized water cyclic washing, to filtrate pH value, be neutral, washing finishes, dry, pulverizing, make silicate clay and rice hull active carbon composite;
Step 2: to the NaOH solution that adds 1.5-4mol/L in the silicate clay of step 1 gained and rice hull active carbon composite, wherein the mass ratio of composite and NaOH is 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 3: add NaAlO in the mixed serum of step 2 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 4: by the crystallization thing of step 3 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
Scheme four fundamental rules comprise the following steps:
Step 1: composition silicate clay and rice husk: be that 0.2 ~ 3:1 carries out mechanical agitation and mixes in mass ratio by silicate clay and rice husk, stir 5 ~ 35 hours, through 50 ~ 300 object filter mesh sieves, make silicate clay and rice husk composite granule;
Step 2: phosphoric acid activation: be 20% ~ 75% H to adding mass percentage concentration in the silicate clay of step 1 gained and rice husk composite granule
3pO
4solution, stirs, wherein composite granule and pure H
3pO
4mass ratio be 0.6 ~ 1:1, flood after 8 ~ 72 hours, macerate is placed under nitrogen atmosphere, is warming up to 250 ~ 620 ℃, activate 0.5 ~ 7 hour, naturally cool to room temperature, by the activation products of gained deionized water cyclic washing, to filtrate pH value, be neutral, washing finishes, dry, pulverizing, make silicate clay and rice hull active carbon composite;
Step 3: to the NaOH solution that adds 1.5-4mol/L in the silicate clay of step 2 gained and rice hull active carbon composite, wherein the mass ratio of composite and NaOH is 0.4～1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 4: add NaAlO in the mixed serum of step 3 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 5: by the crystallization thing of step 4 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
In aforementioned four schemes, the silicate clay in described step 1 is one or more in Concave-convex clay rod, montmorillonitic clay, sepiolite clay.
Adopted after technique scheme, the present invention has following beneficial effect: (1) the present invention be take silicate clay and rice husk and through checking, had excellent absorption property as raw material makes efficient adsorption composite.
(2) the present invention selects H
3pO
4for activator, both can activate rice husk and make rice hull active carbon, can carry out surface active to silicate clay again.
(3) the present invention prepares the required silicon source of molecular sieve process by the silicon stripping in silicate clay and rice husk to obtain with NaOH under hydrothermal condition simultaneously, has improved the absorption property of composite, has shortened the production cycle, has saved production cost.
(4) the present invention be take efficient adsorption composite that silicate clay and rice husk prepared as raw material to have technique simple, the advantage of raw material cheapness and wide material sources.
The specific embodiment
Below by specific embodiment, further describe method of the present invention.
(embodiment 1)
1, to the NaOH solution that adds 2.4mol/L in 2 kilograms of Concave-convex clay rods and 3 kilograms of rice husk powders, also be that silicate clay and rice husk are 2:3 in mass ratio, wherein the mass ratio of composite and NaOH is 0.9:1, is placed in autoclave, be warming up to 160 ℃, be incubated 18 hours;
2, in the mixed serum of step 1 gained, add NaAlO
2solution, under stirring condition, is warming up to 65 ℃, is incubated 18 hours, wherein NaAlO
2attapulgite in solution and step 1 and rice husk composite granule mass ratio are 18:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
3, by the crystallization thing of step 2 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 520 ℃, roasting 9 hours, makes efficient adsorption composite.
(embodiment 2)
1,2 kilograms of Concave-convex clay rods and 3 kilograms of rice husks being placed in mixer, is also that silicate clay and rice husk are 2:3 in mass ratio, stirs 12 hours, crosses 200 mesh sieves, makes attapulgite and rice husk composite granule;
2, to the NaOH solution that adds 2.4mol/L in the Concave-convex clay rod of step 1 gained and rice husk composite granule, wherein the mass ratio of composite and NaOH is 0.9:1, is placed in autoclave, is warming up to 160 ℃, is incubated 18 hours;
3, in the mixed serum of step 2 gained, add NaAlO
2solution, under stirring condition, is warming up to 65 ℃, is incubated 18 hours, wherein NaAlO
2attapulgite in solution and step 1 and rice husk composite granule mass ratio are 18:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
4, by the crystallization thing of step 3 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 520 ℃, roasting 9 hours, makes efficient adsorption composite.
