CN100450606C - Ferrum-silicon modified alta-mud for water treatment and its preparation method - Google Patents
Ferrum-silicon modified alta-mud for water treatment and its preparation method Download PDFInfo
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- CN100450606C CN100450606C CNB2006101351585A CN200610135158A CN100450606C CN 100450606 C CN100450606 C CN 100450606C CN B2006101351585 A CNB2006101351585 A CN B2006101351585A CN 200610135158 A CN200610135158 A CN 200610135158A CN 100450606 C CN100450606 C CN 100450606C
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- bentonite
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Abstract
The invention relates to a water-treatment iron-silicon modified alta-mud and relative preparation, which uses iron modifier as main material, uses iron-silicon inorganic crosslink agent and catabrom (CTMAB) as organic cylinder agent to modify the sodium alta-mud, prepare Fe-Si inorganic crosslink and Fe-Si organic composite modified alta-mud. And the preparation comprises that first preparing crosslink agent, then preparing iron-silicon inorganic crosslink mud, and preparing iron-silicon inorganic composite mud. The inventive alta-mud can be used as novel water treatment agent with low cost and wide application.
Description
Technical field
The present invention relates to a kind of material for water treatment and preparation method thereof, particularly a kind of ferrum-silicon modified alta-mud that is used for water treatment and preparation method thereof.
Background technology
Bentonite is a kind of at distributed in nature clay class mineral comparatively widely, institute's nonmetallic minerals.The bentonite ore resource of China is very abundant, and reserves occupy first place in the world, and account for 60% of world's total amount, and prognostic resources is more than 7,000,000,000 tons, and wide to distribute, bury shallow, easy digging and great variety of goods is characteristics.The bentonite and the remodeling product of purifying thereof all have some superior characteristic to some extent, these characteristics mainly contain dilatancy, hydrophily (or lipophile, as organic bentonite), adsorptivity, cation exchange, catalytic activity, dispersiveness, suspension, cementability, thixotropy, stability, avirulence.Along with science and technology development, people deepen gradually to the understanding of bentonite crystallization property and physicochemical properties, and the use of bentonite aspect industrial and agricultural production and scientific research is increasingly extensive.It as binding agent, suspending agent, thickener, thixotropic agent, flocculant, stabilizing agent, purification and decoloration agent, filler, catalyst and catalyst carrier herd in metallurgy, machine casting, probing, petrochemical industry, light industry, agricultural, there is very application prospects in fields such as architectural engineering, environmental protection.Because bentonite charging property and bigger specific area make it have stronger adsorptivity, so bentonite has good ion-exchange capacity and absorption property, can remove some pollutant in the sewage.But because the surface silicon oxide structure has extremely strong hydrophily and the cationic hydrolysis of a large amount of interchangeabilities of interlayer, make its surface have the thin moisture film of one deck usually, and limited the application in water treatment in the natural montmorillonite; In addition, bentonite Separation of Solid and Liquid speed is slow, and the flocculate costs and poor dehydration results has also influenced its practical application.In order to satisfy certain needs or in order to improve bentonitic result of use, acquisition has the high-performance bentonite of practicality, under certain condition, in bentonite, introduce artificially some inorganic ions or (with) organic compound, bentonitic structure and chemical property are changed, reach purpose bentonite remodeling.At present STUDY OF BENTONITE MODIFICATION is mainly concentrated on inorganic modified, organically-modified and inorganic-organic composite modified.After years of research and found that modified alta-mud has a high potential in all kinds of wastewater treatments especially Application in Industrial Wastewater Treatment as adsorbent, modification soil can be widely used in removing aromatic compound, poisonous and hardly degraded organic substance, remove look etc.Because cheap, applied widely, along with deepening continuously of research, the modified alta-mud adsorbent might replace the status of traditional adsorbent in wastewater treatment, be used widely in wastewater treatment.
Summary of the invention
The objective of the invention is to, provide a kind of based on iron-based modifier, preparation Fe-Si dual element inorganic crosslinking and the organic compound series modified bentonite of Fe-Si-, the series modified bentonite of Fe-Si of this invention preparation, its interlamellar spacing of bentonite and specific area and surface hydroxyl quantity have been increased, improve its hydrophobicity, thereby improved adsorption capacity, expanded bentonitic application.
The objective of the invention is to be achieved through the following technical solutions:
Ferrum-silicon modified alta-mud for water treatment, based on iron-based modifier, utilize iron silicon inorganic crosslinking agent and cetrimonium bronmide (CTMAB) sodium bentonite to be carried out modification, the inorganic and series modified bentonite of the organic composite earth of Fe-Si-of preparation Fe-Si dual element for organic pillaring agent.
Aforesaid ferrum-silicon modified alta-mud for water treatment, its water treatment iron silicon inorganic crosslinking bentonite, interlamellar spacing d is 2.0262nm.
Aforesaid ferrum-silicon modified alta-mud for water treatment, its water treatment organic composite earth of iron silicon, interlamellar spacing d is 1.8332nm.
