CN1831048A - Siliver-carried micron kaolin and its prepn. method - Google Patents

Siliver-carried micron kaolin and its prepn. method Download PDF

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CN1831048A
CN1831048A CN 200610039389 CN200610039389A CN1831048A CN 1831048 A CN1831048 A CN 1831048A CN 200610039389 CN200610039389 CN 200610039389 CN 200610039389 A CN200610039389 A CN 200610039389A CN 1831048 A CN1831048 A CN 1831048A
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kaolin
silver
hours
microns
reaction
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CN 200610039389
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Chinese (zh)
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CN100432157C (en )
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郎建平
曹向前
陈阳
任志刚
尤振根
陈丽昆
李勇
张忠飞
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苏州大学
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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.

Description

载银微米高岭土及其制备方法 Silver and its preparation method micron kaolin

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 a silver kaolin microns. 本发明还涉及新型微米高岭土的制备方法。 The present invention further relates to a novel method for preparing micron kaolin.

背景技术 Background technique

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 antibacterial agent using long, 1939 to Hill et proved by means of experiments with a bactericidal silver ions. 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 the appropriate material as carrier, the prior reports, it is generally employed to make inorganic carrier sepiolite, bentonite, zeolites, phosphates, and silica gel adsorbent such as glass, the 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 Sepiolite silver antibacterial agent" (Wuhan University of Science and Technology 2003.8,63-66) reported in the "development of coal-based silver antibacterial agent" using sepiolite as carrier silver, in ( coal Chemical 2005,4,27-30) reported the use of Shenfu coal as silver carrier, reported in "preparation and properties of nano-silver antibacterial powder material" (Chinese ceramics 2001,2,1-3) in a zirconium phosphate as carrier nano silver antibacterial nano powder materials, reported in the "Study of TiO2 inorganic silver antibacterial agent preparation and properties" (functional materials 2005,3,474-476) TiO2 as a carrier to carrier silver, in the "Study on antibacterial properties of silver bentonite" natural bentonite silver carrier in the preparation of antibacterial agents (non-metallic minerals 2001,9,17-18). 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 required to support the role of ion-exchanged silver to silver exchange, and there is the problem of discoloration of the obtained silver antibacterial agent.

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 main component is silicon oxide and aluminum oxide, such as its use as a carrier, it is possible to improve the stability of silver ions to retard 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 poor ion exchange, can not be formed using the above inorganic carrier a silver ion exchange method. 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, conventional 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。 Object of the present invention to provide a silver microns kaolin, as a novel inorganic antimicrobial agent; while providing the steps of one micron silver kaolin small, easy operation, low cost, mild reaction conditions and methods 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 technical solution adopted by the invention is: A method for preparing a silver microns kaolin carrier, comprising the steps of: (1) Kaolin powder, a basic compound, urea, water at a weight ratio of 0.2 to 1 ~ 10 ~ 0.5:4 :0.1 mixed, electromagnetic stirring, for 4 hours to 12 hours, the basic compound selected from sodium hydroxide, sodium carbonate, one or two; (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) take the above powdery solid, a solution containing silver ions in , electromagnetic stirring at least 15 minutes, filtered off with suction, washed with obtaining the silver-loaded micrometer 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。 In the above technical solution, the use of 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℃。 It preferred technical solution, in the step (1), heating while stirring, and 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), the reaction is heated, temperature controlled 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。 In the above technical solution, said solution containing silver ions may be silver nitrate solution, in a concentration of between 0.02M to 0.06M.

优选的吸银时间在30分钟到2小时之间。 It 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 solution, the solution containing silver ions is a silver 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 uses silver claimed micron kaolin prepared above technical solutions available.

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。 In the present invention, kaolin via intercalation of a first set of reagents and a second set of reagents after the reaction, and finally used as a silver carrier absorption.

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。 Using the above technical solution, the present invention as compared with the prior art has the following advantages: 1. The present inventors obtained a novel inorganic antimicrobial agent silver microns kaolin, on the one hand through the ultra-fine kaolin processing, large specific surface area, silver having good adsorption and ion sustained release action, 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 selection of the intercalant and process parameters, such throughout the preparation of the intercalation step less, thus less environmental pollution; 3 of the present invention is less consumption of raw materials, widely available, are readily available; 4. present invention is simple, does not require mechanical polishing, low equipment requirements; 5. The method of the present invention mild reaction conditions, time is short, the whole process can be completed within a 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 a schematic view of a scanning electron microscope the particle size kaolin material used in the present invention products; Figure 2 a schematic view of a scanning electron microscope the particle size of the product an embodiment of the present embodiment of the invention.

