CN102701230A - Preparation method for inorganic-organic modified attapulgite clay - Google Patents
Preparation method for inorganic-organic modified attapulgite clay Download PDFInfo
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- CN102701230A CN102701230A CN2012101963939A CN201210196393A CN102701230A CN 102701230 A CN102701230 A CN 102701230A CN 2012101963939 A CN2012101963939 A CN 2012101963939A CN 201210196393 A CN201210196393 A CN 201210196393A CN 102701230 A CN102701230 A CN 102701230A
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Abstract
The invention discloses a preparation method for inorganic-organic modified attapulgite clay. The preparation method comprises the steps as follows: dissolving phosphate in water while stirring, then adding the preprocessed attapulgite clay to prepare a suspension liquid with the mass concentration of 5 to 20%; enabling the suspension liquid to pass through a 200-mesh sieve so as to remove impurities, reacting for 1 to 3 h at room temperature, then adding a certain amount of cationic surfactant, and continuously reacting for 1 to 2 h at the temperature of 20 to 90 DEG C so as to obtain pulp; and centrifuging, dehydrating, drying and grinding the obtained pulp so as to obtain the inorganic-organic modified attapulgite clay, wherein the addition amount of the phosphate is 1 to 10% of the attapulgite clay by mass, and the addition amount of the cationic surfactant is 0.05 to 5% of the attapulgite clay by mass. According to the preparation method, the process is easy to operate, the obtained inorganic-organic modified attapulgite clay has the characteristics of high viscosity, shear thinning and the like, and the requirements of fine chemical engineering industries, such as coatings, printing inks and cosmetics, on mineral thickeners are satisfied.
Description
Technical field
The present invention relates to a kind of method of modifying of attapulgite clay, a kind of preparation method of inorganic, organic modified attapulgite clay belongs to nonmetalliferous ore deep processing field specifically.
Background technology
At present; Increasing of many fine chemical products is glutinous, thickening, auxiliary rheological agents mostly are natural polymer or modified natural polymer product such as guar gum, Natvosol, Xylo-Mucine and chitosan derivatives etc., but the natural polymer product cost is higher.In recent years, the inorganic mineral viscosity increaser has received extensive concern, and the wilkinite thickener rheology agent is favored as the inorganic mineral viscosity increaser, and substitutes natural polymer aspect many and be used widely.Yet wilkinite electrolyte-resistant poor-performing.Along with the development of high-end product industries such as coating, printing ink, makeup, to increase that glutinous thickening material requirement improves day by day and consumption also in cumulative year after year.
Attapulgite clay is that a kind of 2:1 type layer catenate that is made up of two-layer silicon-oxy tetrahedron and layer of aluminum oxygen octahedra contains Shuifu County's zeopan mineral, and chemical constitution formula is Mg
5Si
8O
20(HO)
2(OH
2)
44H
2O is a kind of inorganic gel that good colloidal property is arranged, and can be used as suspension stabilizer, increases glutinous, thickening, auxiliary rheological agents is used for coating, paint, printing ink and household chemicals fields such as (makeup, toothpaste, cleansing milk etc.).But natural attapulgite clay is often with impurity such as pearl opal and quartz, and owing to interior reactive force between intensive static and hydrogen bond equimolecular, the suspension of attapulgite clay is relatively poor with dispersiveness simultaneously, thereby has limited the performance of attapulgite clay colloidal property.
Traditional method mainly adopts inorganic salt or organic surface active agent that attapulgite clay is carried out surface modification treatment, improves excellent intergranular reactive force through changing interlayer charge or excellent brilliant surface charge, and then improves colloidal property.Earlier carry out attapulgite clay inorganic modified yet seldom have; Change the interlayer charge of attapulgite clay; And then carry out organically-modifiedly, make excellent brilliant surface have wetting ability to change appropriate hydrophobicity into, thereby further improve the suspension and dispersed report of attapulgite clay.
Summary of the invention
To the deficiency of existing attapulgite clay surface-treated, the object of the invention is to provide a kind of preparation method of inorganic, organic modified attapulgite clay, its objective is the problems such as the existing attapulgite clay suspension of China and dispersiveness be not good that solve.
The technical problem that the present invention will solve realizes through following scheme: it is under whipped state, and phosphoric acid salt is dissolved in the water, adds then through pretreated attapulgite clay, processes the suspension-s of mass concentration 5-20%; Suspension-s is crossed 200 mesh sieves and is removed impurity, at room temperature reacts 1～3h, adds a certain amount of cats product continuation reaction 1～2h under 20-90 ℃ again and gets slurry; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay of two modifications.
Wherein, the attapulgite clay pretreatment process is: the attapulgite clay raw ore adds the moistening one-tenth water cut 35～50% of water, pushes through the twin rollers pair roller again.
