CN101318125B - Method for preparing poly-epoxychloropropane dimethylamine cation alta-mud - Google Patents
Method for preparing poly-epoxychloropropane dimethylamine cation alta-mud Download PDFInfo
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- CN101318125B CN101318125B CN2008101380498A CN200810138049A CN101318125B CN 101318125 B CN101318125 B CN 101318125B CN 2008101380498 A CN2008101380498 A CN 2008101380498A CN 200810138049 A CN200810138049 A CN 200810138049A CN 101318125 B CN101318125 B CN 101318125B
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- dimethylamine
- bentonite
- epoxychloropropane
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Abstract
The invention relates to a preparation method for polyepichlorohydrin dimethylamine cation bentonite, belonging to the technical field of environmental protection; the preparation method prepares thepolyepichlorohydrin dimethylamine/bentonite by taking sodium bentonite as the raw material, dimethylamine, epichlorohydrin and quadrol as intercalation agents and adopting a monomer insertion-interlayer polymerization method. The product is milky white solid powder, which has around100mg/g of organic loading capacity, 1.456nm of interlayer spacing, 27.89m<2>/g of specific surface and more than 90percent of decoloration rate to reactive turquoise blue. The method of the invention has the advantages of reasonable design, simple technique, low cost, etc. The prepared polyepichlorohydrin dimethylamine cation bentonite has the advantages of stable product quality and excellent adsorption performance, which has high application value in the decoloration treatment of printing and dyeing wastewater.
Description
Technical field
The present invention relates to a kind of method for preparing poly-epoxychloropropane dimethylamine cation alta-mud, belong to environmental protection technical field.
Background technology
Bentonite is to be the clay mineral of main component with the montmorillonite, is layer structure, and its crystal unit is made up of in 2: 1 ratios silicon-oxy tetrahedron and alumina octahedral, and theoretical chemistry consists of: Al
2[Al
xSi
4-xO
10] (OH)
2Exist cation (as Fe in silicon-oxy tetrahedron and the alumina octahedral
2+, Fe
3+, Mg
2+, Al
3+) the isomorphous replacement phenomenon, be at a low price the time when replacing cation, structure increase equivalent negative electrical charge adsorbs other cations by interlayer and compensates and reach charge balance, and these ions mainly contain K
+, Na
+, Li
+, Ca
2+Deng, this makes that with other cations exchange taking place becomes possibility.The bentonite clay particle surface is because of adsorbed water molecule generation aquation simultaneously, and hydrone enters between bentonite bed, causes the bentonite volumetric expansion, and specific area enlarges markedly, and produces very strong adsorption capacity.Cation exchange and adsorptivity are bentonitic key properties.Abroad from last century six the seventies just begun one's study and bentonite applied in the middle of the environmental pollution control.Since the nineties in 20th century, China also begins bentonite in the research of environmental protection Application for Field.China's natural montmorillonite aboundresources, cheap, develop bentonite energetically and the modified alta-mud water treatment agent has wide application prospect.
Because natural montmorillonite surface silicon oxide structure has extremely strong hydrophily, add the interlayer cation facile hydrolysis, so during the bentonite in treatment waste water of application non-modified, adsorption effect is not obvious.The bentonite that generally is used for wastewater treatment all must be handled through modification.Bentonite Modification Technologies mainly contains two kinds at present: the one, and activation method; The 2nd, add ionic compound, comprise inorganic compound, organic compound and inorganic-organic composite modifier.Bentonite after modification, its water treatment effect significantly improves.With the organic polymer modified alta-mud is to study focus in recent years, and it is to utilize the stratiform bentonite as main body, and organic polymer is made as the interlayer that object inserts main body.Wherein, through the quaternary ammonium salt-modified dose of compound cation organobentonite that makes of intercalation, interlamellar spacing increases, and interlamination region becomes hydrophobic environment, and surface charge increases, thereby absorption property improves greatly, and organic energy force rate original soil high tens is to hundred times in the removal water.EPI-DMA is a kind of new and effective soluble quaternary ammonium type cationic polymer that contains functional groups such as hydroxyl, amido, ammonium ion, have that molecular weight is big, positive charge density is high, high effect nontoxic, advantage such as cheap, be a kind of widely used water treatment agent.
Method between the organic polymer insert layer can be divided into: 1. monomer insertion-interlayer polymerization; 2. organic polymer solution directly inserts; 3. the organic polymer fusion is directly inserted.At present more with the research of organic polymer solution direct insertion method modified alta-mud, with monomer insertions-interlayer polymerization technique as the present domestic bibliographical information of not seeing of preparation technology.