(embodiment 3)
1, in 2 kilograms of Concave-convex clay rods and 3 kilograms of rice husk powders, add the H that 11.4 kilogram-mass percentage concentrations are 55%
3pO
4solution, is also that silicate clay and rice husk are 2:3 in mass ratio, stirs, flood 35 hours, after being dried, under nitrogen atmosphere, be warming up to 460 ℃, activate 2.5 hours, naturally cool to room temperature, the deionized water cyclic washing by the activation products of gained with 75 ℃, to filtrate pH value, be neutral, washing finishes, and dry, pulverizing, makes attapulgite/rice hull active carbon composite;
2, to the NaOH solution that adds 2.4mol/L in attapulgite/rice hull active carbon composite of step 1 gained, wherein the mass ratio of composite and NaOH is 0.9:1, is placed in autoclave, is warming up to 160 ℃, is incubated 18 hours;
3, in the mixed serum of step 2 gained, add NaAlO
2solution, under stirring condition, is warming up to 65 ℃, is incubated 18 hours, wherein NaAlO
2attapulgite/rice hull active carbon composite mass ratio in solution and step 1 is 18:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
4, by the crystallization thing of step 3 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 520 ℃, roasting 9 hours, makes efficient adsorption composite.
(embodiment 4)
1, the rice husk of the montmorillonitic clay of 1 kilogram and 5 kilograms being placed in mixer, is also that silicate clay and rice husk are 0.2:1 in mass ratio, stirs 5 hours, and mistake 50 mesh sieves, make montmorillonitic clay and rice husk composite granule;
2, in the montmorillonitic clay of step 1 gained and rice husk composite granule, add the H that 50 kilogram-mass percentage concentrations are 20%
3pO
4solution, stirs, and floods 72 hours, after dry, under nitrogen atmosphere, be warming up to 250 ℃, activate 0.5 hour, naturally cool to room temperature, deionized water cyclic washing by the activation products of gained with 50 ℃, is neutral to filtrate pH value, and washing finishes, dry, pulverizing, make montmorillonite/rice hull active carbon composite;
3, to the NaOH solution that adds 4mol/L in montmorillonitic clay/rice hull active carbon composite of step 2 gained, wherein the mass ratio of composite and NaOH is 0.4:1, is placed in autoclave, is warming up to 105 ℃, is incubated 14 hours;
4, in the mixed serum of step 3 gained, add NaAlO
2solution, under stirring condition, is warming up to 30 ℃, is incubated 4 hours, wherein NaAlO
2montmorillonite/rice hull active carbon composite mass ratio in solution and step 2 is 8:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
5, roasting: by the crystallization thing of step 4 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ℃, roasting 2 hours, makes efficient adsorption composite.
(embodiment 5)
1,3 kilograms of sepiolite clays and 1 kilogram of rice husk being placed in mixer, is also that silicate clay and rice husk are 3:1 in mass ratio, stirs 35 hours, crosses 300 mesh sieves, makes sepiolite clay and rice husk composite granule;
2, in the sepiolite clay of step 1 gained and rice husk composite granule, add the H that 5.3 kilogram-mass percentage concentrations are 75%
3pO
4solution, stirs, and floods 8 hours, after dry, under nitrogen atmosphere, be warming up to 620 ℃, activate 7 hours, naturally cool to room temperature, deionized water cyclic washing by the activation products of gained with 90 ℃, is neutral to filtrate pH value, and washing finishes, dry, pulverizing, make sepiolite/rice hull active carbon composite;
3, to the NaOH solution that adds 1.5mol/L in sepiolite/rice hull active carbon composite of step 2 gained, wherein the mass ratio of composite and NaOH is 1.2:1, is placed in autoclave, is warming up to 200 ℃, is incubated 22 hours;
4, in the mixed serum of step 3 gained, add NaAlO
2solution, under stirring condition, is warming up to 95 ℃, is incubated 25 hours, wherein NaAlO
2sepiolite/rice hull active carbon composite mass ratio in solution and step 2 is 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
5, roasting: by the crystallization thing of step 4 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 580 ℃, roasting 16 hours, makes efficient adsorption composite.
