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Publication numberCN1831048 A
Publication typeApplication
Application numberCN 200610039389
Publication dateSep 13, 2006
Filing dateMar 29, 2006
Priority dateMar 29, 2006
Also published asCN100432157C
Publication number200610039389.6, CN 1831048 A, CN 1831048A, CN 200610039389, CN-A-1831048, CN1831048 A, CN1831048A, CN200610039389, CN200610039389.6
Inventors郎建平, 曹向前, 陈阳, 任志刚, 尤振根, 陈丽昆, 李勇, 张忠飞
Applicant苏州大学
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Siliver-carried micron kaolin and its prepn. method
CN 1831048 A
Abstract
This invention discloses a strong practical micrometer kaolin preparation method. The method is that coal series kaolin is continuous agitated with two group reagent for reaction at certain temperature for several hours for fully reaction, then they are filtrated and washed, the micrometer kaolin is got after drying. If the product is used to absorb silver, good effect can be got. The source of material in this invention is wide, its practibility is strong, the reaction condition is mildness, and there is no need of special device.
Claims(8)  translated from Chinese
1.一种载银微米高岭土的制备方法,其特征在于,包括下列步骤:(1)将高岭土粉末、碱性化合物、尿素、水按重量比为1∶0.2~1∶0.1~0.5∶4~10进行混合,电磁搅拌,反应4小时至12小时,所述碱性化合物选自氢氧化钠、碳酸钠中的一种或两种;(2)再加入1~3份冰醋酸,0.05~0.2份阴离子表面活性剂,继续反应4小时至12小时,过滤、洗涤、烘干,获得白色粉末状固体;(3)取上述粉末状固体,加入含银离子的溶液中,电磁搅拌至少15分钟,抽滤、洗涤,获得所述的载银微米高岭土。 A silver microns kaolin production method, characterized by comprising the steps of: (1) Kaolin powder, a basic compound, urea, water weight ratio of 0.2 to 1:0.1 ~ ~ 0.5:4 10 were mixed, electromagnetic stirring, the reaction from 4 to 12 hours, the basic compound selected from sodium hydroxide, sodium carbonate, one or two; and (2) adding 1 to 3 parts of glacial acetic acid, 0.05 to 0.2 parts of an anionic surfactant, reaction was continued for 4-12 hours, filtering, washing and drying, to obtain a white powder; (3) to take the above powdery solid, was added a solution containing silver ions, the electromagnetic stirring at least 15 minutes, filtration, washing, obtaining the silver contained micron kaolin.
2.根据权利要求1所述的微米高岭土的制备方法,其特征在于:所述阴离子表面活性剂采用十二烷基苯磺酸钠。 2.1 The preparation of micron kaolin according to claim, characterized in that: the use of the anionic surfactant sodium dodecylbenzenesulfonate.
3.根据权利要求1所述的微米高岭土的制备方法,其特征在于:在所述步骤(1)中,搅拌的同时进行加热,使反应温度控制在0℃~150℃。 The micrometer according to claim 1 wherein the preparation of kaolin claim, characterized in that: in said step (1), and stirred while heating, the reaction temperature was controlled at 0 ℃ ~ 150 ℃.
4.根据权利要求1所述的微米高岭土的制备方法,其特征在于:在所述步骤(2)中,反应时加热,温度控制在0℃~150℃。 The kaolin clay according to claim 1, wherein the preparation of micron claim, characterized in that: in said step (2), when the reaction was heated, the temperature control at 0 ℃ ~ 150 ℃.
5.根据权利要求1所述的微米高岭土的制备方法,其特征在于:所述含银离子的溶液为硝酸银溶液,浓度在0.02M至0.06M之间。 5. The method for preparing micron kaolin according to claim 1, characterized in that: a solution containing silver ions is silver nitrate solution, in a concentration between 0.02M to 0.06M.
6.根据权利要求5所述的微米高岭土的制备方法,其特征在于:吸银时间在30分钟到2小时之间。 5 6. The method for preparing micron kaolin according to claim, characterized in that: suction silver time between 30 minutes to 2 hours.
7.根据权利要求1所述的微米高岭土的制备方法,其特征在于:所述含银离子的溶液为银氨溶液。 1 according to the method for preparing micron kaolin claim, characterized in that: a solution containing silver ions is silver ammonia solution.
8.采用权利要求1的方法获得的载银微米高岭土。 8. The method of using silver micron claim 1 obtained kaolin.
Description  translated from Chinese
载银微米高岭土及其制备方法 Silver micron kaolin and its preparation method

技术领域 FIELD

本发明涉及微米高岭土载银的制备方法。 The present invention relates to a method for preparing micron silver of kaolin. 本发明还涉及新型微米高岭土的制备方法。 The present invention also relates to a novel method for preparing micron kaolin.

