CN101564676B - Compound bentonite for removing fluorine from water and preparation method thereof - Google Patents
Compound bentonite for removing fluorine from water and preparation method thereof Download PDFInfo
- Publication number
- CN101564676B CN101564676B CN2009100683498A CN200910068349A CN101564676B CN 101564676 B CN101564676 B CN 101564676B CN 2009100683498 A CN2009100683498 A CN 2009100683498A CN 200910068349 A CN200910068349 A CN 200910068349A CN 101564676 B CN101564676 B CN 101564676B
- Authority
- CN
- China
- Prior art keywords
- bentonite
- water
- calcium
- base bentonite
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to compound bentonite for removing fluorine from water and a preparation method thereof, which relates to the water treating field by the absorption method. The compound bentonite consists of calcium-based bentonite and polyacry lamide which is polymerized on the calcium-based bentonite, wherein the polyacry lamide accounts for 10 wt percent-25 wt percent of the total mass percentage and the calcium-based bentonite 75 wt percent-90 wt percent thereof. The polyacry lamide is formed by the solution polymerization of acrylamide monomer acted by polymerization initiator zaodiisobutyronitrile and cross linker formaldehyde. The invention overcomes the weaknesses such as the high price and low absorption property of the absorbing materials removing fluorine from water in prior art and simultaneously overcomes the weaknesses that the existing polyacry lamide/bentonite compound is used only as water absorbent and furthermore the bentonite content is not higher than 70%.
Description
Technical field
Technical scheme of the present invention relates to the technical field of handling water with absorption method, specifically is used for from composite bentonite of removing fluor in water and preparation method thereof.
Background technology
Fluorine element is one of trace element of needed by human, easily suffers from dental caries when fluorine contains quantity not sufficient in the drinking water; But if the long-term drinking high-fluorine water, cause then that gently tooth is rotten, enamel comes off, and is heavy then cause osteosclerosis or osteoporosis, textured bone, even paralyse, make people's disability.China is one of drinking water type endemic fluorosis the widest popular, the most serious country of harm in the world.Stipulate in the Drinking Water in China standard that fluorine content suitable in the drinking water is 0.5～1.0mg/L; According to national wastewater discharge standard, fluoride must be less than 15mg/L in the waste water that requires to discharge again.At the present situation of fluorine ion severe overweight in Drinking Water in China and the industrial wastewater, the research and development that remove fluorine reagent, defluorination method and fluoride-removing equipment become a focus in the water treatment.The method of removal of fluorine from water is a lot of at present, and its pluses and minuses are respectively arranged: though 1. ion-exchange is commonly used, because the anion exchange order is SO
4 2-＞NO
3 -＞CrO
4 2-＞Br
-＞CN
-＞Cl
-＞F
-, fluorine ion is in the position of unfavorable exchange, and selectivity is not high, and equipment investment and operating cost are very big; 2. hyperfiltration power consumption is big, the expense height; 3. aluminium salt precipitation method effect is better, but the consumption of aluminium salt is big, can not regenerate, and produce a large amount of precipitations; 4. electrocoagulation facility compact, effluent quality are good, but power consumption is big, and higher to water quality requirement; 5. the absorption method defluorination effect is good, and regeneration is easy, and sorbing material consumption is few, and chaff interference is few.Be used in the prior art mostly being bone carbon and activated alumina from the sorbing material of removing fluor in water, its shortcoming is the material price height, and absorption property remains further to be improved.To develop adsorption effect higher for this reason, and economical and practical sorbing material, will be the reasonable approach that removal of fluorine from water is promoted, and have remarkable social benefit and economic benefit.
