CN101817536A - Novel process for producing organically modified bentonite - Google Patents
Novel process for producing organically modified bentonite Download PDFInfo
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- CN101817536A CN101817536A CN 201010168880 CN201010168880A CN101817536A CN 101817536 A CN101817536 A CN 101817536A CN 201010168880 CN201010168880 CN 201010168880 CN 201010168880 A CN201010168880 A CN 201010168880A CN 101817536 A CN101817536 A CN 101817536A
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Abstract
The invention relates to a novel process for producing organically modified bentonite, which is characterized by sequentially comprising the following steps of: 1) performing sodium modification on calcium base bentonite with a sodium base salt; 2) performing organic modification on the bentonite obtained by the step 1) with a quaternary ammonium salt; and 3) modifying the bentonite obtained by the step 2) with octadecanoic acid fatty acid. The final product obtained by modifying the common calcium base bentonite has the same viscosifying effect as the American natural sodium base bentonite.
Description
Technical field
The present invention relates to a kind of organic modified bentonite production technique.
Background technology
Wilkinite (Bentonite) claim swelling rock or otaylite again, is to be the clay rock of main component with the montmorillonite---the montmorillonite clay rock.The wilkinite translated name that China occurs is otaylite, bentonite, amargosite etc., and name accurately should be the montmorillonite clay.
Wilkinite is a kind of important nonmetallic minerals, and world's bentonite resource is abundant, is widely distributed, and different continents all have bentonite ore to distribute.Distributed more widely in the world is calcium-base bentonite, and sodium bentonite is then comparatively rare, and the place of production concentrates on a few countries.
The present bentonitic annual production of the U.S. is more than 400 ten thousand tons, along with the aggravation of oil crisis, and the increase of probing workload, the wilkinite product annual turnover of estimating U.S. from now on is about 6,000,000 tons.The insufficient country of Japonica type bentonite resource, but the prosperity of wilkinite processing industry mainly adopt imported raw material soil processing back to export back external.European countries' wilkinite sales volume is bigger, but main bentonite resource is by import.
The existing resources advantage of China's wilkinite has species the advantage again.At present relevant bentonitic main direction of studying is a Purification of Bentonite, the montmorillonite of the low degree of order of synthetic, and artificial modification's magnesium montmorillonite prepares high performance sial film with wilkinite, activation of bentonite and organise etc.
Wilkinite (montmorillonite) is for alumina octahedral sheet and silicon-oxy tetrahedron layer replace arrangement architecture, and this quilt is regarded as octahedral layer and is sandwiched between the two-layer tetrahedrallayer, so this structure is called 2: 1 type laminate structures.Because octahedral layer part A l
3+By Mg
2+Replace and be with negative charge, so often have Na between montmorillonite layer
+, K
+, Ca
+, H
+Plasma, these ions can carry out ion-exchange with other positively charged mineral ion, also can react with organic ion or molecule.
At present, no matter be petroleum drilling or geological prospecting drilling well, all adopt wilkinite preparation drilling mud in a large number.Wilkinite can improve mud yield and drilling benefit greatly as the synergistic agent that adds, and helps creeping into various complicated geologicals, and accident takes place in the prevention well.Because the development of China Petroleum increases with the wilkinite demand year by year to drilling fluid, wilkinite has a extensive future aspect petroleum drilling.
Drilling mud plays an important role in drilling well, and bore slurry and be divided into two classes: a class is to be mud, and carrier mainly is a water, and wilkinite is a thickening material; Another kind of is oil-base mud, and carrier is mainly diesel oil and original, because organic bentonite is mainly adopted in oil loving requirement.
The organic modification of domestic inorganic bentonite only limits to document, does not still have any patent report at present.
" organism is in the absorption contribution rate research at water _ dication organobentonite interface " (Shen Xueyou, Lu Yingying, Zhu Lizhong, journal of Zhejiang university (version of science), the 30th the 1st phase of volume, 69～74) and " organic performance in synthetic organobentonite of microwave and the planar water thereof " (Li Jiwu, Zhu Lizhong, Cai Wei are strong, China Environmental Science, 2004,24 (6) 665～669) CETRIMIDE POWDER (CTMAB) is disclosed and cetylpyridinium chloride (CPC) has carried out modification to wilkinite.
" experimental study of TDTMA_ pillared montmorillonite absorption oil of mirbane " (Wu Weimin, Wu Pingxiao, party's will, Zhu Nengwu, the mineral rock, the 28th the 2nd phase of volume, 17～21) find, utilize long chain quaternary organic cation (as palmityl trimethyl ammonium chloride) to after bentonite modified, cationic N end is adsorbed on electronegative clay surface, and alkyl chain is crowded together mutually and forms an organic phase.
