CN108473319A - 多孔质碳材料及其制造方法、以及过滤器、片材和催化剂用载体 - Google Patents
多孔质碳材料及其制造方法、以及过滤器、片材和催化剂用载体 Download PDFInfo
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- CN108473319A CN108473319A CN201780007080.5A CN201780007080A CN108473319A CN 108473319 A CN108473319 A CN 108473319A CN 201780007080 A CN201780007080 A CN 201780007080A CN 108473319 A CN108473319 A CN 108473319A
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- 239000000463 material Substances 0.000 title claims description 43
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- 239000011148 porous material Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims description 34
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- 241000196324 Embryophyta Species 0.000 claims description 25
- 235000013339 cereals Nutrition 0.000 claims description 23
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- 235000007164 Oryza sativa Nutrition 0.000 claims description 19
- 235000009566 rice Nutrition 0.000 claims description 19
- 239000010903 husk Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
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- 230000000052 comparative effect Effects 0.000 description 15
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- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
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- 244000058871 Echinochloa crus-galli Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 235000013405 beer Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- 230000037213 diet Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
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- 238000000855 fermentation Methods 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000019713 millet Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 239000011592 zinc chloride Substances 0.000 description 1
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Classifications
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Abstract
本发明涉及一种多孔质碳材料,所述多孔质碳材料的粒径为10μm以上且1cm以下,堆比重为0.20g/cm3以上,并且中孔容积为0.10cm3/g以上。
Description
技术领域
本发明涉及一种多孔质碳材料及其制造方法、以及过滤器、片材和催化剂用载体。
背景技术