Bentonite is big at China's reserves, use very extensive, its specific area is big, the heat endurance height, absorption property is good, is a kind of environmental protection adsorbent of potential efficient cheapness, but bentonite also exist swellability big, be difficult to shortcoming such as sedimentation, be to solve the problem of practical application, prepare that a kind of adsorption effect is higher, settling property good and cheap bentonite water purification agent becomes the focus of research.In the prior art, acrylamide and bentonitic compound are almost all developed as a kind of high water absorption composite material, and the preparation method of this composite mainly contains solution polymerization process, inverse suspension polymerization method, radiation polymerization.1. solution polymerization process is meant reaction monomers and initator etc. is dissolved in the appropriate solvent and the polymerization that carries out (Ji Hong gradually waited in " containing in the research of bentonitic partial hydrolysis cross-linked polyacrylamide super absorbent resin ").The conversion ratio of this preparation method's monomer is low, and polymerization speed is slow; The dry difficulty of product; Easily forming block gel in the reactor is difficult to handle; 2. the inverse suspension polymerization method is to be decentralized medium with the organic solvent, and water-soluble monomer is dispersed into suspension water drop under suspending agent and strong agitation effect, and initator is dissolved in the water drop and the polymerization that carries out.(Zhang Xiaohong etc. are in " the synthetic and performance of Sodium Polyacrylate/montmorillonite composite high-water uptake resin ", and CN1769191 is used for bentonite base composite material of water treatment and preparation method thereof).Its disadvantage is a complex technical process, and the post processing of product is difficulty, must remove low molecular reaction thing and the solvent of being carried secretly in the product, will reclaim a large amount of decentralized media simultaneously.3. radiation-initiated polymerization method is to use the method (Li Hong etc. are in " research of super water-absorbent polyacrylamide/montmorillonite composite material mechanical property ") of gamma-radiation or the copolyreaction of ultraviolet light irradiation initiation grafting.But because side reaction for the poor selectivity of chemical reaction, takes place, thereby has limited the range of application of this method in x radiation x energy height easily.
In sum, in water treatment field, existing polyacrylamide/bentonite compound only is used to do water absorbing agent, its water absorption rate descends rapidly along with the increase of bentonite content in the compound, bentonitic content is the highest at 20% o'clock its water absorption rate, and when bentonitic content was 55% left and right sides, its water absorption rate was near substantially minimum, therefore as a kind of super absorbent resin, be applied to that bentonitic content is not higher than 70% in the composite of water absorbing agent.At present, yet there are no polyacrylamide/bentonite material is used for from the report of removing fluor in water and otherwise prior art.
Summary of the invention
Technical problem to be solved by this invention is: be provided for from composite bentonite of removing fluor in water and preparation method thereof, in order to overcome the lower shortcoming of price height, absorption property that is used in the prior art from the sorbing material of removing fluor in water, simultaneously overcome existing polyacrylamide/bentonite compound yet and only be used to do water absorbing agent, and wherein bentonitic content is not higher than 70% shortcoming.
The present invention solves this technical problem the technical scheme that is adopted: be used for the composite bentonite from removing fluor in water, constitute by calcium-base bentonite and the polymerization polyacrylamide on it, wherein the mass percent of the shared integral body of polyacrylamide is 10%～25%, the mass percent of the shared integral body of calcium-base bentonite is 75%～90%, and said here polyacrylamide is to carry out solution polymerization by acrylamide monomer under the effect of initator azodiisobutyronitrile and crosslinking agent formaldehyde to generate.
Above-mentioned being used for from the preparation method of the composite bentonite of removing fluor in water, its step is as follows:
The first step, the preparation of purification calcium-base bentonite
Calcium-base bentonite breeze and running water is reinforced by 1: 6～7 mass ratio, stirred 20～40 minutes, left standstill 20～30 hours, stirred then 10～20 minutes, add running water again or add the supernatant that took out when preparing last time when repeating to prepare, being mixed with mass ratio is the calcium-base bentonite breeze: the feed liquid of water=1: 9～11, continue to stir 9～11 minutes, standing sedimentation is 3～5 hours again, takes out supernatant and is used further to preparation next time feed liquid, takes out the smart soil in upper strata from precipitum, should essence soil temperature in baking oven descend dry for 100 ℃, till the quality of this essence soil remains unchanged, pulverize then, cross 200 mesh sieves and make the purification calcium-base bentonite;
Second step, solution polymerization
According to actual needs, take by weighing the purification calcium-base bentonite and the acrylamide monomer that make by the first step respectively, be dissolved in the deionized water after the mixing, the ratio that is mixed with quality is the purification calcium-base bentonite: acrylamide monomer: the mixed solution of deionized water=1: 0.1～0.35: 2.7～3.8, at room temperature stirred 1～2 hour, be warming up to 60～80 ℃ after mixing, be incorporated as the initator azodiisobutyronitrile of used acrylamide monomer quality 0.16%～1.56% again and be the crosslinking agent formalin of used acrylamide monomer quality 9.25%～28%, this formalin is that reagent is pure, wherein the mass fraction of formaldehyde is 37%～40%, continue to stir, become sticky thick gradually and polymerization is solidified to this mixed solution, reaction finishes, keep 60～80 ℃ of constant temperature then, from being warming up to reaction time of stopping of reaction is 1.5～2.5 hours, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa～1.01 * 10
5Pa, temperature is under 50～70 ℃ of conditions, dry 4～6 hours, take out dry solid matter, get 30～100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%～25%, and the mass percent of the shared integral body of purification calcium-base bentonite is 75%～90%.