背景技术 BACKGROUND

银作为抗菌剂使用由来已久,1939年Hill等用实验手段证明了银离子具有杀菌能力。 Silver as an antimicrobial agent for a long time, in 1939 with Hill and other experimental methods have proven silver ion disinfection. 作为抗菌剂必须有合适的材料作为载体,现有报道中,一般采用海泡石、膨润土、沸石、磷酸盐、吸附性硅胶以及玻璃等做无机载体,构成无机载银抗菌剂。 As an antimicrobial agent must have suitable material as a carrier, existing reports, the general sepiolite, bentonite, zeolite, phosphate, silica and glass adsorption of inorganic carriers do constitute inorganic silver antibacterial agent. 例如:在《海泡石载银抗菌剂的制备研究》(武汉科技学院学报2003.8,63-66)中报道了使用海泡石作载体载银,在《煤基载银抗菌剂的研制》(煤化工2005,4,27-30)中报道了使用神府煤作载体载银,在《纳米载银抗菌粉体材料的制备工艺与性能》(中国陶瓷2001,2,1-3)中报道了以纳米磷酸锆为载体的纳米载银抗菌粉体材料,在《载银TiO2无机抗茵剂的制备及性能研究》(功能材料2005,3,474-476)中报道了以TiO2作为载体载银,在《载银膨润土的抗菌性能研究》(非金属矿2001,9,17-18)中使用天然膨润土作载体载银制备抗菌剂。 For example: In the "Preparation of meerschaum silver antibacterial agent" (Wuhan University of Science and Technology 2003.8,63-66) reported the use of sepiolite as a carrier of silver, in the "development of coal-based silver antibacterial agent" ( Coal Chemical 2005,4,27-30) reported the use of Shenfu coal as a carrier of silver, reported in the "Preparation and properties of nano silver antimicrobial powder material" (Chinese ceramics 2001,2,1-3) in the nano-zirconium phosphate as the carrier nano-silver antibacterial powder materials, "Preparation and Properties of TiO2 silver inorganic antimicrobial agent" (Functional Materials 2005,3,474-476) reports with TiO2 as a carrier Silver, in the "anti-bacterial properties of silver Bentonite" (non-metallic mineral 2001,9,17-18) is used as a carrier of natural bentonite preparation silver antibacterial agent. 然而,这些报道中的载体都须经过离子交换作用交换银才能载银,并且,获得的载银抗菌剂存在变色问题。 However, these reports are subject to carrier ion exchange to exchange silver silver, and there is discoloration silver antibacterial agents obtained.

高岭土的主要成份是氧化硅和氧化铝,如能用其作为载体,有可能提高银离子的稳定性,以延缓其变色过程。 Kaolin is the main component silicon oxide and alumina, as it can be used as a carrier, it is possible to improve the stability of silver ions in order to delay the discoloration process. 我国有丰富的高岭土资源,但因其离子交换能力差,无法采用上述离子交换方法来形成银的无机载体。 China has abundant kaolin resources, but because of the ion exchange capacity of poor, can not use the ion exchange method to form an inorganic carrier silver. 同时,现有的高岭土产品,细度不够,如需作为载体使用,需要进行超细处理,以提高其比表面积。 Meanwhile, existing kaolin products, insufficient fineness, For use as a carrier, the need for ultra-fine processing, to increase its specific surface area.

发明内容 SUMMARY

本发明目的是提供一种载银微米高岭土,以作为一种新的无机抗菌剂;同时提供一种该载银微米高岭土的步骤少、易操作、成本低、反应条件温和的制备方法。 The purpose of the present invention is to provide a silver micron kaolin, as a new kind of inorganic antimicrobial agent; while providing a step that is less silver micron kaolin, easy operation, low cost, mild reaction conditions, method of preparation.

为达到上述目的,本发明采用的技术方案是:一种载银微米高岭土的制备方法,包括下列步骤:(1)将高岭土粉末、碱性化合物、尿素、水按重量比为1∶0.2~1∶0.1~0.5∶4~10进行混合,电磁搅拌,反应4小时至12小时,所述碱性化合物选自氢氧化钠、碳酸钠中的一种或两种;(2)再加入1~3份冰醋酸,0.05~0.2份阴离子表面活性剂,继续反应4小时至12小时,过滤、洗涤、烘干,获得白色粉末状固体;(3)取上述粉末状固体,加入含银离子的溶液中,电磁搅拌至少15分钟,抽滤、洗涤,获得所述的载银微米高岭土。 To achieve the above object, the present invention is used: a method for producing silver micron kaolin carrier, comprising the steps of: (1) Kaolin powder, a basic compound, urea, water weight ratio of 0.2 to 1 :0.1 ~ 0.5:4 to 10 were mixed, electromagnetic stirring, the reaction from 4 to 12 hours, the basic compound selected from sodium hydroxide, sodium carbonate, one or two; and (2) adding 1 to 3 parts of glacial acetic acid, 0.05 to 0.2 parts of an anionic surfactant, reaction was continued for 4-12 hours, filtering, washing and drying, to obtain a white powder; (3) to take the above powdery solid, was added a solution of silver ion-containing , electromagnetic stirring at least 15 minutes, filtration, washing, to obtain said silver microns kaolin.