(embodiment 6)
1,2 kilograms of Concave-convex clay rods and 3 kilograms of rice husks being placed in mixer, is also that silicate clay and rice husk are 2:3 in mass ratio, stirs 12 hours, crosses 200 mesh sieves, makes attapulgite and rice husk composite granule;
2, in the Concave-convex clay rod of step 1 gained and rice husk composite granule, add the H that 11.4 kilogram-mass percentage concentrations are 55%
3pO
4solution, stirs, and floods 35 hours, after dry, under nitrogen atmosphere, be warming up to 460 ℃, activate 2.5 hours, naturally cool to room temperature, deionized water cyclic washing by the activation products of gained with 75 ℃, is neutral to filtrate pH value, and washing finishes, dry, pulverizing, make attapulgite/rice hull active carbon composite;
3, to the NaOH solution that adds 2.4mol/L in attapulgite/rice hull active carbon composite of step 2 gained, wherein the mass ratio of composite and NaOH is 0.9:1, is placed in autoclave, is warming up to 160 ℃, is incubated 18 hours;
4, in the mixed serum of step 3 gained, add NaAlO
2solution, under stirring condition, is warming up to 65 ℃, is incubated 18 hours, wherein NaAlO
2attapulgite/rice hull active carbon composite mass ratio in solution and step 2 is 18:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
5, by the crystallization thing of step 4 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 520 ℃, roasting 9 hours, makes efficient adsorption composite.
(embodiment 7)
1,0.6 kilogram of Concave-convex clay rod, 0.4 kilogram of sepiolite clay and 2 kilograms of rice husks are placed in mixer, also be that silicate clay and rice husk are 1:2 in mass ratio, stir 10 hours, cross 150 mesh sieves, make Concave-convex clay rod, sepiolite clay and rice husk composite granule;
2, in Concave-convex clay rod, sepiolite clay and the rice husk composite granule of step 1 gained, add the H that 10.7 kilogram-mass percentage concentrations are 40%
3pO
4solution, stirs, and floods 30 hours, after dry, under nitrogen atmosphere, be warming up to 400 ℃, activate 5 hours, naturally cool to room temperature, deionized water cyclic washing by the activation products of gained with 60 ℃, is neutral to filtrate pH value, and washing finishes, dry, pulverizing, make attapulgite/sepiolite/rice hull active carbon composite;
3, to the NaOH solution that adds 3mol/L in attapulgite/sepiolite/rice hull active carbon composite of step 2 gained, wherein the mass ratio of composite and NaOH is 0.6:1, is placed in autoclave, is warming up to 130 ℃, is incubated 17 hours;
4, in the mixed serum of step 3 gained, add NaAlO
2solution, under stirring condition, is warming up to 45 ℃, is incubated 15 hours, wherein NaAlO
2attapulgite/sepiolite in solution and step 2/rice hull active carbon composite mass ratio is 15:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio; ;
5, roasting: by the crystallization thing of step 5 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 560 ℃, roasting 14 hours, makes efficient adsorption composite.
In order to obtain intuitively Data Comparison, can carry out to the efficient adsorption composite making the test of adsorptivity:
Silicate clay and rice husk are after raw material is prepared efficient adsorption composite, composite is carried out to absorption property test: the composite of getting certain mass is placed in three-neck flask, add the certain density organic dyestuff of 500mL or the heavy metal ion aqueous solution, stirring and adsorbing under the condition of 30 ℃, after reaching adsorption equilibrium, centrifugation, gets the remaining concentration (equilibrium concentration) that supernatant is measured organic dyestuff or heavy metal ion.
Composite represents the equilibrium adsorption capacity for adsorption capacity (qv) of organic dyestuff or heavy metal ion, equilibrium adsorption
The volume that V is (L), m is the consumption (g) of sorbing material, the concentration (mgL-1) of organic dyestuff or heavy metal ion in solution before C0, Ce are respectively absorption and while reaching adsorption equilibrium.Result of the test is as shown in table 1.
The equilibrium adsorption capacity of table 1 composite to different pollutants
As can be seen from Table 1, the efficient adsorption composite that silicate clay and rice husk prepared as raw material is take in the present invention has excellent absorption property to organic dyestuff and heavy metal ion.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. take silicate clay and rice husk prepares the method for efficient adsorption composite as raw material, it is characterized in that comprising the following steps:
Step 1: the NaOH solution that adds 1.5-4mol/L in the silicate clay that is 0.2 ~ 3:1 to mass ratio and rice husk, wherein the gross weight of silicate clay and rice husk and the mass ratio of NaOH are 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 2: add NaAlO in the mixed serum of step 1 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 3: by the crystallization thing of step 2 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
2. according to claim 1ly take silicate clay and rice husk and prepare the method for efficient adsorption composite as raw material, it is characterized in that: the silicate clay in described step 1 is one or more in Concave-convex clay rod, montmorillonitic clay, sepiolite clay.
