CN102295295A - Method for preparing organoclay by using composite organic modifier - Google Patents
Method for preparing organoclay by using composite organic modifier Download PDFInfo
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- CN102295295A CN102295295A CN2011101574442A CN201110157444A CN102295295A CN 102295295 A CN102295295 A CN 102295295A CN 2011101574442 A CN2011101574442 A CN 2011101574442A CN 201110157444 A CN201110157444 A CN 201110157444A CN 102295295 A CN102295295 A CN 102295295A
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Abstract
The invention belongs to the technical field of fine chemical industry, and relates to a method for preparing organic bentonite by using a composite organic modifier. The method comprises steps that: (1) 40 to 60 parts of sodium-based bentonite dry material are dissolved in 500 to 900 parts of deionized water, the solution is stirred with a high speed, such that a suspension system is formed; (2) 20 to 30 parts of the composite organic modifier are mixed into 200 to 400 parts of a solvent, and are dissolved by stirring, such that a homogenous system is formed; (3) under high-speed stirring, the solution obtained in the steps (2) is quickly added to the suspension system obtained in the step (1), and the mixture is allowed to react for 1 to 4 hours under a temperature of 60 to 85 DEG C; (4) the product obtained in the step (3) is aged for 5 to 12 hours, superfluous ions in the product are removed by washing, the product is filtered, the obtained solid product is dried in a vacuum environment under a temperature of 50 to 80 DEG C, the dried product is crushed, and are sieved by a sieve of 200 meshes, such that the organoclay product is obtained. With the method provided by the invention, property (interlayer spacing) of the organoclay can be substantially improved, organoclay with uniform quality can be prepared, and organoclay property can be improved.
Description
Technical field
The invention belongs to the fine chemical technology field, be specifically related to method for preparing organobentonite.
Background technology
Wilkinite is the moisture clay pit based on montmorillonite, molecular formula: Na
x(H
2O)
4(Al
2-XMg
0.83) Si
4O
10) (OH)
2, because it has special nature, as: swelling, cohesiveness, adsorptivity, catalytic, thixotropy, suspension and cationic exchange or the like; Be widely used in each industrial circle, people are referred to as " omnipotent soil ".
Organobentonite is a natural montmorillonite modification deep processed product, also is a kind of important fine chemical product.Its character has hydrophobic lipophilic characteristics, in organic solvent, have good dispersiveness, lyotropy, emulsifying property, can be used as antisettling agent, viscosifying agent, tackifier and suspension agent etc., obtained using widely at industrial circles such as paint, printing ink, high temperature grease, makeup, casting, petroleum drilling, agricultural chemicals.Organobentonite has the good adsorption performance, can be used for removing pollutents such as organism in the water, heavy metal, gather the organic pollutant in the Atmospheric particulates, separate the gaseous state organic double compound as chromatographic media, also can be used as the Hazardous wastes stablizer, effectively stop the migration of organic pollutant, also be widely used at aspects such as underground water and soil pollution reparations in addition.
Because of montmorillonite has laminate structure, the tradable positively charged ion of its interlayer replaces with organic cation, thereby forms organobentonite.Because the sodium ion in the montmorillonite is easier to be replaced by organic cation,, reacts with organic compounds again and make organobentonite so when producing organobentonite or use the high pure sodium base bentonite, or carry out sodium with calcium-base bentonite and handle.
The bentonite preparation is exactly the process that wilkinite is organised, and normally carries out ion-exchange, the organobentonite product that obtained performance (interlamellar spacing) is superior with the quaternary amine and the wilkinite of carbonatoms between 12-18.Usually preparation bentonite method has: the single cats product of adding prepare organophilic clay or again this basis go up and add sequestrant and prepare organophilic clay; Add negatively charged ion or male-female tensio-active agent and come modification to prepare organophilic clay, or adopt secondary intercalation to prepare organophilic clay.The organophilic clay performance (interlamellar spacing) that these methods obtain is unsatisfactory.
Summary of the invention
The objective of the invention is to propose a kind of method that adopts compound organic modifiers to prepare organophilic clay.
The inventive method can improve organobentonite performance (interlamellar spacing) significantly
,Make the uniform organobentonite of quality, help improving bentonitic performance.