Therefore, utilize above-mentioned principle with sodium bentonite as material of main part, at first dimethylamine inserts between bentonite bed by cation exchange effect and suction-operated, adds epoxychloropropane and ethylenediamine then, polyepoxy chloropropane dimethylamine cationic bentonite is prepared in polymerization between complete layer.Monomer carries out polymerisation at interlayer, has further supportted interlamellar spacing big, can increase organic load capacity, and its adsorption effect to pollutant can strengthen.This research has important theoretical and practical significance.
About the bentonitic research report of poly-epoxychloropropane dimethylamine cation polymer; referring to Li Qian; Yue Qinyan etc.; cationic bentonite is to the adsorption dynamics adsorption kinetics research [J] of disperse dyes; SCI; 2006; 27 (6): 1113～1117. Li Qian; Yue Qinyan etc.; the performance of cationic polymer/bentonite nano composite adsorbing material reaches the decolouring [J] to orchil; the chemical industry journal, 2006,57 (2): 436～441. but the polyepoxy chloropropane dimethylamine cationic bentonite mentioned in the article obtain by " organic polymer solution directly inserts " method.
Summary of the invention
The present invention is directed to the deficiency of present preparation of organic bentone, polyepoxy chloropropane dimethylamine cationic bentonite and preparation method thereof is provided.This method is a kind of than the direct graft process of the polymer new preparation process of cationic bentonite more efficiently.
Method of the present invention is to be primary raw material with sodium bentonite and dimethylamine, epoxychloropropane, ethylenediamine, adopts monomer insertion-interlayer polymerization synthesizing cationic bentonite, and step is as follows:
(1) take by weighing sodium bentonite after the oven dry in three mouthfuls of round-bottomed flasks, adding the water management solid-to-liquid ratio is 1.5-2%, dispersed with stirring 1-1.5h in electric mixer, suspension;
(2) add dimethylamine in above-mentioned suspension, the dimethylamine quality is 1/10～1/2 of a used sodium bentonite quality, and the control temperature stirs 1.5-2h under 18-22 ℃ of condition,
(3) in step (2) gained solution, add epoxychloropropane, epoxychloropropane and dimethylamine mol ratio are (0.75～1.75): 1, perhaps add a small amount of ethylenediamine again, the ethylenediamine dosage is 1%～5% of epoxychloropropane and a dimethylamine gross mass, stirs 2h～7h under 50 ℃～80 ℃ temperature;
(4) reactant liquor of suction filtration step (3), the gained solids is the poly-epoxychloropropane dimethylamine cation bentonite, with distilled water washing gained solids to filtrate chloride ion-containing not, 60～80 ℃ of oven dry down, grind, cross 200 mesh sieves, activate 2.0 hours down, make the polyepoxy chloropropane dimethylamine cationic bentonite finished product at 104～110 ℃.
Preferably, sodium bentonite, its main component is a montmorillonite, and expand doubly＞15 in colloid index＞100, and cation exchange capacity CEC is 750mmol/kg; Chemical composition, in mass fraction, SiO
2: 69.32%, Al2O3:14.27%, CaO:1.99%, MgO:2.69%, Fe
2O
3: 1.84%, Na
2O:1.85%, K
2O:1.38%.
Preferably, used dimethylamine is that mass fraction is the dimethylamine agueous solution of 30-33%.
Temperature control in above-mentioned steps (2), (3) is realized by the water-bath heating.
The polyepoxy chloropropane dimethylamine cationic bentonite that the present invention prepares, outward appearance are the milky powdery solid of homogeneous, and organic load capacity is about 100mg/g, and interlamellar spacing is 1.456nm, and specific area is 27.89m
2/ g can be used as a kind of adsorbent of novel Cheap highly effective.
Characteristics of the present invention are: with dimethylamine, epoxychloropropane and/or ethylenediamine as intercalator, adopt monomer insertion-interlayer polymerization synthesizing cationic bentonite, the process conditions of strict each step of control, synergy mutually under preferred condition, the polyepoxy chloropropane dimethylamine cationic bentonite constant product quality, outward appearance homogeneous, the good adsorption performance that obtain, and cost is lower.
The specific embodiment
The invention will be further described below in conjunction with embodiment.Used raw material, the equipment of embodiment is as follows:
Sodium bentonite is Weifang China bentonite factory product.