" the bentonitic development of drilling fluid " (Wang Qingwei, Cui Yuncheng, Xuan Lifu, nonmetalliferous ore, the 23rd the 6th phase of volume, 29～30) point out, organobentonite in the mud mostly adopts distearyl dimethyl ammonium chloride salt and efficient wilkinite reaction to form, and this cationic bentonite has good affinity to oils.
" preparation of organo montmorillonite and sign " (Wang Chunyan, Li Xia, Harbin Teachers' Univ.'s natural science journal, the 19th the 1st phase of volume, 63～69) point out that in petroleum drilling industry, mud thickener, latex stablizer contained in organic drilling mud are organobentonite, this class mud is mainly used in deep-well, ultra deep well and offshore drilling, because of it has rheological and Portability preferably,, prevent corrosion so drilling well can be lubricated effectively; Simultaneously, it also be a kind of well carry glutinous, carry and cut auxiliary agent, can be mixed with good oil-base mud and high temperature resistance releasing stuck agent, the generation that improves drilling speed and minimizing accident greatly.
Nearly 10,000,000,000 tons of the natural montmorillonite ore reserves of finding out at present, wherein the reserves of the U.S., USSR (Union of Soviet Socialist Republics) and China account for 1/4 of world's geologic reserve.But distributed more widely in the world is calcium-base bentonite, accounts for the 70-80% of proven reserve, and the fine sodium bentonite is then more rare, and the place of production concentrates on Wyoming State, the South Dakota State, the North Dakota State, Montana State of the U.S. etc.Therefore, the prospecting of sodium bentonite resource is all attached great importance in countries in the world.
China's wilkinite kind has sodium base and hydrogen base, al bentonite concurrently substantially based on calcium-base bentonite.
In the oil drilling field, sodium bentonite mud yield height, tackifying is good, than calcium-base bentonite natural advantage is arranged.Even if after carrying out same organic modification, the thickening properties of sodium bentonite in oil-base mud also is much better than calcium-base bentonite.
Because China's wilkinite is substantially based on the calcium base, applicability is relatively poor, and can only be used to paint, coating etc. requires low industry, the application in the drilling well field to be difficult to out product, maybe can only be from external high price import sodium bentonite.
Summary of the invention
The novel process that the object of the present invention is to provide a kind of organic bentonite to produce, simple and easy to do, the product viscosity performance is good.
The concrete technical scheme that the present invention adopts is:
The novel process that a kind of organic bentonite of the present invention is produced is characterized in that, in turn includes the following steps:
1) adopt sodium base salt pair calcium-base bentonite to carry out sodium modification;
2) adopt quaternary ammonium salt that the wilkinite of step 1) is carried out organic modification;
3) wilkinite employing stearic acid lipid acid step 2) carries out modification.
Specifically be in turn include the following steps:
1) in reactor, drops into 150-250 weight part calcium-base bentonite, add 25-55 weight part sodium base salt, add the 25-35 weight parts water, stir in the spray mode;
2) add 40-60 weight part quaternary ammonium salt, after stirring, be rapidly heated to 80-95 ℃ confined reaction 15-25min;
3) methanol solution of adding stearic acid lipid acid stirs;
4) blanking, dry organic bentonite of the present invention.
The sodium base salt that adopts among the present invention, preferably a kind of in the inorganic salt such as sodium-chlor, yellow soda ash, sodium sulfate, sodium bicarbonate.
Described quaternary ammonium salt is a kind of in 4 bromide, tetraethylammonium bromide, distearyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, the palmityl trimethyl ammonium chloride, preferred distearyl dimethyl ammonium chloride.
Described stearic acid lipid acid is a kind of in stearic acid, sodium stearate and the calcium stearate.
Calcium ion exchange capacity in the calcium-base bentonite is relatively poor, is unfavorable for organic modification, thereby in the reaction starting stage, displaces calcium ion in the wilkinite in advance with the sodium ion in the inorganic salt, has improved bentonitic ion-exchange capacity.Especially with yellow soda ash, when sodium sulfate carries out modification, the calcium ion that displaces can form with carbonate, sulfate radical and be difficult for ionized lime carbonate, calcium sulfate, impels the permutoid reaction of sodium, calcium to carry out towards favourable direction.
It is organic modifiers that the present invention adopts distearyl dimethyl ammonium chloride, based on semidrying, by adding sodium base salt in the production process, common homemade calcium-base bentonite is carried out modification, compare with the U.S. natural sodium bentonite, on the tackify effect quite.
Embodiment
Embodiment 1
In reactor, drop into the homemade calcium-base bentonite of 200Kg, and add 25Kg yellow soda ash simultaneously, add 30Kg water in the spray mode, fully stir 30min after, add the 55Kg distearyl dimethyl ammonium chloride, continue to stir 10min.After stirring finishes, be rapidly heated to 90 ℃ confined reaction 20min.Reaction adds stearic methanol solution in the spray mode after finishing.Blanking changes baking procedure over to.