Above-mentioned being used for from the preparation method of the composite bentonite of removing fluor in water, used acrylamide monomer is the commercial goods, and calcium-base bentonite is common commercially available calcium-base bentonite, and stirring and pulverizing are general chemical process.
Beneficial effect of the present invention is:
That the present invention is used for is big at the bentonite swellability from composite bentonite of removing fluor in water and preparation method thereof, be difficult to Separation of Solid and Liquid and the low problem of defluorination ability, with the calcium-base bentonite is that main body and less acrylamide are carried out solution polymerization under the effect of initator azodiisobutyronitrile and crosslinking agent formaldehyde, thereby makes the polyacrylamide/bentonite composite material product that is used for from removing fluor in water.Compared with prior art, its advantage is:
(1) the present invention is used for from the composite bentonite product of the removing fluor in water absorption property to fluorine ion, be better than existing natural montmorillonite, remodeling bentonite and clinoptilolite, suitable with the active alundum (Al of tradition, bentonitic content is higher than 70% in this product, be higher than the report in the existing document, this product does not have the swelling row and settling property good (leaving standstill basic all sedimentations about 1 minute).Compare with the preparation technology of common pillared bentonite, active alundum (Al and bone black, the present invention is used for from the composite bentonite preparation method's of removing fluor in water synthesis step few, handling safety, easy to control, energy consumption is little, and manufacturing cycle is short, cost of material is cheap and be easy to get, and production cost is low.
(2) the present invention is used for adopting water solution polymerization process from the preparation method of the composite bentonite of removing fluor in water, gradually wait people's existing synthetic method with respect to Ji Hong, the inventive method does not need to add alkali lye and be hydrolyzed, and the content of calcium-base bentonite is higher in the product, thus overcome Ji Hong gradually wait people's development as the strongly hydrophilic of the acrylamide of suction and the compound existence of calcium-base bentonite and swellability, problem that the defluorination ability is low.
(3) from architectural feature, compare with existing Powdered bentonite goods, it is shaped granule shape structure that the present invention is used for from the composite bentonite product of removing fluor in water, can separate voluntarily with handled solution, be convenient to practical application in industry, also be convenient to recycling.
Embodiment in the following specific embodiment and table 1 data and analysis thereof have further proved beneficial effect of the present invention.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is the XRF diffraction pattern of purification calcium-base bentonite among the embodiment 1.
Fig. 2 is the sem photograph of purification calcium-base bentonite among the embodiment 1.
Fig. 3 is the XRF diffraction pattern of composite bentonite product among the embodiment 3.
Fig. 4 is the sem photograph of composite bentonite product among the embodiment 3.
The specific embodiment
The first step, the preparation of purification calcium-base bentonite
Commercially available calcium-base bentonite breeze and running water is reinforced by 1: 6～7 mass ratio, stirred 20～40 minutes, left standstill 20～30 hours, stirred then 10～20 minutes, add running water again or add the supernatant that took out when preparing last time when repeating to prepare, being mixed with mass ratio is the calcium-base bentonite breeze: the feed liquid of water=1: 9～11, continue to stir 9～11 minutes, standing sedimentation is 3～5 hours again, takes out supernatant and is used further to preparation next time feed liquid, takes out the smart soil in upper strata from precipitum, should essence soil in baking oven 100 ℃ dry down, till the quality of this essence soil remains unchanged, pulverize then, cross 200 mesh sieves and make the purification calcium-base bentonite;
Fig. 1 is the XRF diffraction pattern of purification calcium-base bentonite, by the characteristic peak calculating d of figure
(001)Thereby, determine that the bentonite type is a calcium-base bentonite.