Wherein, described phosphoric acid salt is any one or more in trisodium phosphate, sodium phosphate, Sodium phosphate, dibasic, SODIUM PHOSPHATE, MONOBASIC, Sodium hexametaphosphate 99, the sodium polyphosphate, and its add-on is 1%～10% of an attapulgite clay ore quality.
Wherein, Described cats product is any one or more in dodecyl trimethylammonium chlorine (bromine) change ammonium, tetradecyl trimethylammonium chlorine (bromine) change ammonium, cetyl trimethyl chlorine (bromine) change ammonium, octadecyl trimethylammonium chlorine (bromine) change ammonium, hexadecyldimethyl benzyl ammonium benzyl chloride (bromine) change ammonium, octadecyl dimethyl benzyl chlorine (bromine) change ammonium, didodecyldimethylammbromide bromide, two tetradecyl dimethyl-brometo de amonio, double hexadecyl dimethyl-brometo de amonio, two octadecyl dimethyl-brometo de amonio, benzyl trimethyl chlorine (bromine) change ammonium, benzyl triethyl ammonium chlorine (bromine) change ammonium, benzyl tripropyl chlorine (bromine) change ammonium, benzyl tributyl chlorine (bromine) the change ammonium, and add-on is 0.05～5% of an attapulgite clay ore quality.
Attapulgite clay be with the attapulgite be staple a kind of layer chain molecule structure with special performance contain Shuifu County's zeopan mineral since in forming process Si in the tetrahedron
4+By Fe
3+, Al
3+Al in ion exchange or the octahedron
3+By Fe
2+, Mg
2+Ion exchange, thereby produce electronegativity; For making charge balance, can carry out cationic exchange; For this reason, earlier with Na in the phosphoric acid salt
+Mg with the attapulgite clay interlayer
2+Or Ca
2+Exchange, and pass through the extension of phosphate molecule chain, increase brilliant steric hindrance repulsive interaction and the aquation repulsive interaction of attapulgite clay rod, thereby improve the dispersing property of attapulgite clay in water; On inorganic salt modification basis, adopt cats product, it is hydrophobic to make attapulgite clay rod crystalline substance change appropriateness into from wetting ability, the suspension property when further strengthening the attapulgite clay hydration, thus realize that increasing of attapulgite clay is glutinous.
The present invention has the following advantages:
(1) phosphoric acid salt modified attapulgite clay, the steric hindrance repulsive interaction and the aquation repulsive interaction that can increase attapulgite clay improve the dispersing property of attapulgite clay in water.
(2) attapulgite clay carries out cats product modification processing on phosphoric acid salt modification basis, and it is hydrophobic to make attapulgite clay rod crystalline substance change appropriateness into from wetting ability, the suspension property when strengthening the attapulgite clay hydration.
(3) product has excellent pH stability and shear shinning characteristic, with other colloids consistency and compatibility is preferably arranged, and can satisfy the demand of industry thickenings such as coating, printing ink, makeup.
Specific embodiments
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is the restriction to technical scheme.
Embodiment 1: water cut is pushed through twin rollers at 35% attapulgite clay; Under whipped state; Attapulgite clay after the extruding is added in the sodium phosphate aqueous solution, process the attapulgite clay mass concentration and be 5% suspension-s, the sodium phosphate add-on is 1% of an attapulgite clay ore quality; Suspension-s is crossed 200 mesh sieves and is removed impurity, and stirring reaction 1h adds palmityl trimethyl ammonium chloride continuation reaction 2h under 20 ℃ again and gets slurry, and the palmityl trimethyl ammonium chloride add-on is 0.05% of an attapulgite clay siccative quality; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay product of two modifications.Attapulgite clay raw ore k value is 942mPa.s, and its viscosity is 2682mPa.s after the said process modification, and rate of descent is less than 1% behind the 24h.
Embodiment 2: water cut is pushed through twin rollers at 40% attapulgite clay; Under whipped state; Attapulgite clay after the extruding is added in the trisodium phosphate aqueous solution, process the attapulgite clay mass concentration and be 10% suspension-s, the trisodium phosphate add-on is 3% of an attapulgite clay ore quality; Suspension-s is crossed 200 mesh sieves and is removed impurity, and stirring reaction 2h adds cetyl dimethyl benzyl ammonium bromide continuation reaction 1.5h under 40 ℃ again and gets slurry, and the cetyl dimethyl benzyl ammonium bromide add-on is 1% of an attapulgite clay ore quality; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay product of two modifications.Attapulgite clay raw ore k value is 942mPa.s, and its viscosity is 2825mPa.s after the said process modification, and rate of descent is less than 1% behind the 24h.