33% dimethylamine agueous solution (chemical pure); Hydrin (analyzing pure); Anhydrous ethylenediamine (analyzing pure); Reactive turquoise blue (K-GL).
Main laboratory apparatus is JJ-1 reinforcement electric mixer, instrument thermostat water bath.
Embodiment 1:
The step that monomer insertion-interlayer polymerization prepares polyepoxy chloropropane dimethylamine cationic bentonite is as follows:
(1) takes by weighing sodium bentonite after the oven dry of 2.00g in three mouthfuls of round-bottomed flasks that fill the 100mL deionized water, dispersed with stirring 1h in JJ-1 reinforcement electric mixer;
(2) add the intercalator dimethylamine (dimethylamine be used sodium bentonite quality 2/5) of 0.800g in above-mentioned suspension, the control temperature stirs 2h under 20 ℃ of conditions, it is fully exchanged;
(3) more in molar ratio for epoxychloropropane: dimethylamine=1: 1 adds epoxychloropropane quantitatively, by quality than ethylenediamine: (epoxychloropropane+dimethylamine)=2% adds ethylenediamine quantitatively, stirs 3h under 65 ℃ temperature;
(4) suction filtration reactant liquor washs above-mentioned cationization bentonite to filtrate chloride ion-containing not with distilled water, and 60～80 ℃ of oven dry are ground, and cross 200 mesh sieves, 104～110 ℃ of activation 2.0 hours down, prepares the polyepoxy chloropropane dimethylamine cationic bentonite finished product.
Embodiment 2: as described in embodiment 1, the consumption of different is dimethylamine is 1/5 of a used sodium bentonite quality, and epoxychloropropane and dimethylamine mol ratio are 1.25: 1, and the ethylenediamine dosage is 1% of epoxychloropropane and a dimethylamine gross mass.
Poly-epoxychloropropane dimethylamine polymer/bentonite by the above-mentioned steps preparation is carried out performance characterization, and the result is as shown in table 1:
The architectural feature of table 1 bentonite and polyepoxy chloropropane dimethylamine cationic bentonite relatively
By above result as seen, the interlamellar spacing of the direct intercalation EPI-DMA/Bt of polymer is 1.4.1nm, has increased 0.147nm than the 1.254nm of original soil; The interlamellar spacing of monomer insertion-interlayer polymerization EPI-DMA/Bt is 1.456nm, has increased 0.202nm than original soil, and direct intercalation EPI-DMA/Bt has increased 0.055nm than polymer solution.The specific area of original soil is 13.46m2/g, and the specific area of the direct intercalation EPI-DMA/Bt of polymer solution is 20.51m2/g, has increased 7.05m2/g than original soil; The EPI-DMA/Bt specific area of monomer insertion-interlayer polymerization is 27.89m2/g, has increased 14.43m2/g than original soil.In addition, because the increase of interlamellar spacing and specific area, the content of organics of the EPI-DMA/Bt of monomer insertion-interlayer polymerization preparation is far longer than the bentonite of the direct intercalation of EPI-DMA polymer solution.As seen the synthetic EPI-DMA/Bt of monomer insertion-interlayer polymerization has better architectural feature.
The use amount of finding dimethylamine in the preparation process in the experiment has the greatest impact to the decoloration performance of synthetic EPI-DMA/Bt.Table 2 is depicted as the relation of dimethylamine dosage in percent of decolourization and the EPI-DMA/Bt preparation process.As can be seen, along with the increase of dimethylamine dosage in the preparation process, percent of decolourization raises very fast; When the dimethylamine dosage was 3mmol/g (promptly 4 times to bentonitic cation exchange capacity), the EPI-DMA/Bt decolorizing efficiency that makes reached more than 90%; The dimethylamine dosage continues to increase, and absorption tends towards stability, and clearance increases not obvious.
The decolorizing effect of the different dimethylamine dosage of table 2 EPI-DMA/Bt
Polyepoxy chloropropane dimethylamine cationic bentonite (EPI-DMA/Bt) product of monomer insertion-interlayer polymerization preparation is used for the decolouring processing of dye wastewater reactive turquoise blue K-GL, simultaneously, the results are shown in table 3 with the comparison of opposing of the decolorizing effect of bentonite original soil, the direct intercalation EPI-DMA/Bt of polymer solution, Powdered Activated Carbon:
The different adsorbents of table 3 to active emerald green blue decolorizing effect relatively
Annotate: dye strength 50mg/L; Dosage is 2g/L.