上述技术方案中,所述阴离子表面活性剂采用十二烷基苯磺酸钠。 The above-described technical solution, using the anionic surfactant sodium dodecylbenzenesulfonate.

优选的技术方案,在所述步骤(1)中,搅拌的同时进行加热,使反应温度控制在0℃~150℃。 Preferable embodiment, in the step (1), and stirred while heating, the reaction temperature was controlled at 0 ℃ ~ 150 ℃. 在所述步骤(2)中,反应时加热,温度控制在0℃~150℃。 In the step (2), when the reaction was heated, the temperature control at 0 ℃ ~ 150 ℃.

上述技术方案中,所述含银离子的溶液可以是硝酸银溶液,浓度在0.02M至0.06M之间。 The above-described technical solution, a solution containing silver ions may be silver nitrate solution, at a concentration between 0.02M to 0.06M.

优选的吸银时间在30分钟到2小时之间。 Preferred silver suction time between 30 minutes to 2 hours.

另一种技术方案,所述含银离子的溶液为银氨溶液。 Another aspect, the silver ion-containing solution is a silver containing ammonia solution.

本发明同时请求保护采用上述技术方案制备获得的载银微米高岭土。 The present invention also claimed silver micron kaolin using the technical proposal preparation obtained.

本发明中,高岭土经第一组试剂插层反应后再和第二组试剂反应,最后用做吸银的载体。 The present invention, the first set of reagent kaolin intercalation reaction and then a second set of reagent and reaction, and finally used as carrier absorption silver.

由于上述技术方案运用,本发明与现有技术相比具有下列优点:1.本发明获得了一种新的无机抗菌剂载银微米高岭土,一方面高岭土经过超细处理,比表面积大,对银离子具有很好的吸附和缓释作用,另一方面,由于铝的存在,提高了银离子的稳定性,延缓了其变色过程;2.本发明通过对插层剂和工艺参数的选择,使得整个制备过程插层步骤少,因而对环境污染较小;3.本发明原料消耗少,来源广泛,容易获得;4.本发明操作简单,不需要机械研磨,设备要求低;5.本发明方法的反应条件温和,时间短,一天内可完成全过程。 Due to the use of the technical proposal, the present invention over the prior art has the following advantages: 1. The present invention to obtain a new inorganic antibacterial agent containing silver micron kaolin, on the one hand through ultrafine kaolin processing, large surface area, for silver has good adsorption and ion sustained release, on the other hand, due to the presence of aluminum, to improve the stability of silver ions, delaying the discoloration process; 2. the present invention by intercalating agent and the choice of process parameters, such that The whole preparation process intercalation step less, and thus less environmental pollution; 3. less consumption of raw materials of the present invention, a wide range of sources, readily available; 4. The present invention is simple, does not require mechanical grinding, low equipment requirements; 5. method of the present invention The mild reaction conditions, the time is short, the whole process can be completed within one day.

附图说明 Brief Description

附图1为本发明产品所用原料高岭土的扫描电镜粒径示意图;附图2为本发明实施例一产品的扫描电镜粒径示意图。 Figure 1 of the present invention product SEM schematic raw kaolin with particle size; Figure 2 is a schematic diagram illustrating a scanning electron microscope of a particle size of the product embodiments.

具体实施方式 DETAILED DESCRIPTION

下面对本发明作进一步描述:实施例一:取5克煤系高岭土,加2.5克氢氧化钠、2.5克尿素、40毫升去离子水在75℃下电磁搅拌4小时,加入10毫升冰醋酸、0.1克十二烷基苯磺酸钠,继续反应4小时,抽滤,用热去离子水洗涤,得白色粉末,105℃烘干后,即得到微米高岭土,进一步用于制备载银微米高岭土,产率为99.7%。 The present invention will be further described: Example One: Take 5 g coal, kaolin, plus 2.5 g of sodium hydroxide, 2.5 g of urea, 40 ml of deionized water and stirred for 4 h at 75 ℃ under electromagnetic, adding 10 ml of glacial acetic acid, 0.1 g of sodium dodecylbenzenesulfonate, reaction was continued for 4 hours, suction filtered, washed with hot deionized water to give a white powder, 105 ℃ after drying, to obtain micron kaolin is further used for the preparation of silver microns kaolin, production was 99.7%.

