CN102451662A - High-efficiency fluorine-removing adsorbent and preparation method thereof - Google Patents
High-efficiency fluorine-removing adsorbent and preparation method thereof Download PDFInfo
- Publication number
- CN102451662A CN102451662A CN2011102868778A CN201110286877A CN102451662A CN 102451662 A CN102451662 A CN 102451662A CN 2011102868778 A CN2011102868778 A CN 2011102868778A CN 201110286877 A CN201110286877 A CN 201110286877A CN 102451662 A CN102451662 A CN 102451662A
- Authority
- CN
- China
- Prior art keywords
- siderite
- adsorbent
- powder
- natural
- fluorine
- 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.)
- Pending
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a high-efficiency fluorine-removing adsorbent and a preparation method thereof. The preparation method comprises steps that: step S102, natural siderite powder is selected; step S104, proper amounts of deionized water, aluminum salt, and an adhesive are added to the selected natural siderite powder, such that a mixed dope is obtained; step S106, wet extrusion granulation is carried out upon the obtained mixed dope; and step S108, granules obtained through the wet extrusion granulation process is calcined. According to the invention, the granular fluorine-removing adsorbent is formed through wet extrusion granulation and calcining. The adsorbent is used in rural areas with undeveloped economy. Because the structure and mineral components of the siderite are changed, the fluorine removing effect is further improved.
Description
Technical field
The invention belongs to water-treatment technology field, particularly a kind of preparation method of de-fluoridation adsorbent and de-fluoridation adsorbent.
Background technology
Fluorine is as the requisite trace element of a kind of human body, and an amount of fluorine not only can take care of one's teeth, and the formation and the metabolism of bone all played an important role, but long-term excessive absorption fluorine then is prone to cause dental fluorosis, fluorosis of bone, meat fiber to degenerate, even cancer.In world health organization's regulation drinking water fluorine content on be limited to 1.5 mg.L-1.Stipulate in the Drinking Water in China sanitary standard that fluorine content should surpass this value and be high-fluorine water less than 1.0 mg.L-1 in the drinking water.
At present, the high-fluorine water purification method mainly contains absorption method, the precipitation method, membrane separation process, electrocoagulation, ion-exchange etc., but because adsorbent is with low cost, the advantage that conveniently is easy to get etc., makes absorption method become and purify high-fluorine water method the most commonly used.Adsorbent commonly used has activated alumina, zeolite, bone black etc.There are some researches show that arsenic has effect preferably to siderite in the water to removing, but utilizes siderite defluorination few people research.For this reason, proposed to utilize the method for aluminum salt modified natural siderite powder as de-fluoridation adsorbent, think research high-quality, defluorination material provides theoretical foundation efficiently.
Summary of the invention
The preparation method and the de-fluoridation adsorbent that the purpose of this invention is to provide a kind of de-fluoridation adsorbent have the problem of certain restriction with the de-fluoridation adsorbent that solves in the correlation technique on defluorination effect.
In order to realize it being above-mentioned purpose, according to an aspect of the present invention, a kind of preparation method of de-fluoridation adsorbent is provided, it comprises: step S102, choose natural siderite powder; Step S104 in selected natural siderite powder, adds proper amount of deionized water, aluminium salt and an amount of adhesive, obtains mixing dope; Step S106 carries out the wet method extruder grain to resulting mixing dope; Step S108 calcines the particle that is obtained by the wet method extruder grain.
Further, above-mentioned steps S108 comprises: in Muffle furnace, adopt 450 ℃ temperature that the particle that is obtained by said wet method extruder grain was calcined 3 hours.
Further, above-mentioned steps S102 comprises: said natural siderite is ground into the powder of granularity less than 0.10 mm.
Further, among the above-mentioned steps S106, obtain the particle that granularity is 3-4 mm through the wet method extruder grain.
Further, the binding agent that is added among the above-mentioned steps S104 is the 54.9%-61.9% of said mixing dope gross weight.
Further, above-mentioned aluminium salt is aluminum sulfate, and binding agent is that solid-to-liquid ratio is 25% aluminium colloidal sol.
Further, among the above-mentioned steps S104, the weight ratio of said deionized water and said natural siderite powder is: 1:50-1:25.
Further, among the above-mentioned steps S102, the content of siderite is 85.6% of total content in the natural siderite of choosing.
In order to realize it being above-mentioned purpose, according to another aspect of the present invention, a kind of de-fluoridation adsorbent is provided, it is prepared by above-mentioned a kind of of natural siderite method of modifying who is used for strengthening defluorination.