活性炭所代表的多孔质碳材料是将以植物性原料(例如木浆、椰子壳、稻壳等)、矿物性原料(例如石炭、焦油、石油沥青等)、以及合成树脂等为原料的碳化物在高温下用气体或药品进行处理以活化,从而形成微细孔而得到的。该微细孔在碳内部构成网状,该微细孔产生了大的表面积,因此上述多孔质碳材料的吸附能力优异。因此,一直以来上述多孔质碳材料被用于除去恶臭、除去溶液中的杂质、回收及除去溶剂蒸气等各种用途。而且,上述多孔质碳材料还被用于担载催化剂的催化剂用载体。
作为来自植物的多孔质碳材料,例如公开了一种通过将来自植物的材料碳化后用酸或碱进行处理而得到的多孔质碳材料,该多孔质碳材料基于氮BET法的比表面积值为10m2/克以上,硅的含有率为1重量%以下,并且细孔的容积为0.1cm3/克以上(参照专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2008-273816号公报
发明内容
技术问题
在多孔质碳材料中,中孔发达的碳材料在大分子的吸附或高速吸附能力上优异。然而,这样的多孔质碳材料由于空隙多、堆比重小,所以例如在滤芯等重视单位体积性能的情况下,与一般的来自椰子壳的活性炭相比,只能填充1/5~1/4的重量。
因此,中孔发达的碳材料,虽然单位重量的吸附特性优异,但在观察单位体积的性能时,无法发挥其优越性的例子较多,存在着难以将作为滤芯等的性能发挥出比以往材料更高性能的问题。
本发明的课题在于:解决上述现有的诸多问题,达到以下目的。
即,本发明的目的在于:提供一种中孔发达、同时堆比重大的多孔质碳材料及其制造方法、以及使用了上述多孔质碳材料的过滤器、滤芯、片材和催化剂用载体。
解决问题的方案
用于解决上述课题的方法如下。即:
<1>一种多孔质碳材料,其特征在于,
粒径为10μm以上且1cm以下,
堆比重为0.20g/cm3以上,并且
中孔容积为0.10cm3/g以上。
<2>上述<1>所述的多孔质碳材料,其中,包含来自植物的材料。
<3>上述<2>所述的多孔质碳材料,其中,上述来自植物的材料为稻壳。
<4>一种过滤器,其特征在于,具有上述<1>~<3>中任一项所述的多孔质碳材料。
<5>上述<4>所述的过滤器,上述过滤器为净水用过滤器。
<6>上述<4>所述的过滤器,上述过滤器为空气净化用过滤器。
<7>一种滤芯,其特征在于,具有上述<4>~<6>中任一项所述的过滤器。
<8>一种片材,其特征在于,具有上述<1>~<3>中任一项所述的多孔质碳材料。
<9>一种催化剂用载体,其特征在于,具有上述<1>~<3>中任一项所述的多孔质碳材料。
<10>一种多孔质碳材料的制造方法,其特征在于,该制造方法是上述<1>~<3>中任一项所述的多孔质碳材料的制造方法,包括以下工序:
将来自植物的材料加压成型,得到成型物;
将上述成型物碳化,得到碳化物;以及
将上述碳化物活化。
<11>上述<10>所述的多孔质碳材料的制造方法,其中,上述来自植物的材料为稻壳。
<12>上述<10>~<11>中任一项所述的多孔质碳材料的制造方法,其中,上述得到成型物的工序是指将含水率为3质量%以上且30质量%以下的上述来自植物的材料加压成型的工序。
发明效果
根据本发明,可以解决上述现有的诸多问题,达到上述目的,可以提供一种中孔发达、同时堆比重大的多孔质碳材料及其制造方法、以及使用了上述多孔质碳材料的过滤器、滤芯、片材和催化剂用载体。
附图说明
图1是显示实施例1和比较例1的粒径与堆比重的关系的曲线图。
图2是显示实施例1和比较例1的残留氯除去性能的曲线图。
图3是显示实施例2和比较例2的残留氯除去性能的曲线图。
具体实施方式
(多孔质碳材料)
本发明的多孔质碳材料满足以下的(1)~(3)。
(1)粒径为10μm以上且1cm以下。
(2)堆比重为0.20g/cm3以上。
(3)中孔容积为0.1cm3/g以上。
<粒径>
上述粒径不足10μm的多孔质碳材料,其堆比重不易变大(例如不易达到0.2g/cm3以上)。上述粒径超过1cm的多孔质碳材料,通过酸处理或碱处理除去其灰分所需的时间容易变长,制造效率会降低。
上述粒径例如可以通过使用激光衍射/散射式粒径分布测定装置LA-950(HORIBA公司制造)来求出。使用LA-950,通过湿式法在粒径为0.01μm~3,000μm的范围测定粒径分布。上述粒径是指,在横轴代表粒径、纵轴代表个数频率进行作图的粒径分布中,分布的中央值所对应的粒径(中值粒径)。
<堆比重>
上述多孔质碳材料的堆比重为0.20g/cm3以上,优选为0.20g/cm3以上且0.40g/cm3以下,更优选为0.20g/cm3以上且0.35g/cm3以下。
中孔发达的(即中孔容积为0.1cm3/g以上的)多孔质碳材料,通常堆比重为0.10g/cm3左右。因此,以单位体积来看,无法发挥大分子的吸附或高速吸附能力优异的优越性。另一方面,堆比重为0.20g/cm3以上时,无论是从单位体积来看、还是从单位重量来看,均可发挥大分子的吸附或高速吸附能力优异的优越性。