From above result as seen, compare with sodium base original soil, the EPI-DMA/Bt that monomer insertion-interlayer polymerization is synthesized has significant improvement to the percent of decolourization of dyestuff.In addition, because sodium base original soil is difficult to separate with powdered activated carbon absorption back solid-liquid, settling property is bad.
Above result shows that " monomer insertion-interlayer polymerization " synthetic more former bentonitic absorption property of poly-epoxychloropropane dimethylamine has clear improvement, and is a kind of adsorbent of function admirable.
Claims (3)
1. method for preparing poly-epoxychloropropane dimethylamine cation alta-mud is a raw material with sodium bentonite and dimethylamine, epoxychloropropane, ethylenediamine, it is characterized in that adopt monomer insertion-interlayer polymerization synthesizing cationic bentonite, step is as follows:
(1) take by weighing sodium bentonite after the oven dry in three mouthfuls of round-bottomed flasks, adding water management solid-liquid percentage is 1.5-2%, dispersed with stirring 1-1.5h in electric mixer, suspension;
(2) add dimethylamine in above-mentioned suspension, dimethylamine dosage and used sodium bentonite mass ratio are 1: 10～2, and the control temperature stirs 1.5-2h under 18-22 ℃ of condition; The dimethylamine that is added is that mass percent is the dimethylamine agueous solution of 30-33%;
(3) in step (2) gained suspension, add epoxychloropropane, epoxychloropropane and dimethylamine mol ratio are (0.75～1.75): 1, add a small amount of ethylenediamine again, the ethylenediamine dosage is 1%～5% of epoxychloropropane and a dimethylamine gross mass, stirs 2～7h under 50 ℃～80 ℃ temperature;
(4) product after suction filtration step (3) stirs, the gained solids is the poly-epoxychloropropane dimethylamine cation bentonite, with distilled water washing gained solids to filtrate chloride ion-containing not, 60～80 ℃ of oven dry down, grind, cross 200 mesh sieves, activate 2.0 hours down, make the polyepoxy chloropropane dimethylamine cationic bentonite finished product at 104～110 ℃.
2. method for preparing poly-epoxychloropropane dimethylamine cation alta-mud as claimed in claim 1 is characterized in that, the main component of described sodium bentonite is a montmorillonite, expands doubly＞15 in colloid index＞100, and cation exchange capacity is 750mmol/kg; Chemical composition, in mass percent, SiO
2: 69.32%, Al
2O
3: 14.27%, CaO:1.99%, MgO:2.69%, Fe
2O
3: 1.84%, Na
2O:1.85%, K
2O:1.38%, other: 6.66%.
3. method for preparing poly-epoxychloropropane dimethylamine cation alta-mud as claimed in claim 1 is characterized in that, the stirring described in step (2) and (3) is to realize temperature controlled by the water-bath heating.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769191A (en) * | 2005-09-05 | 2006-05-10 | 暨南大学 | Bentonite base composite material for water treatment and its preparation method |
| CN1986044A (en) * | 2006-11-30 | 2007-06-27 | 山东大学 | Polyepoxy chloropropane dimethylamine cationic bentonite and its preparing method |
| CN101195664A (en) * | 2006-12-06 | 2008-06-11 | 新疆大学 | Method for producing organic/inorganic mixed mode semi-interpenetrating network configuration superpower water absorber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1769191A (en) * | 2005-09-05 | 2006-05-10 | 暨南大学 | Bentonite base composite material for water treatment and its preparation method |
| CN1986044A (en) * | 2006-11-30 | 2007-06-27 | 山东大学 | Polyepoxy chloropropane dimethylamine cationic bentonite and its preparing method |
| CN101195664A (en) * | 2006-12-06 | 2008-06-11 | 新疆大学 | Method for producing organic/inorganic mixed mode semi-interpenetrating network configuration superpower water absorber |
Non-Patent Citations (3)
| Title |
|---|
| Qian Li et al.Cationic polyelectrolyte/bentonite prepared by ultrasonictechnique and its use as adsorbent for Reactive Blue K-GLdye.Jounal of Hazardous Material147.2007,147370-380. * |
| 李倩等.阳离子聚合物聚环氧氯丙烷二甲胺/膨润土纳米复合材料的制备与性能.过程工程学报7 3.2007,7(3),598-603. |
| 李倩等.阳离子聚合物聚环氧氯丙烷二甲胺/膨润土纳米复合材料的制备与性能.过程工程学报7 3.2007,7(3),598-603. * |
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