Further, contain 85.6% siderite in the above-mentioned arsenic-removing adsorption agent at least, 5.5% clay mineral.
The present invention has following beneficial effect:
1) through aluminum salt modified natural siderite powder is carried out wet method extruder grain and calcining, make the lattice of natural siderite that variation take place, and some natural siderite changes into bloodstone, thereby generated de-fluoridation adsorbent.Because the present invention adopts a kind of raw material (being natural siderite) to realize the preparation of high-efficiency defluorinating adsorbent, thereby has simplified preparation technology.In addition, because calcination processing makes the structure of siderite and bloodstone that change take place, thereby has improved defluorination effect.
2) because de-fluoridation adsorbent is graininess, makes the user easily arsenic-removing adsorption agent to be placed in the filter (cylindrical reactor) high-fluorine water is filtered, not only easy to use, and be convenient to the material absorption activating and regenerating after saturated.
Description of drawings
Fig. 1 is the flow chart according to the preparation method of the de-fluoridation adsorbent of the embodiment of the invention.Fig. 2 is the X-ray diffraction analysis spectrogram according to adsorbent after the natural siderite former state of the embodiment of the invention and the modification, wherein the unmodified natural siderite particle of 1 representative; The modified natural siderite particle of aluminium salt binding agent is not added in 2 representatives; The modified natural siderite particle of aluminium salt binding agent is added in 3 representatives.
This section deletion
The specific embodiment
Be noted that following detailed description all is an exemplary, being intended to provides further explanation to the present invention.Unless otherwise, all technology used of this paper and scientific terminology have with the present invention under the identical meanings of those of ordinary skill common sense of technical field.
The preparation method of de-fluoridation adsorbent at first, is described in conjunction with exemplifying embodiment.
Fig. 1 is the flow chart according to the preparation method of the de-fluoridation adsorbent of the embodiment of the invention.As shown in Figure 1, in a kind of preferred implementation of the present invention, can may further comprise the steps according to the preparation method of the de-fluoridation adsorbent of the embodiment of the invention:
Step S102 chooses natural siderite powder;
Step S104 in selected natural siderite powder, adds proper amount of deionized water, aluminium salt and an amount of adhesive, obtains mixing dope;
Step S106 carries out the wet method extruder grain to resulting mixing dope;
Step S108 calcines the particle that is obtained by the wet method extruder grain.
Through natural siderite powder is carried out wet method extruder grain and calcining, make a part of natural siderite FeCO3 that chemical reaction take place and generated bloodstone Fe2O3 (reaction equation 1).Because siderite FeCO3 and bloodstone Fe2O3 can react with fluorine ion in the water, thereby have reduced the content of fluorine in the water, reach the effect of defluorination.
The interpolation of aluminium salt make Al3+, aluminium salt hydrolysis intermediate product and reactions such as the last Al (OH) 3 (am) that generates adsorbs with F –, ion-exchange and complex-precipitation, make that fluorine ion is able to removal in the water.
4FeCO
3+O
2->?2Fe
2O
3+4CO
2 （1）
Fig. 2 is the X-ray diffraction analysis spectrogram of adsorbent after natural siderite former state and the modification.In Fig. 2,1. represent natural siderite former state; 2. the adsorbent after aluminium salt and binding agent are calcined is not added in expression; 3. the adsorbent after expression interpolation aluminium salt and binding agent are calcined.Natural siderite main component is: siderite (Siderite), bloodstone (Hematite), pyrite (Pyrite), quartzy (Quartz), dolomite (Dolomite), clay mineral (Clay Minerals).
From Fig. 2, can know, and bloodstone content increase in the adsorbent after the modification (2. 3. be respectively 39.5%--with 66%).In addition, add that corresponding variation has taken place the lattice of siderite behind aluminium salt and the binding agent: make originally to be about relative stronger peak, 32o place (among Fig. 2 1. 2.) at 2 θ and obviously to weaken (among Fig. 2 3.).
In addition, in embodiments of the present invention, the particle that calcining is obtained is as de-fluoridation adsorbent.Because de-fluoridation adsorbent is graininess, make the user easily de-fluoridation adsorbent to be placed in the filter (cylindrical reactor) high-fluorine water is filtered, not only easy to use, and be convenient to the activating and regenerating of material absorption after saturated.