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%。 Further described below of the present invention: Example I: 5g Kaolin, add 2.5 g of sodium hydroxide, 2.5 g of urea and 40 ml of deionized water was stirred for 4 hours at the solenoid 75 ℃, 10 ml of glacial acetic acid, 0.1 g of sodium dodecyl benzene sulfonate, the reaction was continued for 4 hours and filtered off with suction, washed with hot deionized water to give a white powder, after drying 105 deg.] C, to obtain micron kaolin is further used to prepare the silver microns kaolin yield It 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, a schematic diagram of a scanning electron microscope the particle size of the product invention.

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: Example take a soil resulting 8 parts, 1 g portions, each of 0.02M silver nitrate solution was added 10ml of 30 deg.] C under magnetic stirring time was 15 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 4 hours, 5 hours, filtered off with suction, washed with. 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 make the indicator, the amount of silver absorbed is measured to calculate the absorbance of silver, silver absorbance ratio (%) 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。 It showed overall longer the reaction time, the higher absorption rate 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。 But a few inflection described adsorption and desorption take some time to reach equilibrium, a short time-based adsorption reaction, such as 15 minutes, 30 minutes, 1 hour after the gradual desorption reaction strongly and finally reached equilibrium after 4 to 5 hours .

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 Three: Take a obtained in Example 1 gram of soil, 0.06M silver nitrate solution was added 10ml, the same operation according to the second embodiment. 吸银率从58.7%到73.3%,同样可得与时间的正比关系。 Also available silver absorption rate proportional to 73.3% from 58.7%, and 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 respective suction rate value is lower than the silver according to a second embodiment, and the amount of silver absorbed, but much larger than the value according to the second embodiment.

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 IV: Example take a one gram of soil obtained, 0.06M silver nitrate solution was added to 10ml, at 38 ℃ magnetic stirring for 10 hours, suction filtered, washed, and the filtrate titration. 吸银率为56.4%。 Silver absorption was 56.4%.

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。 Fifth Embodiment: Example take a one gram of soil obtained, 0.06M silver nitrate solution was added 10ml, add a few drops of nitric acid at 25 deg.] C Electromagnetic stirred for 1 hour, filtered off with suction, washed, 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。 Sixth Embodiment: Example take a soil obtained 1 g, 0.06M silver nitrate solution was added 10ml, add a few drops of nitric acid, 60 deg.] C under magnetic stirring for 4 hours and filtered off with suction, washed, and the filtrate titration. 吸银率仅为2.8%。 Silver absorption rate was 2.8%.

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 Seven: Take a resultant soil Example 1 g, was added a solution of 0.06M silver ammonia 10ml, 30 ℃ electromagnetic stirred for 40 minutes, suction filtered, and the filtrate titration. 吸银率为66.6%。 Silver absorption was 66.6%.

Claims (8)

  1. 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 preparation, characterized by comprising the steps of: (1) Kaolin powder, a basic compound, urea, water at a weight ratio of 0.2 to 1:0.1 ~ ~ 0.5:4 10 were mixed, electromagnetic stirring, for 4 hours to 12 hours, the basic compound selected from sodium hydroxide, sodium carbonate, one or two; (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) take the above powdery solid, a solution containing silver ions, the electromagnetic stirring at least 15 minutes, filtered off with suction, washed to obtain the silver kaolin microns.
  2. 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. Preparation method of claim 1 micron kaolin claim, wherein: said anionic surfactant is sodium dodecylbenzene sulfonate employed.
  3. 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 production method according to claim 1 micron kaolin, wherein: in said step (1), heating while stirring, the reaction temperature was controlled at 0 ℃ ~ 150 ℃.
  4. 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 production method according to claim 1 micron kaolin, wherein: in said step (2), the reaction is heated, temperature controlled at 0 ℃ ~ 150 ℃.
  5. 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。 The kaolin microns prepared according to the method according to claim 1, wherein: the solution containing silver ions is a silver nitrate solution, in a concentration of between 0.02M to 0.06M.
  6. 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。 6. The production method of claim 5 microns kaolin claim, wherein: Silver absorption time is between 30 minutes to 2 hours.
  7. 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。 The production method according to claim 1 micron kaolin, characterized in that: a solution containing silver ions is a silver-ammonia solution.
  8. 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 claim 1 using the obtained silver microns kaolin.
CN 200610039389 2006-03-29 2006-03-29 Siliver-carried micron kaolin and its prepn. method CN100432157C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101983568A (en) * 2010-11-25 2011-03-09 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
CN101347124B (en) 2008-06-20 2011-05-18 中国高岭土公司 Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent
CN105983386A (en) * 2015-02-26 2016-10-05 天津市四维康环保科技发展有限公司 Preparation and application of non-woven fabric

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101347124B (en) 2008-06-20 2011-05-18 中国高岭土公司 Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent
CN101983568A (en) * 2010-11-25 2011-03-09 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
CN105983386A (en) * 2015-02-26 2016-10-05 天津市四维康环保科技发展有限公司 Preparation and application of non-woven fabric

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