Be configured to the oil-base mud system, measure R600, R300 reading respectively, calculate the YP value according to YP=2*R300-R600 with the Fann35 viscometer.
Embodiment 2
In reactor, drop into the homemade calcium-base bentonite of 250Kg, and add 40Kg yellow soda ash simultaneously, add 30Kg water in the spray mode, fully stir 30min after, add the 50Kg distearyl dimethyl ammonium chloride, continue to stir 10min.After stirring finishes, be rapidly heated to 90 ℃ confined reaction 20min.Reaction adds stearic methanol solution in the spray mode after finishing.Blanking changes baking procedure over to.
Be configured to the oil-base mud system, measure R600, R300 reading respectively, calculate the YP value according to YP=2*R300-R600 with the Fann35 viscometer.
Embodiment 3
In reactor, drop into the homemade calcium-base bentonite of 150Kg, and add 55Kg yellow soda ash simultaneously, add 30Kg water in the spray mode, fully stir 30min after, add the 50Kg distearyl dimethyl ammonium chloride, continue to stir 10min.After stirring finishes, be rapidly heated to 90 ℃ confined reaction 20min.Reaction adds stearic methanol solution in the spray mode after finishing.Blanking changes baking procedure over to.
Be configured to the oil-base mud system, measure R600, R300 reading respectively, calculate the YP value according to YP=2*R300-R600 with the Fann35 viscometer.
Embodiment 4
In reactor, drop into the homemade calcium-base bentonite of 170Kg, and add 25Kg sodium-chlor simultaneously, add 30Kg water in the spray mode, fully stir 30min after, add the 40Kg distearyl dimethyl ammonium chloride, continue to stir 10min.After stirring finishes, be rapidly heated to 90 ℃ confined reaction 20min.Reaction adds stearic methanol solution in the spray mode after finishing.Blanking changes baking procedure over to.
Be configured to the oil-base mud system, measure R600, R300 reading respectively, calculate the YP value according to YP=2*R300-R600 with the Fann35 viscometer.
Embodiment 5
In reactor, drop into the homemade calcium-base bentonite of 190Kg, and add 25Kg sodium sulfate simultaneously, add 30Kg water in the spray mode, fully stir 30min after, add the 45Kg distearyl dimethyl ammonium chloride, continue to stir 10min.After stirring finishes, be rapidly heated to 90 ℃ confined reaction 20min.Reaction adds stearic methanol solution in the spray mode after finishing.Blanking changes baking procedure over to.
Be configured to the oil-base mud system, measure R600, R300 reading respectively, calculate the YP value according to YP=2*R300-R600 with the Fann35 viscometer.
Embodiment 6
In reactor, drop into the homemade calcium-base bentonite of 160Kg, and add the 25Kg sodium bicarbonate simultaneously, add 30Kg water in the spray mode, fully stir 30min after, add the 50Kg distearyl dimethyl ammonium chloride, continue to stir 10min.After stirring finishes, be rapidly heated to 90 ℃ confined reaction 20min.Reaction adds stearic methanol solution in the spray mode after finishing.Blanking changes baking procedure over to.
Be configured to the oil-base mud system, measure R600, R300 reading respectively, calculate the YP value according to YP=2*R300-R600 with the Fann35 viscometer.
The different sodium carbonate amounts of table 1. are to the influence of product performance
The dissimilar sodium salts of table 2. are to the influence of product performance
Claims (4)
1. the novel process that organic bentonite is produced is characterized in that, in turn includes the following steps:
1) adopt sodium base salt pair calcium-base bentonite to carry out sodium modification;
2) adopt quaternary ammonium salt that the wilkinite of step 1) is carried out organic modification;
3) adopt stearic acid lipid acid to step 2) wilkinite carry out modification.
2. the novel process that organic bentonite according to claim 1 is produced is characterized in that, in turn includes the following steps:
1) in reactor, drops into 150-250 weight part calcium-base bentonite, add 25-55 weight part sodium base salt, add the 25-35 weight parts water, stir in the spray mode;
2) add 40-60 weight part quaternary ammonium salt, after stirring, be rapidly heated to 80-95 ℃ confined reaction 15-25min;
3) methanol solution of adding stearic acid lipid acid stirs;
4) blanking, dry organic bentonite of the present invention.
3. the novel process that organic bentonite according to claim 1 and 2 is produced is characterized in that, described sodium base salt is a kind of in sodium-chlor, yellow soda ash, sodium sulfate, the sodium bicarbonate.
4. the novel process that organic bentonite according to claim 1 and 2 is produced is characterized in that described quaternary ammonium salt is a distearyl dimethyl ammonium chloride.