In a preferred embodiment of the invention, above-mentioned steps S108 can comprise: the temperature that in Muffle furnace, adopts 450 ℃ was to the particle calcination that obtained by said wet method extruder grain 3 hours.
After adding certain moisture, aluminium salt and aluminium colloidal sol, through 450 ℃, the calcination of 3 h can make that each mineral content reaches an optimal proportion in the modified adsorbent, and this ratio is more favourable to its defluorination process.Described in table 1 and table 2, the described adsorbent of the embodiment of the invention all is much higher than the adsorbent under natural siderite former state and other modified condition to the removal efficient of F; And reach under the higher fluoride removing rate circumstances in assurance, the adsorbent that the present invention makes is behind defluorination, and the iron aluminum concentration all meets national drinking water standard in the water outlet.
Show 1:450 ℃, the different adsorbent defluorination effects comparisons of 3h (liquid-solid ratio is 10 g/L)
| Adsorbent | Initial concentration (mg/L) | Defluorination capacity (mg/g) | Clearance (%) |
| Natural siderite powder | 5.0 | 0.105 | 21 |
| Do not add aluminium salt binding agent product | 5.0 | 0.248 | 49.5 |
| Add aluminium salt binding agent product | 5.0 | 0.486 | 97.2 |
450 ℃ in table 2,3h fluoride removing rate add the variation (liquid-solid ratio is 10 g/L) of aluminium amount with adsorbent
| Binding agent/mg.g-1 aluminium salt/mg.g-1 | 20 | 60 | 100 | 150 | 200 |
| 6 | 90.1 | 91.1 | 95 | 96.8 | 97．2 |
| 36 | 98.8 | 97.5 | 94.1 | 78.3 | 72.1 |
| 48 | 99.1 | 98．9 | 98．4 | 97．5 | 97．3 |
| 60 | 99．6 | 99．3 | 99．2 | 98．9 | 98．9 |
In a preferred embodiment of the invention, among the step S104, the binding agent that is added is the 54.9%-61.9% of said mixing dope gross weight.When adhesive consumption was 54.9%, adsorbent reached 96.8% to the clearance of F; When adhesive consumption was 61.9%, adsorbent reached 97.2% to the clearance of F.
Because the binding agent that is added is the 54.9%-61.9% of said mixed solution gross weight, can make the density of de-fluoridation adsorbent particle moderate, intensity increases, and can promote defluorination effect to a certain extent again.
In a preferred embodiment of the invention, the above-mentioned binding agent that uses is aluminium colloidal sol.
In a preferred embodiment of the invention, among the step S104, the weight ratio of deionized water and natural siderite powder is 1:50-1:25.This weight ratio can make dope when wet granulation, obtain optimum condition, can when natural siderite calcination modification, accelerate its reaction rate again.When the weight ratio of deionized water and natural siderite powder was 1:50, adsorbent was 96. 4% to the clearance of F; Clearance was 97.2% when the weight ratio of deionized water and natural siderite powder was 1:25.
In a preferred embodiment of the invention, among the step S102, the content of siderite is 85.6% of total content in the selected natural siderite.On the one hand, the natural siderite of this content is abundant relatively at the reserves of China, and cost is relatively low; On the other hand, in the time of satisfying optimum modification to the requirement of siderite content.Natural siderite adsorbent is 97.2% to the clearance of F after the modification.
Claims (8)
1. the preparation method of a de-fluoridation adsorbent is characterized in that, comprising:
Step S102 chooses natural siderite powder;
Step S104 in selected natural siderite powder, adds proper amount of deionized water, aluminium salt and an amount of adhesive, obtains mixing dope;
Step S106 carries out the wet method extruder grain to resulting mixing dope;
Step S108 calcines the particle that is obtained by the wet method extruder grain.
2. method according to claim 1 is characterized in that, said step S108 comprises:
In Muffle furnace, adopt 450 ℃ temperature that the particle that is obtained by said wet method extruder grain was calcined 3 hours.
3. method according to claim 1 is characterized in that, said step S102 comprises:
Said natural siderite is ground into the powder of granularity less than 0.10 mm.
4. method according to claim 1 is characterized in that, among the said step S106, obtains the particle that granularity is 3-4 mm through the wet method extruder grain.
5. method according to claim 1 is characterized in that, among the said step S104, the aluminium salt that is added is 2.6% of said mixing dope gross weight, and binding agent is 54.9%-61.9%.