Fig. 2 is the sem photograph of purification calcium-base bentonite, and it shows that original soil is a layered porous road structure, has bigger specific area.
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 6.00g and the commercially available monomer acrylamide 2.00g that make by the first step respectively, be dissolved in after the mixing in the 20mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 1.5 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 6 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 25%, and the mass percent of the shared integral body of purification calcium-base bentonite is 75%.
The prepared product of present embodiment is the sample 1 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 2
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 8.00g and the commercially available monomer acrylamide 2.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 4 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 20%, and the mass percent of the shared integral body of purification calcium-base bentonite is 80%.
The prepared product of present embodiment is the sample 2 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 3
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2.5 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 3 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Fig. 3 is used for for present embodiment makes from the XRF diffraction pattern of the composite bentonite product of removing fluor in water.
Fig. 4 is used for for present embodiment makes from the sem photograph of the composite bentonite product of removing fluor in water, and it shows that product is the mesh structural porous road of a particle structure, has bigger specific area.
Embodiment 4
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0032g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2.5 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 4 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 5
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0156g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2.5 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 5 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 6
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.30g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 1.5 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 50 ℃ of conditions, dry 6 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 6 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 7
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.70g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa, temperature is under 70 ℃ of conditions, dry 4 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 7 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 8
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 60 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 60 ℃ of constant temperature then, is 2 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 1.01 * 10 in vacuum
5Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 8 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 9
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 80 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 80 ℃ of constant temperature then, is 1.5 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 9.85 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 9 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 9.85 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 30～40 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 10 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 11
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 9.85 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 40～60 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 11 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Embodiment 12
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, solution polymerization
Take by weighing the purification calcium-base bentonite 9.00g and the commercially available monomer acrylamide 1.00g that make by the first step respectively, be dissolved in after the mixing in the 25mL deionized water, the preparation mixed solution, at room temperature stirred 1 hour, be warming up to 70 ℃ after mixing, the back adds 0.0096g initator azodiisobutyronitrile and 0.50g crosslinking agent formalin, continue to stir, become sticky thick gradually and polymerization is solidified to solution, reaction finishes, keeping 70 ℃ of constant temperature then, is 2 hours from being warming up to reaction time of stopping of reaction, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 9.85 * 10 in vacuum
4Pa, temperature is under 60 ℃ of conditions, dry 5 hours, take out dry solid matter, get 60～80 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%, and the mass percent of the shared integral body of purification calcium-base bentonite is 90%.
The prepared product of present embodiment is the sample 12 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Comparative Examples 1
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, Acidic Bentonite synthetic
Get the purification calcium-base bentonite 5.00g that makes by the first step, add 150mL, the HCl of 0.05moL/L, reaction is after 6 hours in 60 ℃ of waters bath with thermostatic control, and washing is to there not being Cl
-, vacuum filtration separates solid phase in 105 ℃ of oven dry down, grinds 200 mesh sieves and gets Acidic Bentonite.
The prepared product of present embodiment is the Comparative Examples 1 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Comparative Examples 2
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, sodium bentonite synthetic
Get the purification calcium-base bentonite 15.00g that makes by the first step, add 450mL, the NaCl of 0.15mol/L, reaction is after 2 hours in 80 ℃ of waters bath with thermostatic control, and washing is to there not being Cl
-, vacuum filtration separates solid phase in 105 ℃ of oven dry down, grinds 200 mesh sieves and gets sodium bentonite.
The prepared product of present embodiment is the Comparative Examples 2 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
Comparative Examples 3
The first step, the preparation of purification calcium-base bentonite
With embodiment 1 first step;
Second step, sodium bentonite synthetic
Get the purification calcium-base bentonite 30.00g that makes by the first step, add 900mL, the NaCl of 0.15mol/L, reaction is after 2 hours in 80 ℃ of waters bath with thermostatic control, and washing is to there not being Cl
-, vacuum filtration separates solid phase in 105 ℃ of oven dry down, grinds 200 mesh sieves and gets sodium bentonite.
In the 3rd step, bentonite is synthetic
Take by weighing the sodium bentonite that second step of 2.00g softex kw (CTMAB) and 15.00g makes, be dissolved in the ethanolic solution of 150mL10%, after the reaction hour, washing is to there not being Br in 70 ℃ of waters bath with thermostatic control
-, vacuum filtration separates solid phase 80 ℃ of oven dry down, grinds 100 mesh sieves and gets organobentonite.