堆比重是指,使粉末自然落到一定容积的容器中进行填充等,用形成了规定形状的粉末的质量除以此时的体积而求得的比重(单位体积的质量),堆比重越小越蓬松。
<中孔容积>
上述多孔质碳材料的中孔容积为0.1cm3/g以上,优选0.1cm3/g以上且0.3cm3/g以下,更优选0.1cm3/g以上且0.2cm3/g以下。上述中孔容积不足0.1cm3/g时,很难说中孔发达,无法得到大分子的吸附或高速吸附能力优异的优越性。另一方面,若上述中孔容积过大,则难以得到大的堆比重。
上述多孔质碳材料具有多个细孔(孔隙)。细孔分为中孔、微孔、大孔。这里,中孔是指孔径为2nm~50nm的细孔,微孔是指孔径小于2nm的细孔,大孔是指孔径大于50nm的细孔。
上述中孔容积例如可以使用以下的装置进行测定。
使用Micromeritics Japan合同会社制造的3FLEX测定氮吸附等温线,根据BJH法可以算出中孔容积。
上述BJH法被广泛用作细孔分布分析法。在根据BJH法进行细孔分布分析时,首先,通过使氮作为吸附分子吸脱附于吸附剂(多孔质碳材料),求出脱附等温线。然后,根据求出的脱附等温线,求出从细孔被吸附分子(例如氮)填满的状态到吸附分子阶段性地脱离时的吸附层的厚度、和此时产生的孔的内径(芯半径的2倍),根据式(1)算出细孔半径rp,根据式(2)算出细孔容积。然后,通过由细孔半径和细孔容积将相对于细孔径(2rp)的细孔容积变化率(dVp/drp)作图,得到细孔分布曲线(参照日本Bell株式会社制造BELSORP-mini和BELSORP分析软件的手册、第85页~第88页)。
rp=t+rk (1)
Vpn=Rn·dVn-Rn·dtn·c·ΣApj (2)
其中,Rn=rpn 2/(rkn-1+dtn)2 (3)
这里,
rp:细孔半径;
rk:细孔半径rp的细孔内壁在其压力下吸附了厚度为t的吸附层时的芯半径(内径/2)
Vpn:发生氮的第n次脱离时的细孔容积;
dVn:此时的变化量;
dtn:发生氮的第n次脱离时的吸附层的厚度tn的变化量;
rkn:此时的芯半径;
c:固定值;
rpn:发生氮的第n次脱离时的细孔半径。
另外,ΣApj表示从j=1到j=n-1的细孔的壁面面积的累积值。
[具体的测定方法]
通过准备30mg多孔质碳材料,使用设定为测定相对压力为(P/P0)0.0000001~0.995的范围的条件的3FLEX能够测定中孔容积。
<多孔质碳材料的原材料>
上述多孔质碳材料的原材料优选为来自植物的材料。当原材料来自植物时,容易将中孔容积值调整至上述所期望的值。另外,即使在环境负担少方面,也具有以植物为来源的优点。
对上述来自植物的材料没有特别限定,可以根据目的而适当选择,例如可以列举:米(稻)、大麦、小麦、黑麦、稗(紫穗稗)、粟(小米)等的稻壳或麦秆、或者芦苇、裙带菜茎。而且,例如还可以列举陆生的维管束植物、蕨类植物、苔藓植物、藻类、海草。尚需说明的是,以这些材料作为原料,可以单独使用,也可以将多种混合使用。另外,对来自植物的材料的形状或形态也没有特别限定,例如可以是稻壳或麦秆其本身,或者可以是干燥处理品。而且,在啤酒或洋酒等饮食品加工中,还可以使用进行了发酵处理、焙煎处理、萃取处理等各种处理的产物。特别是,从谋求资源化产业废弃物的角度考虑,优选使用脱粒等加工后的麦秆或稻壳。这些加工后的麦秆或稻壳例如可易于从农业合作社或酒类制造公司、食品公司大量获取。
对上述多孔质碳材料的制造方法没有特别限定,可以根据目的而适当选择,优选后述的多孔质碳材料的制造方法。
(多孔质碳材料的制造方法)
本发明的多孔质碳材料的制造方法包括以下工序:成型物制作工序、碳化物制作工序、活化工序,优选包括脱灰分工序,根据需要,还包括其他工序。
上述多孔质碳材料的制造方法是制造本发明的上述多孔质碳材料的方法。
<成型物制作工序>
作为上述成型物制作工序,只要是将来自植物的材料加压成型而得到成型物的工序即可,没有特别限定,可以根据目的而适当选择。
对上述来自植物的材料没有特别限定,可以根据目的而适当选择,例如可以列举上述多孔质碳材料的说明中例示的上述来自植物的材料。其中,在容易制造所期望的多孔质碳材料方面,优选稻壳。
对上述成型物的形状没有特别限定,可以根据目的而适当选择。
在上述加压成型中,例如使用通常用于生物质成型的造粒机来进行,加入水分使破碎的稻壳达到3质量%以上且30质量%以下、优选5质量%以上且20质量%以下的含水率进行成型。此时的压力根据通过成型机时的金属模与稻壳的摩擦阻抗来决定,因此优选根据成型物的大小来调整水分量。
另外,在上述加压成型中,有时会因摩擦而产生热,但也可以利用加热装置进行加热。
通过适当调整水分、压力和热,提取上述来自植物的材料中所含的水溶性成分,推测其将粉体彼此粘合,形成成型物。
通过将上述来自植物的材料加压成型,与未进行加压成型时相比,可得到中孔发达、同时堆比重大的多孔质碳材料。
<碳化物制作工序>
作为上述碳化物制作工序,只要是将上述成型物炭化(碳化)而得到炭化物(碳质物质)的工序即可,没有特别限定,可以根据目的而适当选择。