Main technical schemes of the present invention is: compound organic modifiers prepares the method for organophilic clay, is undertaken by following step:
(1) 40～60 parts sodium bentonite siccative is dissolved in 500～900 parts the deionized water, high-speed stirring forms suspension system;
(2) with 20～30 parts of compound organic modifiers, miscible in 200-400 part solvent, stirring and dissolving forms the homogeneous system;
(3) under the high-speed stirring state, the solution in the step (2) is joined rapidly in the suspension system of step (1), 60～85 ℃ of reactions 1-4 hour;
(4) with aging 5～12 hours of the product that obtains in the step (3), unnecessary ion in the flush away product filters, and is then that the solid product of gained is dry under 50～80 ℃ of vacuum environments, pulverizes 200 mesh sieves, promptly obtains the organophilic clay product.
Usually, described sodium bentonite is a pulverulent mixture, montmorillonite weight percentage 80～100%, and its cation exchange capacity (CEC) is 80～300mmol/100g.
Described compound organic modifiers is that two or more quaternary amine allotment forms, between the carbon chain lengths C12～C18 of quaternary amine, as Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, cetyl pyridinium, octadecyl trimethylammonium bromide, stearyl dimethyl benzyl ammonium chloride etc.; The add-on of quaternary amine is 70～120% molar equivalents of sodium bentonite cation exchange capacity (CEC).
Described solvent is deionized water or lower alcohol.
Embodiment:Further specify content of the present invention below in conjunction with embodiment:
Embodiment 1
50 parts sodium base soil is distributed in 700 parts of deionized waters, and high-speed stirring obtains steady suspension, adjusts pH value to 7 ~ 8 of suspension, and is standby; 10.02 parts of Trimethyllaurylammonium bromides and 11.84 parts of cetyl trimethylammonium bromides are added in 300 parts of deionized waters together, stir, make it to become the solution for standby of clear.Under the high-speed stirring state, Trimethyllaurylammonium bromide and cetyl trimethylammonium bromide composite solution are added to rapidly in the suspension, reaction is 2 hours in the time of 60 ℃, and aging 12 hours of product is removed Br remaining in the product repeatedly with deionized water
-, filter, the organobentonite of preparation in 60 ℃ of vacuum-dryings, pulverizing and cross 200 mesh sieves, is promptly obtained the organobentonite product.
Embodiment 2
50 parts sodium base soil is distributed in 700 parts of deionized waters, and high-speed stirring obtains steady suspension, adjusts pH value to 7 ~ 8 of suspension, and is standby; 10.92 parts of Tetradecyl Trimethyl Ammonium Bromide and 11.84 parts of cetyl trimethylammonium bromides are added in 300 parts of deionized waters together, stir, make it to become the solution for standby of clear.Under the high-speed stirring state, Tetradecyl Trimethyl Ammonium Bromide and cetyl trimethylammonium bromide composite solution are added to rapidly in the suspension, reaction is 2 hours in the time of 70 ℃, and aging 12 hours of product is removed Br remaining in the product repeatedly with deionized water
-, filter, the organobentonite of preparation in 60 ℃ of vacuum-dryings, pulverizing and cross 200 mesh sieves, is promptly obtained the organobentonite product.
Embodiment 3
50 parts sodium base soil is distributed in 700 parts of deionized waters, and high-speed stirring obtains steady suspension, adjusts pH value to 7 ~ 8 of suspension, and is standby; 10.92 parts of bromohexadecane yl pyridines and 11.84 parts of cetyl trimethylammonium bromides are added in 300 parts of deionized waters together, stir, make it to become the solution for standby of clear.Under the high-speed stirring state, bromohexadecane yl pyridines and cetyl trimethylammonium bromide composite solution are added to rapidly in the suspension, reaction is 2 hours in the time of 75 ℃, and aging 12 hours of product is removed Br remaining in the product repeatedly with deionized water
-, filter, the organobentonite of preparation in 60 ℃ of vacuum-dryings, pulverizing and cross 200 mesh sieves, is promptly obtained the organobentonite product.
Embodiment 4
50 parts sodium base soil is distributed in 700 parts of deionized waters, and high-speed stirring obtains steady suspension, adjusts pH value to 7 ~ 8 of suspension, and is standby; 12.70 parts of octadecyl trimethylammonium bromides and 11.84 parts of cetyl trimethylammonium bromides are added in 300 parts of methyl alcohol together, stir, make it to become the solution for standby of clear.Under the high-speed stirring state, octadecyl trimethylammonium bromide and cetyl trimethylammonium bromide composite solution are added to rapidly in the suspension, reaction is 2 hours in the time of 80 ℃, and aging 12 hours of product is removed Br remaining in the product repeatedly with deionized water
-, filter, the organobentonite of preparation in 60 ℃ of vacuum-dryings, pulverizing and cross 200 mesh sieves, is promptly obtained the organobentonite product.