参见附图2,所述发明产品的扫描电镜粒径示意图。 Referring to Figure 2, the invention is a schematic diagram of a scanning electron microscope the particle size of the product.

实施例二:取实施例一所得土8份,每份1克,各加0.02M硝酸银溶液10ml,30℃下电磁搅拌时间分别为15分钟、30分钟、1小时、1.5小时、2小时、2.5小时、4小时、5小时,抽滤、洗涤。 Example II: Take a resultant soil embodiment 8 parts, each 1 g, 0.02M silver nitrate solution was added to each 10ml, 30 ℃ under magnetic stirring for 15 minutes, respectively, 30 minutes, 1 hour, 1.5 hours, 2 hours cases, 2.5 hours, 4 hours, 5 hours, suction filtered, and washed. 滤液用0.04M的硫氰酸铵溶液滴定,以硫酸铁铵做指示剂,测量吸收的银量,计算出吸银率,吸银率(%)依次为95.3、96.1、96.4、95.3、95.1、98.0、99.0。 The filtrate was titrated with a 0.04M solution of ammonium thiocyanate, ammonium ferric sulfate to do an indicator measuring the absorption of silver, calculated the rate of absorption of silver, silver absorption rate (%) followed 95.3,96.1,96.4,95.3,95.1, 98.0,99.0. 总体表明反应时间越长,吸银率越高。 Overall showed longer reaction time, the higher the rate of absorption of silver. 但有几个拐点,说明吸附和解吸达到平衡需要一定的时间,短时间内以吸附反应为主,如15分钟、30分钟,1小时后解吸反应逐渐强烈,最后在4~5小时后达到平衡。 However, there are several inflection point, indicating equilibrium adsorption and desorption take some time, a short time with the main adsorption reaction, such as 15 minutes, 30 minutes, 1 hour after the desorption reaction gradually strongly and finally reached equilibrium at 4 to 5 hours after the .

实施例三:取实施例一所得土1克,加0.06M硝酸银溶液10ml,操作同实施例二。 EXAMPLE III: Take one embodiment, the resulting one gram of soil, plus 0.06M silver nitrate solution 10ml, operating same as in Example II. 吸银率从58.7%到73.3%,同样可得与时间的正比关系。 Silver absorption rate from 58.7% to 73.3%, the same can have positive relationship with time. 虽然相应吸银率的数值低于实施例二的值,而吸收银的量却远大于实施例二的值。 Although the corresponding silver absorption rate value is lower than the second example of implementation, and the amount of absorption of silver has a value far greater than the implementation of the two cases.

实施例四:取实施例一所得土1克,加0.06M硝酸银溶液10ml,38℃下电磁搅拌10小时,抽滤、洗涤,滤液滴定。 Example Four: Take one obtained in Example 1 g soil, plus 0.06M silver nitrate solution 10ml, at 38 ℃ electromagnetic stirring 10 hours, suction filtered, washed, and the filtrate titration. 吸银率为56.4%。 Absorption rate of 56.4% silver.

实施例五:取实施例一所得土1克,加0.06M硝酸银溶液10ml,加几滴硝酸,25℃下电磁搅拌1小时,抽滤、洗涤,滤液滴定。 Example Five: Take one obtained in Example 1 g soil, plus 0.06M silver nitrate solution 10ml, add a few drops of nitric acid, at 25 ℃ electromagnetic stirring 1 hour, filtration, washing, and the filtrate titration. 吸银率仅为0.8%。 Silver absorption rate was 0.8%.

实施例六:取实施例一所得土1克,加0.06M硝酸银溶液10ml,加几滴硝酸,60℃下电磁搅拌4小时,抽滤、洗涤,滤液滴定。 Example Six: Take one obtained in Example 1 g soil, plus 0.06M silver nitrate solution 10ml, add a few drops of nitric acid, at 60 ℃ electromagnetic stirring for 4 hours, filtration, washing, and the filtrate titration. 吸银率仅为2.8%。 Absorption rate was 2.8% silver.

实施例七:取实施例一所得土1克,加0.06M银氨溶液10ml,30℃下电磁搅拌40分钟,抽滤、洗涤,滤液滴定。 EXAMPLE VII: Take one embodiment, the resulting one gram of soil, plus 0.06M silver ammonia solution 10ml, 30 ℃ under electromagnetic stirring for 40 minutes, filtration, washing, and the filtrate titration. 吸银率为66.6%。 Absorption rate of 66.6% silver.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
CN101347124BJun 20, 2008May 18, 2011中国高岭土公司Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent
CN101983568A *Nov 25, 2010Mar 9, 2011中国地质大学(武汉);重庆国际复合材料有限公司Halloysite Ag-carrying antibacterial agent and preparation method thereof
Classifications
International ClassificationC09C1/42, C09C3/06
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