The prepared product of present embodiment is the Comparative Examples 3 in the table 1, and its absorption switching performance to fluorine ion, monoxone and lead ion in the aqueous solution is listed in the table 1.
To be reagent pure for used formalin in the foregoing description, and wherein the mass fraction of formaldehyde is 37%～40%.
Below F in the table 1
-The assay method of adsorbance: under the situation of room temperature, laboratory apparatus is a WL-15A type microprocessor ionometer, pipettes C
F-=3.9809mg/L 40mL adds 10mL cushioning liquid then, and the composite bentonite quality that adds different samples again is about 0.5g, adsorbs up to balance, obtains the experimental data in the table 1.Wherein total ion concentration is as follows in the cushioning liquid: sodium chloride 0.1mol/L, and acetic acid 0.25mol/L, sodium acetate 0.75mol/L, natrium citricum 0.001mol/L, pH are 5.0, the total ionic strength adjustment buffer degree is 1.75.
Below the assay method of monoxone and lead ion adsorbance in the table 1: pipette 0.0104mol/L solution, the composite bentonite quality that adds different samples is about 0.5g, adsorbs up to balance, obtains the experimental data in the table 1.
According to data in the table 1 as can be known, the F that is used for composite bentonite product (sample 1～12 of table 1) that the present invention makes from removing fluor in water
-The adsorbance of ion all is higher than the Acidic Bentonite (0.1940mg/g) of Comparative Examples 1, the sodium bentonite (0.1817mg/g) of Comparative Examples 2 and the organobentonite (0.2186mg/g) of Comparative Examples 3, and wherein the adsorbance of sample 3 is the highest, is 0.2963mg/g.The present invention makes is used for not only fluorine ion being had higher adsorptivity from the composite bentonite of removing fluor in water, simultaneously monoxone and lead ion also had good adsorptivity, from the optimized angle analysis of engineering, by to adsorption capacity, the cost of product with separate complexity etc. the aspect is comprehensive and relatively can select more excellent product, the present invention makes is used for from the porous network structure characteristic of the composite bentonite of removing fluor in water metal ion and organic matter also being had bigger absorption potential quality, makes it to become a kind of multipurpose water purification agent of high-efficiency and economic.
Table 1 composite bentonite is to F
-, monoxone and lead ion absorption property
| Sample | F -The equilibrium concentration mg/L of ion | F -The adsorbance mg/g of ion | Chloroacetic equilibrium concentration mol/L | Chloroacetic adsorbance mg/g | The equilibrium concentration mol/L of lead ion | The adsorbance mg/g of |
| Sample | ||||||
| 1 | 0.7197 | 0.2465 | 0.004478 | 55.37 | 0.007504 | 60.00 |
| Sample 2 | 0.4897 | 0.2695 | 0.003907 | 60.64 | 0.007401 | 62.13 |
| Sample 3 | 0.2217 | 0.2963 | 0.002373 | 75.05 | 0.007286 | 64.52 |
| Sample 4 | 0.6607 | 0.2524 | 0.004519 | 54.99 | 0.007511 | 59.85 |
| Sample 5 | 0.6587 | 0.2526 | 0.004219 | 57.79 | 0.007628 | 57.43 |
| Sample 6 | 0.7047 | 0.2480 | 0.004389 | 56.02 | 0.007334 | 63.52 |
| Sample 7 | 0.3877 | 0.2797 | 0.004489 | 55.27 | 0.007667 | 54.55 |
| Sample 8 | 0.5717 | 0.2613 | 0.004655 | 53.72 | 0.007754 | 54.82 |
| Sample 9 | 0.9417 | 0.2243 | 0.004821 | 52.16 | 0.007743 | 55.05 |
| |
0.8597 | 0.2325 | 0.004617 | 54.07 | 0.007646 | 57.07 |
| Sample 11 | 0.7477 | 0.2437 | 0.004339 | 56.67 | 0.007513 | 59.81 |
| Sample 12 | 0.6477 | 0.2537 | 0.004091 | 58.99 | 0.007395 | 62.26 |
| Comparative Examples 1 | 1.2447 | 0.1940 | 0.005575 | 45.11 | 0.008102 | 47.61 |
| Comparative Examples 2 | 1.3677 | 0.1817 | 0.005881 | 42.25 | 0.008248 | 44.59 |
| Comparative Examples 3 | 0.9997 | 0.2185 | 0.004966 | 50.81 | 0.007812 | 53.62 |
Claims (2)
1. be used for composite bentonite from removing fluor in water, it is characterized in that: constitute by calcium-base bentonite and the polymerization polyacrylamide on it, wherein the mass percent of the shared integral body of polyacrylamide is 10%～25%, the mass percent of the shared integral body of calcium-base bentonite is 75%～90%, and said here polyacrylamide is to carry out solution polymerization by acrylamide monomer under the effect of initator azodiisobutyronitrile and crosslinking agent formaldehyde to generate.