The preparation method of ferrum-silicon modified alta-mud for water treatment,
At first prepare crosslinking agent:
The preparation of iron crosslinking agent: NaOH (NaOH) solution is slowly joined ferric trichloride (FeCl
3) in the solution, at room temperature continuous stirring leaves standstill, the iron crosslinking agent;
The preparation of silicon crosslinking agent: with sulfuric acid (H
2SO4) slowly add to sodium metasilicate (Na
2SiO3) stir in the solution, leave standstill under the room temperature, display, get the silicon crosslinking agent;
Prepare iron silicon inorganic crosslinking soil then:
Get original soil and make the clay slip, crosslinking agent is added drop-wise in the clay slip, add sulfuric acid (H
2SO4) or NaOH (NaOH), regulate pH value, stir, leave standstill, ageing is filtered, drying, and activation gets the crosslinked soil of iron silicon;
Prepare the organic composite earth of iron silicon again:
Get the crosslinked soil of iron silicon and make suspension, add the water-ethanol solution contain 5.0% cetab, stir, after reaction is finished, be cooled to room temperature, filtration under diminished pressure is with the distilled water washing, until checking out bromide ion (Br
-) and the filtrate non-foam, the oven dry of gained filter cake, activation, crushing screening gets the organic composite earth of iron silicon.
The preparation method of aforesaid ferrum-silicon modified alta-mud for water treatment, iron silicon inorganic crosslinking soil: suspension concentration 4%, iron silicon dosage 8mmol/g, iron silicon ratio 2: 1,70 ℃ of reaction temperatures, reaction time 7h; The organic composite earth of iron silicon: suspension concentration 4%, cetrimonium bronmide (CTMAB) dosage 0.9mmol/g, 70 ℃ of reaction temperatures, reaction time 2h.
Advantage of the present invention and effect are:
The present invention has changed bentonite bed spacing and specific area and surface hydroxyl quantity, improved bentonitic adsorption capacity, organic modifiers is introduced the cross-linked bentonite interlayer, not only increased the ion-exchange capacity of crosslinked soil, and improved its hydrophobicity, thus improved adsorption capacity, expanded bentonitic application, as a kind of novel water-treatment medicament, it is low to have price.Characteristics such as performance is good, applied widely.
The present invention is as a kind of novel water-treatment medicament, the waste water that contains organic pollution (paper waste, sip wine waste water, slaughtering wastewater etc.) be can use and the organic matter of metal ion waste water (electroplating wastewater) such as cadmium and the removal of heavy metal ion contained, good to the removal effect of colourity in the waste water and turbidity simultaneously.Be used to handle COD
CrConcentration is the paper waste about 2000mg/L, and iron silicon inorganic crosslinking soil is to COD
CrClearance reaches 79%; The organic composite earth of iron silicon is to COD
CrClearance reaches 87% respectively, through after-treatment, and remaining COD
CrConcentration (mg/L) all is lower than national paper waste discharge standard (450mg/L); To the clearance of chroma in waste water all greater than 90%; To turbidity removal rate all greater than 95%.Be used for processing and contain Cr (VI) waste water, modified alta-mud obviously improves the removal ability of Cr (VI).In initial concentration is the scope of 20～50mg/L, Cr (VI) is had removal effect preferably, the clearance of the crosslinked soil of iron silicon is more than 82%, the clearance of the organic composite earth of iron silicon is more than 87%.Be applied to Cr (VI) concentration and be the electroplating wastewater about 20mg/L: the crosslinked soil of iron silicon to the clearance of Cr (VI) all more than 99%, residual Cr (VI) concentration is below 0.2mg/L, be lower than national comprehensive discharge standard (0.5mg/L), can qualified discharge, be fit to handle low concentration and contain Cr (VI) waste water.
Description of drawings
Fig. 1 is preparation technology's flow chart of the crosslinked soil of the present invention;
Fig. 2 is preparation technology's flow chart of the crosslinked organic composite earth of the present invention.
The specific embodiment
The present invention is described in detail with reference to the accompanying drawings.