Embodiment 5
50 parts sodium base soil is distributed in 700 parts of deionized waters, and high-speed stirring obtains steady suspension, and the pH value of adjusting suspension is to 7-~ 8, and is standby; 13.78 parts of stearyl dimethyl benzyl ammonium chlorides and 11.84 parts of cetyl trimethylammonium bromides are added in 300 parts of ethanol together, stir, make it to become the solution for standby of clear.Under the high-speed stirring state, stearyl dimethyl benzyl ammonium chloride and cetyl trimethylammonium bromide composite solution are added to rapidly in the suspension, reaction is 2 hours in the time of 80 ℃, and aging 12 hours of product is removed Br remaining in the product repeatedly with deionized water
-And Cl
-, filter, the organobentonite of preparation in 60 ℃ of vacuum-dryings, pulverizing and cross 200 mesh sieves, is promptly obtained the organobentonite product.
Comparative Examples 1
50 parts sodium base soil is distributed in 700 parts of deionized waters, and high-speed stirring obtains steady suspension, and the pH value of adjusting suspension is to 7-~ 8, and is standby; 23.68 parts of cetyl trimethylammonium bromides are added 300 parts go to stir in the ethanol, make it to become the solution for standby of clear.Under the high-speed stirring state, cetyl trimethylammonium bromide solution is added to rapidly in the suspension, reaction is 2 hours in the time of 80 ℃, and aging 12 hours of product is removed Br remaining in the product repeatedly with deionized water
-, filter, the organobentonite of preparation in 60 ℃ of vacuum-dryings, pulverizing and cross 200 mesh sieves, is promptly obtained the organobentonite product.
Interlamellar spacing test: adopt x-ray powder diffraction instrument, according to the Bragg equation: (wherein d is an interlamellar spacing to 2dsin2 θ=n λ, θ is an input angle, λ=0.1540nm, wavelength for incident ray, n is a diffraction progression, gets 1) can calculate sodium bentonite and bentonite interlamellar spacing d (001).
Evaluation result is as follows:
| Sequence number | Project | Incident angle 2 θ ( 0) | Interlamellar spacing d (001)/nm |
| １ | Sodium base soil | 7.15 | 1.235 |
| ２ | Reference examples 1 | 4.01 | 2.196 |
| ３ | Example 1 | 3.44 | 2.562 |
| ４ | Example 2 | 3.16 | 2.785 |
| ５ | Example 3 | 2.89 | 3.048 |
| ６ | Example 4 | 2.54 | 3.462 |
| ７ | Example 5 | 2.44 | 3.607 |
By above-mentioned data as can be seen: the organobentonite interlamellar spacing of the present invention's development is significantly improved, and shows the organobentonite superior performance of present method preparation.
Claims (5)
1. compound organic modifiers prepares the method for organophilic clay, it is characterized in that the preparation method is undertaken by following step:
(1) 40～60 parts sodium bentonite siccative is dissolved in 500～900 parts the deionized water, high-speed stirring forms suspension system;
(2) with 20～30 parts of compound organic modifiers, miscible in 200-400 part solvent, stirring and dissolving forms the homogeneous system;
(3) under the high-speed stirring state, the solution in the step (2) is joined rapidly in the suspension system of step (1), 60～85 ℃ of reactions 1-4 hour;
(4) with aging 5～12 hours of the product that obtains in the step (3), unnecessary ion in the flush away product filters, and is then that the solid product of gained is dry under 50～80 ℃ of vacuum environments, pulverizes 200 mesh sieves, promptly obtains the organophilic clay product.
2. preparation method according to claim 1 is characterized in that sodium bentonite is a pulverulent mixture, montmorillonite weight percentage 80～100%, and its cation exchange capacity (CEC) is 80～300mmol/100g.
3. method according to claim 1 is characterized in that compound organic modifiers is that two or more quaternary amine allotment forms, between the carbon chain lengths C12～C18 of quaternary amine; Add-on is 70～120% molar equivalents of sodium bentonite cation exchange capacity (CEC).
4. method according to claim 3 is characterized in that quaternary amine is a Trimethyllaurylammonium bromide, Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethylammonium bromide, cetyl pyridinium, octadecyl trimethylammonium bromide, stearyl dimethyl benzyl ammonium chloride.