2. be used for from the preparation method of the composite bentonite of removing fluor in water, it is characterized in that its step is as follows:
The first step, the preparation of purification calcium-base bentonite
Calcium-base bentonite breeze and running water is reinforced by 1: 6～7 mass ratio, stirred 20～40 minutes, left standstill 20～30 hours, stirred then 10～20 minutes, add running water again or add the supernatant that took out when preparing last time when repeating to prepare, being mixed with mass ratio is the calcium-base bentonite breeze: the feed liquid of water=1: 9～11, continue to stir 9～11 minutes, standing sedimentation is 3～5 hours again, takes out supernatant and is used further to preparation next time feed liquid, takes out the smart soil in upper strata from precipitum, should essence soil temperature in baking oven descend dry for 100 ℃, till the quality of this essence soil remains unchanged, pulverize then, cross 200 mesh sieves and make the purification calcium-base bentonite;
Second step, solution polymerization
According to actual needs, take by weighing the purification calcium-base bentonite and the acrylamide monomer that make by the first step respectively, be dissolved in the deionized water after the mixing, the ratio that is mixed with quality is the purification calcium-base bentonite: acrylamide monomer: the mixed solution of deionized water=1: 0.1～0.35: 2.7～3.8, at room temperature stirred 1～2 hour, be warming up to 60～80 ℃ after mixing, be incorporated as the initator azodiisobutyronitrile of used acrylamide monomer quality 0.16%～1.56% again and be the crosslinking agent formalin of used acrylamide monomer quality 9.25%～28%, this formalin is that reagent is pure, wherein the mass fraction of formaldehyde is 37%～40%, continue to stir, become sticky thick gradually and polymerization is solidified to this mixed solution, reaction finishes, keep 60～80 ℃ of constant temperature then, from being warming up to reaction time of stopping of reaction is 1.5～2.5 hours, the wet solid thing phase product that makes;
In the 3rd step, vacuum drying makes the composite bentonite product that is used for from removing fluor in water
The wet solid thing phase product that second step was made places vacuum drying chamber, is 8.64 * 10 in vacuum
4Pa～1.01 * 10
5Pa, temperature is under 50～70 ℃ of conditions, dry 4～6 hours, take out dry solid matter, get 30～100 purpose granular products behind the crushing screening, promptly make the composite bentonite product that is used for from removing fluor in water, wherein the mass percent of the shared integral body of polyacrylamide is 10%～25%, and the mass percent of the shared integral body of purification calcium-base bentonite is 75%～90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100683498A CN101564676B (en) | 2009-04-03 | 2009-04-03 | Compound bentonite for removing fluorine from water and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100683498A CN101564676B (en) | 2009-04-03 | 2009-04-03 | Compound bentonite for removing fluorine from water and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101564676A CN101564676A (en) | 2009-10-28 |
| CN101564676B true CN101564676B (en) | 2011-04-20 |
Family
ID=41281143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100683498A Expired - Fee Related CN101564676B (en) | 2009-04-03 | 2009-04-03 | Compound bentonite for removing fluorine from water and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101564676B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102371146B (en) * | 2010-08-12 | 2013-09-04 | 北京林业大学 | Forming method of efficient composite type electrical fluoride removing adsorbent |
| CN102513056A (en) * | 2011-12-20 | 2012-06-27 | 江苏四方锅炉有限公司 | Preparation method of absorbent used for removing mercury vapor pollutant |
| CN102580697B (en) * | 2012-02-21 | 2014-02-05 | 河北工业大学 | Sodium bentonite-AM-AA composite lead ion absorbing agent |
| CN104353436A (en) * | 2014-11-05 | 2015-02-18 | 朱忠良 | Method for preparing modified bentonite for removing sulfide in fume |