Embodiment 3: water cut is pushed through twin rollers at 45% attapulgite clay; Under whipped state; Attapulgite clay after the extruding is added in the biphosphate sodium water solution; Process the attapulgite clay mass concentration and be 15% suspension-s, the SODIUM PHOSPHATE, MONOBASIC add-on is 5% of an attapulgite clay ore quality; Suspension-s is crossed 200 mesh sieves and is removed impurity, and stirring reaction 3h adds didodecyldimethylammbromide bromide continuation reaction 2h under 60 ℃ again and gets slurry, and the didodecyldimethylammbromide bromide add-on is 2% of an attapulgite clay ore quality; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay product of two modifications.Attapulgite clay raw ore k value is 942mPa.s, and its viscosity is 2930mPa.s after the said process modification, and rate of descent is less than 1% behind the 24h.
Embodiment 4: water cut is pushed through twin rollers at 50% attapulgite clay; Under whipped state; Attapulgite clay after the extruding is added in the Sodium phosphate, dibasic aqueous solution; Process the attapulgite clay mass concentration and be 20% suspension-s, the SODIUM PHOSPHATE, MONOBASIC add-on is 7% of an attapulgite clay ore quality; Suspension-s is crossed 200 mesh sieves and is removed impurity, and stirring reaction 2h adds benzyl trimethyl ammonium chloride continuation reaction 1.5h under 80 ℃ again and gets slurry, and the benzyl trimethyl ammonium chloride add-on is 3% of an attapulgite clay ore quality; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay product of two modifications.Attapulgite clay raw ore k value is 942mPa.s, and its viscosity is 2766mPa.s after the said process modification, and rate of descent is less than 1% behind the 24h.
Embodiment 5: water cut is pushed through twin rollers at 45% attapulgite clay; Under whipped state; Attapulgite clay after the extruding is added in the aqueous solution of Sodium hexametaphosphate 99; Process the attapulgite clay mass concentration and be 10% suspension-s, the Sodium hexametaphosphate 99 add-on is respectively 9% of attapulgite clay ore quality; Suspension-s is crossed 200 mesh sieves and is removed impurity; Stirring reaction 1h; Add OTAC and benzyl triethyl ammonium bromide continuation reaction 1h under 90 ℃ again and get slurry, OTAC and benzyl triethyl ammonium bromide add-on are respectively 2% of attapulgite clay ore quality; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay product of two modifications.Attapulgite clay raw ore k value is 942mPa.s, and its viscosity is 2872mPa.s after the said process modification, and rate of descent is less than 2% behind the 24h.
Embodiment 6: water cut is pushed through twin rollers at 35% attapulgite clay; Under whipped state; Attapulgite clay after the extruding is added in the aqueous solution of sodium polyphosphate; Process the attapulgite clay mass concentration and be 5% suspension-s, the sodium polyphosphate add-on is respectively 10% of attapulgite clay ore quality; Suspension-s is crossed 200 mesh sieves and is removed impurity; Stirring reaction 3h; Add stearyl dimethyl benzyl ammonium chloride and distearyl dimethyl ammonium chloride continuation reaction 1h under 90 ℃ again and get slurry, stearyl dimethyl benzyl ammonium chloride and distearyl dimethyl ammonium chloride add-on are respectively 2.5% of attapulgite clay ore quality; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains the high glutinous attapulgite clay product of two modifications.Attapulgite clay raw ore k value is 942mPa.s, and its viscosity is 2862mPa.s after the said process modification, and rate of descent is less than 2% behind the 24h.
Claims (4)
1. the preparation method of inorganic, organic modified attapulgite clay, it is characterized in that: it is under whipped state, and phosphoric acid salt is dissolved in the water, adds then through pretreated attapulgite clay, processes the suspension-s of mass concentration 5-20%; Suspension-s is crossed 200 mesh sieves and is removed impurity, at room temperature reacts 1～3h, adds a certain amount of cats product continuation reaction 1～2h under 20-90 ℃ again and gets slurry; With the pulp centrifuged dehydration of gained, drying is pulverized, and obtains two modified attapulgite clays.
2. the preparation method of inorganic, organic modified attapulgite clay according to claim 1, it is characterized in that: the attapulgite clay pretreatment process is: the attapulgite clay raw ore adds the moistening one-tenth water cut 35～50% of water, pushes through the twin rollers pair roller again.
3. the preparation method of inorganic, organic modified attapulgite clay according to claim 1; It is characterized in that: described phosphoric acid salt is any one or more in trisodium phosphate, sodium phosphate, Sodium phosphate, dibasic, SODIUM PHOSPHATE, MONOBASIC, Sodium hexametaphosphate 99, the sodium polyphosphate, and its add-on is 1%～10% of an attapulgite clay ore quality.