5. method according to claim 1 is characterized in that described solvent is deionized water or lower alcohol.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303934A (en) * | 2013-05-20 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method of organic bentonite with high specific surface area |
| CN103773324A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for improving gel forming rate of organic soil in oil-base drilling fluid mud |
| CN104745169A (en) * | 2015-02-15 | 2015-07-01 | 中国石油集团西部钻探工程有限公司 | Compound emulsifying viscosity reducer for thickened oil and preparation method of compound emulsifying viscosity reducer |
| CN105733529A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Method for preparing organobentonite for white oil based drilling fluid |
| CN106040242A (en) * | 2016-06-12 | 2016-10-26 | 常州大学 | Method for preparing bentonite-based porous material loaded cobalt oxide catalysts |
| CN106040229A (en) * | 2016-06-12 | 2016-10-26 | 常州大学 | Method for preparing load manganese dioxide catalyst |
| CN106076328A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of the porous material loading silver oxide for processing waste gas |
| CN106076341A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of porous material loading nickel oxide catalyst |
| CN106076309A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of the cerium oxide catalyst processing vehicle exhaust |
| CN107282000A (en) * | 2017-07-20 | 2017-10-24 | 安徽国能亿盛环保科技有限公司 | A kind of preparation method of modified silver type bentonite organic wastewater adsorbent |
| CN108597676A (en) * | 2017-11-27 | 2018-09-28 | 昆明贵金属研究所 | A kind of preparation method and application containing organobentonite low-temperature solidified silver paste |
| CN108912802A (en) * | 2018-08-20 | 2018-11-30 | 杭州海迪斯新材料有限公司 | Bentonite activity thickens anti-settling rheological agent and preparation method thereof |
| CN111377638A (en) * | 2018-12-29 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Liquid alkali-free accelerator for improving cohesiveness of sprayed concrete and preparation method thereof |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103773324A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Method for improving gel forming rate of organic soil in oil-base drilling fluid mud |
| CN103773324B (en) * | 2012-10-25 | 2016-08-24 | 中国石油化工股份有限公司 | Improve organoclay method of plastic rate in oil base drilling fluid mud |
| CN103303934A (en) * | 2013-05-20 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method of organic bentonite with high specific surface area |
| CN103303934B (en) * | 2013-05-20 | 2015-04-08 | 中国石油天然气股份有限公司 | Preparation method of organic bentonite with high specific surface area |
| CN105733529A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Method for preparing organobentonite for white oil based drilling fluid |
| CN104745169A (en) * | 2015-02-15 | 2015-07-01 | 中国石油集团西部钻探工程有限公司 | Compound emulsifying viscosity reducer for thickened oil and preparation method of compound emulsifying viscosity reducer |
| CN106076328A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of the porous material loading silver oxide for processing waste gas |
| CN106040229A (en) * | 2016-06-12 | 2016-10-26 | 常州大学 | Method for preparing load manganese dioxide catalyst |
| CN106040242A (en) * | 2016-06-12 | 2016-10-26 | 常州大学 | Method for preparing bentonite-based porous material loaded cobalt oxide catalysts |
| CN106076341A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of porous material loading nickel oxide catalyst |
| CN106076309A (en) * | 2016-06-12 | 2016-11-09 | 常州大学 | A kind of preparation method of the cerium oxide catalyst processing vehicle exhaust |
| CN106040242B (en) * | 2016-06-12 | 2018-12-28 | 常州大学 | A kind of preparation method of bentonite base porous material loading cobalt oxide catalyst |
| CN106076341B (en) * | 2016-06-12 | 2018-12-28 | 常州大学 | A kind of preparation method of porous material loading nickel oxide catalyst |
| CN107282000A (en) * | 2017-07-20 | 2017-10-24 | 安徽国能亿盛环保科技有限公司 | A kind of preparation method of modified silver type bentonite organic wastewater adsorbent |
| CN108597676A (en) * | 2017-11-27 | 2018-09-28 | 昆明贵金属研究所 | A kind of preparation method and application containing organobentonite low-temperature solidified silver paste |
| CN108597676B (en) * | 2017-11-27 | 2019-09-27 | 昆明贵金属研究所 | A kind of preparation method and application containing organobentonite low-temperature solidified silver paste |
| CN108912802A (en) * | 2018-08-20 | 2018-11-30 | 杭州海迪斯新材料有限公司 | Bentonite activity thickens anti-settling rheological agent and preparation method thereof |
| CN111377638A (en) * | 2018-12-29 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | Liquid alkali-free accelerator for improving cohesiveness of sprayed concrete and preparation method thereof |
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Application publication date: 20111228 |