| CN104773784B (en) * | 2015-04-28 | 2017-04-26 | 阳原县仁恒精细粘土有限责任公司 | Printing and dyeing wastewater treatment agent |
| CN104828917B (en) * | 2015-04-28 | 2017-11-07 | 浙江长安仁恒科技股份有限公司 | A kind of Multifunctional waste liquid inorganic agent and its application |
| CN105214444A (en) * | 2015-11-13 | 2016-01-06 | 无锡清杨机械制造有限公司 | A kind of pressure swing adsorption method reclaims the method for toluene in tail gas |
| CN110129561B (en) * | 2019-05-20 | 2020-11-24 | 中南大学 | Method for removing fluorine in lepidolite neutral leaching solution by using modified bentonite adsorbent |
| CN112110563B (en) * | 2020-08-17 | 2023-07-25 | 江苏开放大学（江苏城市职业学院） | Method for treating sewage and sludge from chrome tanning |
| CN112273244A (en) * | 2020-10-28 | 2021-01-29 | 上海耐威克宠物用品有限公司 | Bentonite cat litter and preparation method thereof |
-
2009
- 2009-04-03 CN CN2009100683498A patent/CN101564676B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101564676A (en) | 2009-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101564676B (en) | Compound bentonite for removing fluorine from water and preparation method thereof | |
| He et al. | Review of fluoride removal from water environment by adsorption | |
| Wang et al. | Fast removal of copper ions from aqueous solution by chitosan-g-poly (acrylic acid)/attapulgite composites | |
| US6146539A (en) | Treatment of swimming pool water | |
| Dhillon et al. | Recent advances and spectroscopic perspectives in fluoride removal | |
| CN105214612A (en) | A kind of application of metal-organic framework functionalization material | |
| Zhang et al. | Removal of Cd (II) by modified maifanite coated with Mg-layered double hydroxides in constructed rapid infiltration systems | |
| CN106423045B (en) | A kind of modified montmorillonoid sorbent preparation method of Treatment of Zinc-containing Wastewater | |
| CN101234792B (en) | Method for removing fluorine ion from water by using oxide of lanthanum-carried aluminum oxide | |
| CN103253788B (en) | Method for removing fluorides in water through aluminum base composite metal oxide-based fluorine removing absorption material complexation-absorption | |
| CN104353436A (en) | Method for preparing modified bentonite for removing sulfide in fume | |
| CN111530427A (en) | Resin-based hybrid material modified based on zirconium-based metal organic framework and application thereof | |
| Jung et al. | Entrapment of powdered drinking water treatment residues in calcium-alginate beads for fluoride removal from actual industrial wastewater | |
| CN103223327A (en) | Preparation method and applications of synchronous nitrogen and phosphorus absorption agent | |
| CN108970589B (en) | Hydrotalcite-based composite gel ball and preparation method and application thereof | |
| CN102580697B (en) | Sodium bentonite-AM-AA composite lead ion absorbing agent | |
| Naghizadeh et al. | Synthesis of nanochitosan for the removal of fluoride from aqueous solutions: a study of isotherms, kinetics, and thermodynamics. | |
| S Dragan et al. | Progress in polysaccharide/zeolites and polysaccharide hydrogel composite sorbents and their applications in removal of heavy metal ions and dyes | |
| Zhang et al. | Defluorination and regeneration study of lanthanum-doped sewage sludge-based activated carbon | |
| CN103055824B (en) | Calcium bentonite -AA- (AA-Na) composite cadmium ion adsorbent | |
| Zeng et al. | The model and mechanism of adsorptive technologies for wastewater containing fluoride: A review | |
| CN110105486A (en) | A kind of electric conductivity aluminium based lithium-ion adsorption column material and preparation method thereof | |
| CN104229966B (en) | A kind of magnetic collagen aleurone modified cation flocculation agent and preparation method thereof | |
| CN1817438A (en) | Production of sewage dephosphor adsorbent by adsorptive ion rare earth | |
| CN1270820C (en) | Collagen fiber solid borne metallic ion adsorbing material, preparation method and purpose thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110420 Termination date: 20150403 |
|
| EXPY | Termination of patent right or utility model |