6. method according to claim 5 is characterized in that, said aluminium salt is aluminum sulfate, and binding agent is that solid-to-liquid ratio is 25% aluminium colloidal sol.
7. method according to claim 1 is characterized in that, among the said step S104, the weight ratio of said deionized water and said natural siderite powder is: 1:50-1:25.
8. method according to claim 1 is characterized in that, among the said step S102, the content of siderite is 85.6% of total content in the selected natural siderite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102868778A CN102451662A (en) | 2011-09-26 | 2011-09-26 | High-efficiency fluorine-removing adsorbent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102868778A CN102451662A (en) | 2011-09-26 | 2011-09-26 | High-efficiency fluorine-removing adsorbent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102451662A true CN102451662A (en) | 2012-05-16 |
Family
ID=46035591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102868778A Pending CN102451662A (en) | 2011-09-26 | 2011-09-26 | High-efficiency fluorine-removing adsorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102451662A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583606A (en) * | 2017-09-27 | 2018-01-16 | 天津大学 | The volcanic rock base porous ceramic grain and preparation method and application of high-effective defluorination |
| CN111346601A (en) * | 2020-03-12 | 2020-06-30 | 河北工业大学 | Ceramsite for adsorbing perfluorinated compounds in water and preparation method thereof |
-
2011
- 2011-09-26 CN CN2011102868778A patent/CN102451662A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 刘琼等: "菱铁矿改性对饮用水除氟效果的影响研究", 《第四届中国城镇水务发展国际研讨会暨中国城镇供水排水协会2009年年会论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107583606A (en) * | 2017-09-27 | 2018-01-16 | 天津大学 | The volcanic rock base porous ceramic grain and preparation method and application of high-effective defluorination |
| CN111346601A (en) * | 2020-03-12 | 2020-06-30 | 河北工业大学 | Ceramsite for adsorbing perfluorinated compounds in water and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100415361C (en) | Rare earth adsorbent and production thereof | |
| CN101733067A (en) | Adsorbing material, preparation thereof and method for purifying sewage by using adsorbing material | |
| CN110193342A (en) | A kind of modified attapulgite earth adsorbing and preparation method thereof | |
| CN104071861A (en) | Sewage purifying agent and preparation method thereof | |
| CN102145947A (en) | Water treatment method for removing Tl<+> and/or Cd2<+> by producing nanometer iron and manganese oxides in situ | |
| CN100366337C (en) | Method for preparing absorbent with phosphor concentration and phosphor reclaim function | |
| Oladoja et al. | Green reactive material for phosphorus capture and remediation of aquaculture wastewater | |
| CN104829219A (en) | Multifunctional composite tourmaline energy ceramic ball and manufacturing method thereof | |
| CN103111256A (en) | Preparation method of efficient calcium-based sepiolite phosphorus adsorbent and application thereof | |
| CN109502677A (en) | A kind of efficient dephosphorization agent and preparation method thereof | |
| CN103071450B (en) | Defluorination adsorbent as well as preparation method and application thereof | |
| CN106744766B (en) | A kind of production method of magnesium doped hydroxyapatite defluoridation filter material | |
| CN101456617A (en) | Method for removing bromate ion in drinking water | |
| CN102451662A (en) | High-efficiency fluorine-removing adsorbent and preparation method thereof | |
| CN103011434A (en) | Filter cartridge material | |
| CN105664842A (en) | Calcium-based adsorbent for defluorination and application thereof | |
| CN101428208B (en) | Methods for producing and using high-efficiency defluorination adsorption agent | |
| CN102233256A (en) | Preparation method of arsenic removal adsorbent and arsenic removal adsorbent | |
| CN113164850A (en) | Health function customized natural mineral substance activated composite filter and manufacturing method thereof | |
| Huang et al. | A comparative study of phosphate removal technologies using adsorption and fluidized bed crystallization process | |
| Shi et al. | Preparation of hydroxyapatite (HAP) from waste eggshells for enhancing the granulation and treatment performance of aerobic granular sludge: Enhancement effects and mechanism insights | |
| CN103910418A (en) | Compound flocculating agent for processing sewage | |
| Kabir et al. | Synthesis, optimization and characterization of mesoporous Mg-Al-Fe tri-metal nanocomposite targeting defluoridation: synergistic interaction of molar ratio and thermal activation | |
| Nur | Nitrate, phosphate and fluoride removal from water using adsorption process | |
| CN110876919B (en) | Preparation method of high-salinity wastewater nitrate radical adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120516 |