3. take silicate clay and rice husk prepares the method for efficient adsorption composite as raw material, it is characterized in that comprising the following steps:
Step 1: composition silicate clay and rice husk: be that 0.2 ~ 3:1 carries out mechanical agitation and mixes in mass ratio by silicate clay and rice husk, stir 5 ~ 35 hours, through 50 ~ 300 object filter mesh sieves, make silicate clay and rice husk composite granule;
Step 2: to the NaOH solution that adds 1.5-4mol/L in the silicate clay of step 1 gained and the compound split of rice hull active carbon, wherein the mass ratio of composite and NaOH is 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 3: add NaAlO in the mixed serum of step 2 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 4: by the crystallization thing of step 3 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
4. according to claim 3ly take silicate clay and rice husk and prepare the method for efficient adsorption composite as raw material, it is characterized in that: the silicate clay in described step 1 is one or more in Concave-convex clay rod, montmorillonitic clay, sepiolite clay.
5. take silicate clay and rice husk prepares the method for efficient adsorption composite as raw material, it is characterized in that comprising the following steps:
Step 1: the silicate clay that is 0.2 ~ 3:1 to mass ratio and rice husk in to add mass percentage concentration be 20% ~ 75% H
3pO
4solution, stirs, wherein composite granule and pure H
3pO
4mass ratio be 0.6 ~ 1:1, flood after 8 ~ 72 hours, macerate is placed under nitrogen atmosphere, is warming up to 250 ~ 620 ℃, activate 0.5 ~ 7 hour, naturally cool to room temperature, by the activation products of gained deionized water cyclic washing, to filtrate pH value, be neutral, washing finishes, dry, pulverizing, make silicate clay and rice hull active carbon composite;
Step 2: to the NaOH solution that adds 1.5-4mol/L in the silicate clay of step 1 gained and rice hull active carbon composite, wherein the mass ratio of composite and NaOH is 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 3: add NaAlO in the mixed serum of step 2 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 4: by the crystallization thing of step 3 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
6. according to claim 5ly take silicate clay and rice husk and prepare the method for efficient adsorption composite as raw material, it is characterized in that: the silicate clay in described step 1 is one or more in Concave-convex clay rod, montmorillonitic clay, sepiolite clay.
7. take silicate clay and rice husk prepares the method for efficient adsorption composite as raw material, it is characterized in that comprising the following steps:
Step 1: composition silicate clay and rice husk: be that 0.2 ~ 3:1 carries out mechanical agitation and mixes in mass ratio by silicate clay and rice husk, stir 5 ~ 35 hours, through 50 ~ 300 object filter mesh sieves, make silicate clay and rice husk composite granule;
Step 2: phosphoric acid activation: be 20% ~ 75% H to adding mass percentage concentration in the silicate clay of step 1 gained and rice husk composite granule
3pO
4solution, stirs, wherein composite granule and pure H
3pO
4mass ratio be 0.6 ~ 1:1, flood after 8 ~ 72 hours, macerate is placed under nitrogen atmosphere, is warming up to 250 ~ 620 ℃, activate 0.5 ~ 7 hour, naturally cool to room temperature, by the activation products of gained deionized water cyclic washing, to filtrate pH value, be neutral, washing finishes, dry, pulverizing, make silicate clay and rice hull active carbon composite;
Step 3: to the NaOH solution that adds 1.5-4mol/L in the silicate clay of step 2 gained and rice hull active carbon composite, wherein the mass ratio of composite and NaOH is 0.4 ~ 1.2:1, be placed in autoclave, be warming up to 150 ~ 250 ℃, be incubated 10 ~ 24 hours;
Step 4: add NaAlO in the mixed serum of step 3 gained
2solution, under stirring condition, is warming up to 30 ~ 95 ℃, is incubated 4 ~ 25 hours, wherein NaAlO
2silicate clay/rice hull active carbon composite mass ratio in solution and step 2 is 8 ~ 25:1, NaAlO
2solution is by NaAlO
2with deionized water be that 3:10 is formulated in mass ratio;
Step 5: by the crystallization thing of step 4 gained after filtration, washing and dry after, under nitrogen atmosphere, be warming up to 430 ~ 580 ℃, roasting 2 ~ 16 hours, makes efficient adsorption composite.