4. the preparation method of inorganic, organic modified attapulgite clay according to claim 1; It is characterized in that: described cats product is any one or more in dodecyl trimethylammonium chlorine (bromine) change ammonium, tetradecyl trimethylammonium chlorine (bromine) change ammonium, cetyl trimethyl chlorine (bromine) change ammonium, octadecyl trimethylammonium chlorine (bromine) change ammonium, hexadecyldimethyl benzyl ammonium benzyl chloride (bromine) change ammonium, octadecyl dimethyl benzyl chlorine (bromine) change ammonium, didodecyldimethylammbromide bromide, two tetradecyl dimethyl-brometo de amonio, double hexadecyl dimethyl-brometo de amonio, two octadecyl dimethyl-brometo de amonio, benzyl trimethyl chlorine (bromine) change ammonium, benzyl triethyl ammonium chlorine (bromine) change ammonium, benzyl tripropyl chlorine (bromine) change ammonium, benzyl tributyl chlorine (bromine) the change ammonium, and add-on is 0.05～5% of an attapulgite clay ore quality.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145919A (en) * | 2013-03-11 | 2013-06-12 | 中科院广州能源所盱眙凹土研发中心 | Method for preparing cellulose cationic flocculant by modifying attapulgite |
| CN103708482A (en) * | 2013-12-23 | 2014-04-09 | 杨立新 | Preparation method of medicinal attapulgite powder preparation |
| CN103749571A (en) * | 2013-12-23 | 2014-04-30 | 杨立新 | Attapulgite sterilization mite suppressor and preparation method thereof |
| CN104479422A (en) * | 2014-12-24 | 2015-04-01 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Preparation method of photochromic Maya blue pigment |
| CN104772107A (en) * | 2015-03-23 | 2015-07-15 | 广州优克日用品有限公司 | Modified attapulgite material, preparation method and application thereof |
| CN104893730A (en) * | 2015-05-14 | 2015-09-09 | 江苏玖力纳米材料科技有限公司 | Petroleum soil adsorption-degradation modified material |
| CN106118679A (en) * | 2016-06-28 | 2016-11-16 | 安徽金联地矿科技有限公司 | A kind of attapulgite base soil conditioner and preparation method thereof |
| CN106948214A (en) * | 2017-04-12 | 2017-07-14 | 明光市国星凹土有限公司 | A kind of preparation method of attapulgite filler |
| CN108812880A (en) * | 2018-05-03 | 2018-11-16 | 中国科学院兰州化学物理研究所 | A kind of fruit and vegetable fresh-keeping agent with suppression sterilizing function living |
| CN109824300A (en) * | 2019-03-01 | 2019-05-31 | 中兴文物建筑装饰工程有限公司 | A kind of glutinous rice mortar and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145919A (en) * | 2013-03-11 | 2013-06-12 | 中科院广州能源所盱眙凹土研发中心 | Method for preparing cellulose cationic flocculant by modifying attapulgite |
| CN103708482B (en) * | 2013-12-23 | 2016-01-20 | 杨立新 | A kind of preparation method of medicinal attapulgite powder preparation |
| CN103708482A (en) * | 2013-12-23 | 2014-04-09 | 杨立新 | Preparation method of medicinal attapulgite powder preparation |
| CN103749571A (en) * | 2013-12-23 | 2014-04-30 | 杨立新 | Attapulgite sterilization mite suppressor and preparation method thereof |
| CN103749571B (en) * | 2013-12-23 | 2016-01-20 | 杨立新 | A kind of attapulgite sterilization mite suppressor and preparation method thereof |
| CN104479422A (en) * | 2014-12-24 | 2015-04-01 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Preparation method of photochromic Maya blue pigment |
| CN104772107A (en) * | 2015-03-23 | 2015-07-15 | 广州优克日用品有限公司 | Modified attapulgite material, preparation method and application thereof |
| CN104772107B (en) * | 2015-03-23 | 2018-03-16 | 广州优克日用品有限公司 | A kind of modified attapulgite soil material and its preparation method and application |
| CN104893730A (en) * | 2015-05-14 | 2015-09-09 | 江苏玖力纳米材料科技有限公司 | Petroleum soil adsorption-degradation modified material |
| CN106118679A (en) * | 2016-06-28 | 2016-11-16 | 安徽金联地矿科技有限公司 | A kind of attapulgite base soil conditioner and preparation method thereof |
| CN106948214A (en) * | 2017-04-12 | 2017-07-14 | 明光市国星凹土有限公司 | A kind of preparation method of attapulgite filler |
| CN108812880A (en) * | 2018-05-03 | 2018-11-16 | 中国科学院兰州化学物理研究所 | A kind of fruit and vegetable fresh-keeping agent with suppression sterilizing function living |
| CN109824300A (en) * | 2019-03-01 | 2019-05-31 | 中兴文物建筑装饰工程有限公司 | A kind of glutinous rice mortar and preparation method thereof |
| CN109824300B (en) * | 2019-03-01 | 2021-04-09 | 中兴文物建筑装饰工程有限公司 | Glutinous rice mortar and preparation method thereof |
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Application publication date: 20121003 |