Composition principle
Natural earth is a kind of lamellar aluminosilicate, the layer with layer between combine by electrostatic interaction, utilize the interchangeability of interlayer cation, can with inorganic poly hydroxy metal ion as: exchanges such as Al, Cr, Fe, Bi, Zr, Co, Si enter interlayer, with the elementary layer bridging and strut, form the new mineral of " layer net " shape structure of a kind of two-dimensional channel, i.e. pillared bentonite.Pillared bentonite has very high specific area and heat endurance, and its lewis acid activity is very high.While is owing to polarity, pore-size distribution and the high-specific surface area of pillared bentonite uniqueness, thereby its absorption property strengthens greatly.Bentonite is through ion-exchange, make electric charge on the plane of crystal band, expand thereby can make hydrone be easy to enter between structure cell, and can make clay particle surface spontaneously adsorb cation, thereby bentonite shows great dilatancy and adsorptivity, caking property and thixotropy preferably.The multiple cation of bentonite surface absorption fully disperses bentonite clay particle through hydration, and the sun that its degree of scatter depends on absorption again is from kind.And contain Na
+Bentonitic hydration capability greater than the hydration capability of other bivalent cation, thereby has quickened the aquation of clay particle, helps the carrying out that organises and react.Again because Ca
2+Ionic radius is bigger, and difficult quilt replaces, so in bentonite organises reaction, select sodium bentonite usually for use.Pass through Na
+Exchange with the cation in the organic compound, be used for replacing the cation of the original absorption of montmorillonite particle surface, the material that interlayer forms macroscopic void is introduced in the organic anion that volume is bigger, makes its structural change, thereby reaches organically-modified purpose.This through the bentonite after the organic process, because of the content increase of its organic carbon, the ability of stronger adsorb organic compound is arranged.Because it is big not enough as the pillared bentonite interlamellar spacing of pillaring agent preparation with poly hydroxy metal cation, thereby the researcher with some surfactants introduce synthesize between bentonite bed more wide-aperture inorganic-organic-pillared bentonite, and its heat endurance also is significantly improved.
The preparation of crosslinking agent
The preparation of iron crosslinking agent: NaOH (NaOH) solution is slowly joined ferric trichloride (FeCl
3) in the solution, continuous stirring at room temperature;
The preparation of silicon crosslinking agent: with sulfuric acid (H
2SO4) slowly add to sodium metasilicate (Na
2SiO
3) stir in the solution, leave standstill under the room temperature, display;
The preparation of iron silicon inorganic crosslinking soil
Get original soil and make the clay slip, crosslinking agent is added drop-wise in the clay slip, adding sulfuric acid (H2SO4) or NaOH (NaOH) are regulated the pH value, stir, and is still aging, filter, and drying, activation gets the crosslinked soil of iron silicon;
The preparation of the organic composite earth of iron silicon:
Get the crosslinked soil of iron silicon and make suspension, add the water-ethanol solution contain 5.0% cetab and stir, after reaction is finished, be cooled to room temperature, filtration under diminished pressure is with the distilled water washing, to checking out bromide ion (Br
-) and the filtrate non-foam, the oven dry of gained filter cake, activation, crushing screening gets the organic composite earth of iron silicon.
Optimum preparating condition is:
The crosslinked soil of iron silicon: suspension concentration 4%, iron silicon dosage 8mmol/g, iron silicon ratio 2: 1,70 ℃ of reaction temperatures, reaction time 7h;
Iron silicon machine composite earth: suspension concentration 4%, CTMAB (cetrimonium bronmide) dosage 0.9mmol/g, 70 ℃ of reaction temperatures, reaction time 2h.
Described water treatment iron silicon inorganic crosslinking bentonite, interlamellar spacing d is 2.0262nm; The water treatment organic composite earth of iron silicon, interlamellar spacing d is 1.8332nm.
Claims (4)
1. ferrum-silicon modified alta-mud for water treatment, it is characterized in that based on iron-based modifier, utilizing iron silicon inorganic crosslinking agent and cetrimonium bronmide is that organic pillaring agent carries out modification to sodium bentonite, the inorganic and series modified bentonite of the organic composite earth of Fe-Si-of preparation Fe-Si dual element.
2. according to the described ferrum-silicon modified alta-mud for water treatment of claim 1, it is characterized in that water treatment iron silicon inorganic crosslinking bentonite, interlamellar spacing d is 2.0262nm.
3. according to the described ferrum-silicon modified alta-mud for water treatment of claim 1, it is characterized in that the water treatment organic composite earth of iron silicon, interlamellar spacing d is 1.8332nm.
4. the preparation method of ferrum-silicon modified alta-mud for water treatment is characterized in that:
At first prepare iron crosslinking agent, silicon crosslinking agent, prepare iron silicon inorganic crosslinking soil then, prepare the organic composite earth of iron silicon again, wherein iron silicon inorganic crosslinking soil: suspension concentration 4%, iron silicon dosage 8mmol/g, iron silicon ratio 2: 1,70 ℃ of reaction temperatures, reaction time 7h; The organic composite earth of iron silicon: suspension concentration 4%, cetrimonium bronmide dosage 0.9mmol/g, 70 ℃ of reaction temperatures, reaction time 2h.
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| CN100450606C true CN100450606C (en) | 2009-01-14 |
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| CN105905915B (en) * | 2016-04-14 | 2018-02-02 | 浙江红宇新材料股份有限公司 | A kind of preparation method of Bentonite modifier |
| CN111393134A (en) * | 2020-02-19 | 2020-07-10 | 佛山市山有海科技有限公司 | Silicate system-based modified bentonite body reinforcing agent |
| CN114395281A (en) * | 2022-02-10 | 2022-04-26 | 天津蓝海优贝科技有限公司 | Bottom surface integrated shell powder coating and preparation method thereof |
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