8. according to claim 7ly take silicate clay and rice husk and prepare the method for efficient adsorption composite as raw material, it is characterized in that: the silicate clay in described step 1 is one or more in Concave-convex clay rod, montmorillonitic clay, sepiolite clay.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947486A (en) * | 2017-04-13 | 2017-07-14 | 常州纳欧新材料科技有限公司 | A kind of attapulgite activated carbon from activated sludge soil remediation material and preparation method thereof |
| CN107876008A (en) * | 2017-10-20 | 2018-04-06 | 福建省农业科学院农业生态研究所 | A kind of fen adsorbent, preparation method and applications |
| CN109046341A (en) * | 2018-08-28 | 2018-12-21 | 中国科学院兰州化学物理研究所 | A kind of preparation method of visible light-responded silver silicate/concave convex rod composite catalyst |
| CN109305685A (en) * | 2017-07-26 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of preparation and application of Si-Al molecular sieve, the molecular sieve |
| CN110314639A (en) * | 2019-07-11 | 2019-10-11 | 沈阳理工大学 | A kind of modified birnessite and its preparation method and application |
| WO2021238083A1 (en) * | 2020-05-27 | 2021-12-02 | 常州大学 | Method for preparing silicate/carbon composite by using attapulgite, and application of material |
| CN117024088A (en) * | 2023-07-25 | 2023-11-10 | 桐庐鼎力建材有限公司 | High-corrosion-resistance concrete and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114280A (en) * | 1996-05-06 | 2000-09-05 | Agritec, Inc. | Highly activated carbon from caustic digestion of rice hull ash and method |
| CN102145280A (en) * | 2011-02-15 | 2011-08-10 | 常州大学 | Method for preparing rice hull active carbon/silicon dioxide/titanium dioxide composite material |
| CN102861554A (en) * | 2012-08-28 | 2013-01-09 | 常州大学 | Composite adsorbing material for removing copper ions in natural water body and preparation method of composite adsorbing material |
-
2013
- 2013-01-16 CN CN201310016366.3A patent/CN103920459B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114280A (en) * | 1996-05-06 | 2000-09-05 | Agritec, Inc. | Highly activated carbon from caustic digestion of rice hull ash and method |
| CN102145280A (en) * | 2011-02-15 | 2011-08-10 | 常州大学 | Method for preparing rice hull active carbon/silicon dioxide/titanium dioxide composite material |
| CN102861554A (en) * | 2012-08-28 | 2013-01-09 | 常州大学 | Composite adsorbing material for removing copper ions in natural water body and preparation method of composite adsorbing material |
Non-Patent Citations (3)
| Title |
|---|
| YANPING GUO等: "Activated carbons prepared from rice hull by one-step phosphoric acid activation", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 秦泽勇等: "凹凸棒石/稻壳活性炭复合材料的制备及对阳离子黄X-GL的吸附性能", 《非金属矿》 * |
| 陈正行等: "稻壳灰同时制备脱色剂和水玻璃的研究", 《林产化学与工业》 * |
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| CN106947486B (en) * | 2017-04-13 | 2019-10-01 | 常州纳欧新材料科技有限公司 | A kind of attapulgite-activated carbon from activated sludge soil remediation material and preparation method thereof |
| CN109305685A (en) * | 2017-07-26 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of preparation and application of Si-Al molecular sieve, the molecular sieve |
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| CN110314639A (en) * | 2019-07-11 | 2019-10-11 | 沈阳理工大学 | A kind of modified birnessite and its preparation method and application |
| CN110314639B (en) * | 2019-07-11 | 2022-03-11 | 沈阳理工大学 | Modified birnessite and preparation method and application thereof |
| WO2021238083A1 (en) * | 2020-05-27 | 2021-12-02 | 常州大学 | Method for preparing silicate/carbon composite by using attapulgite, and application of material |
| US11623210B2 (en) | 2020-05-27 | 2023-04-11 | Changzhou University | Method for preparing silicate/carbon composite from attapulgite, and use of silicate/carbon composite |
| CN117024088A (en) * | 2023-07-25 | 2023-11-10 | 桐庐鼎力建材有限公司 | High-corrosion-resistance concrete and preparation method thereof |
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