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| CN 201010168880 CN101817536A (en) | 2010-05-14 | 2010-05-14 | Novel process for producing organically modified bentonite |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102259881A (en) * | 2011-06-20 | 2011-11-30 | 浙江丰虹新材料股份有限公司 | Method for preparing high-viscosity organic bentonite by virtue of calcium-based bentonite |
| CN102295295A (en) * | 2011-06-13 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing organoclay by using composite organic modifier |
| 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 |
| CN103896294A (en) * | 2014-03-26 | 2014-07-02 | 芜湖恒杰膨润土科技有限公司 | Artificial sodium bentonite |
| CN103964453A (en) * | 2014-04-24 | 2014-08-06 | 福建鸿强有机膨润土有限公司 | Production method of organobentonite |
| CN105002353A (en) * | 2015-08-31 | 2015-10-28 | 中南大学 | Preparation method for pellet material by using dust containing carbon and iron and difficult to pelletize, and application thereof in iron ore power composite agglomeration process |
| CN105087912A (en) * | 2015-08-31 | 2015-11-25 | 中南大学 | Preparation method for humic acid modified bentonite for iron ore pellets and application of humic acid modified bentonite |
| CN107252873A (en) * | 2017-06-20 | 2017-10-17 | 广西大学 | A kind of hot investment casting is with bentonitic half-dried preparation method |
| CN109503945A (en) * | 2018-11-30 | 2019-03-22 | 广东威林工程塑料股份有限公司 | A kind of method that bicarbonate expands cheating engaging layer spacing and its application in modified high-molecular nanocomposite |
| CN112357929A (en) * | 2020-11-23 | 2021-02-12 | 江苏博联新材料科技有限公司 | Environment-friendly bentonite additive and preparation method thereof |
| CN113101863A (en) * | 2021-03-22 | 2021-07-13 | 吾尚良品环境服务(上海)有限公司 | Nano functional material composition and preparation method thereof |
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2010
- 2010-05-14 CN CN 201010168880 patent/CN101817536A/en active Pending
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| 《化工学报》 20040430 方晓明等 硬脂酸/ 膨润土纳米复合相变储热材料的制备、结构与性能 678-681 1-4 第55卷, 第4期 2 * |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295295A (en) * | 2011-06-13 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing organoclay by using composite organic modifier |
| CN102259881B (en) * | 2011-06-20 | 2013-03-20 | 浙江丰虹新材料股份有限公司 | Method for preparing high-viscosity organic bentonite by virtue of calcium-based bentonite |
| CN102259881A (en) * | 2011-06-20 | 2011-11-30 | 浙江丰虹新材料股份有限公司 | Method for preparing high-viscosity organic bentonite by virtue of calcium-based bentonite |
| 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 |
| CN103896294A (en) * | 2014-03-26 | 2014-07-02 | 芜湖恒杰膨润土科技有限公司 | Artificial sodium bentonite |
| CN103896294B (en) * | 2014-03-26 | 2016-08-24 | 芜湖恒杰膨润土科技有限公司 | A kind of artificial natridization's bentonite |
| CN103964453B (en) * | 2014-04-24 | 2016-03-09 | 福建鸿强有机膨润土有限公司 | A kind of bentonite making method |
| CN103964453A (en) * | 2014-04-24 | 2014-08-06 | 福建鸿强有机膨润土有限公司 | Production method of organobentonite |
| CN105087912A (en) * | 2015-08-31 | 2015-11-25 | 中南大学 | Preparation method for humic acid modified bentonite for iron ore pellets and application of humic acid modified bentonite |
| CN105002353A (en) * | 2015-08-31 | 2015-10-28 | 中南大学 | Preparation method for pellet material by using dust containing carbon and iron and difficult to pelletize, and application thereof in iron ore power composite agglomeration process |
| CN107252873A (en) * | 2017-06-20 | 2017-10-17 | 广西大学 | A kind of hot investment casting is with bentonitic half-dried preparation method |
| CN109503945A (en) * | 2018-11-30 | 2019-03-22 | 广东威林工程塑料股份有限公司 | A kind of method that bicarbonate expands cheating engaging layer spacing and its application in modified high-molecular nanocomposite |
| CN109503945B (en) * | 2018-11-30 | 2021-12-28 | 广东威林工程塑料股份有限公司 | Method for expanding interlayer spacing of montmorillonite by using bicarbonate and application of bicarbonate in modified polymer nanocomposite |
| CN112357929A (en) * | 2020-11-23 | 2021-02-12 | 江苏博联新材料科技有限公司 | Environment-friendly bentonite additive and preparation method thereof |
| CN113101863A (en) * | 2021-03-22 | 2021-07-13 | 吾尚良品环境服务(上海)有限公司 | Nano functional material composition and preparation method thereof |
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