上述炭化(碳化)通常是指,对有机物质(本发明中是指来自植物的材料)进行热处理将其转化成碳质物质(例如参照JIS M0104-1984)。尚需说明的是,作为用于碳化的环境,可以列举隔绝了氧的环境,具体而言,可以列举真空环境、氮气或氩气的惰性气体环境、将上述成型物形成一种蒸烤状态的环境。作为达到碳化温度为止的升温速度,在所述环境下可以列举1℃/分钟以上、优选3℃/分钟以上、更优选5℃/分钟以上。另外,作为碳化时间的上限,可以列举10小时、优选7小时、更优选5小时,但并不限于此。碳化时间的下限只要是上述成型物确实被碳化的时间即可。
作为上述热处理的温度,例如可以列举300℃~1,000℃等。
<活化工序>
作为上述活化工序,只要是活化上述碳化物的工序即可,没有特别限定,可以根据目的而适当选择,例如可以列举气体活化法、药品活化法等。
这里,活化是指使碳材料的细孔结构发达、并附加细孔。
作为上述气体活化法,是指使用氧或水蒸气、二氧化碳、空气等作为活化剂,在所述气体环境下、例如在700℃~1,000℃下加热上述碳化物数十分钟~数小时,从而利用上述碳化物中的挥发成分或碳分子使微细结构发达。尚需说明的是,加热温度只要根据来自植物的材料的种类、气体的种类或浓度等适当选择即可,优选为800℃~950℃。
上述药品活化法是指,使用氯化锌、氯化铁、磷酸钙、氢氧化钙、碳酸镁、碳酸钾、硫酸等代替气体活化法中使用的氧或水蒸气,使上述碳化物活化,用盐酸清洗,并用碱性水溶液调整pH,再使其干燥。
<脱灰分工序>
作为上述脱灰分工序,只要是除去上述碳化物中的灰分的工序即可,没有特别限定,可以根据目的而适当选择,例如可以列举将上述碳化物浸在酸水溶液或碱水溶液中的方法等。
在上述脱灰分工序之前,优选将上述碳化物粉碎,使上述碳化物达到酸水溶液或碱水溶液容易渗透的大小。
以下给出上述多孔质碳材料的制造方法之一例。
将稻壳加压成型得到的成型物在氮气流中、在500℃下加热5小时使其碳化,得到碳化物。之后,将10g该碳化物装入氧化铝制坩埚中,在氮气流中(10升/分钟)以5℃/分钟的升温速度升温至1,000℃。之后,在1,000℃下碳化5小时,转化成碳质物质(多孔质碳材料前体),之后冷却至室温。尚需说明的是,在碳化和冷却中,继续流入氮气。接下来,将碳质物质粗粉碎至容易进行碱处理的1cm以下的大小,用1mol%的氢氧化钠水溶液除去材料内的灰分。之后,清洗材料,除去材料表面的碱,再进行清洗。之后,在水蒸气环境下对材料进行950℃的热处理,得到堆比重高的来自植物的多孔质碳材料。
(片材)
本发明的片材具有本发明的上述多孔质碳材料,根据需要,还具有其他构件。
上述片材例如可以通过将含有上述多孔质碳材料的粉末进行湿式抄纸而得到。例如,使用捣碎机、打浆机、匀浆机等装置混合含有上述多孔质碳材料的粉末,进行剪切,得到均匀分散的浆料,将所得浆料以规定的流量流到线材上,进行脱水,从而可以调整至任意的基重。之后,经过加压部分,通过干燥器部分将片材干燥,使用压延机部分使片材表面变得平滑,之后通过用卷轴卷绕等公知的技术,制造片材即可。片材的厚度只要使用热压辊等调整至任意的厚度等即可。
(过滤器)
本发明的过滤器具有本发明的上述多孔质碳材料,根据需要,还具有其他构件。
上述过滤器例如用作净水用过滤器、空气净化用过滤器等。
上述过滤器例如将上述片材成型而获得。
作为用于获得上述过滤器的成型法,例如可以列举:将本发明的上述片材缠绕、进行热处理以形成圆柱状或圆筒状过滤器的方法;或者,将片材层叠后冲裁成任意的形状以形成过滤器的方法等,但并不限于这些。
(滤芯)
本发明的滤芯至少具有本发明的上述过滤器,根据需要,还具有外壳等其他构件。
上述过滤器例如收纳在上述外壳中。
上述外壳例如具有外壳本体、流体流入部和流体流出部。
上述流体流入部设于上述外壳本体,可以流入被过滤流体。
上述流体流出部设于上述外壳本体,可以流出已过滤的流体。
(催化剂用载体)
本发明的催化剂用载体具有本发明的上述多孔质碳材料,根据需要,还具有其他构件。
例如,上述催化剂用载体为上述多孔质碳材料本身。
上述催化剂用载体能够保持大量的贵金属等催化剂。因此,在上述催化剂用载体中担载催化剂而形成的催化剂担载体会促进各种化学反应,能够提高收率。
另外,除上述用途以外,本发明的上述多孔质碳材料还可用于电容器的电极材料、各种吸附剂、面具、吸附片材等。
实施例
下面,说明本发明的实施例,但本发明并不受这些实施例的任何限定。
在本实施例中,粒径、堆比重、中孔容积按照上述方法进行测定。
残留氯除去性能通过以下的通水试验来测定。
<通水试验和残留氯测定>
在实施例、比较例中,均是在柱中填充通过10目的筛、且未通过32目的筛的样品,以入口的残留氯浓度为0.5±0.1mg/L进行送液,以空间速度SV=2000/小时进行通水试验。
按照邻联甲苯胺法,使用分光光度计测定435nm的显色,定量通过柱后的液体中的游离残留氯。
(实施例1)
使用稻壳作为原材料。使用新兴工机株式会社制造的S-5型平模式造粒机将已粉碎的稻壳成型,使成型物的直径达到6mm、长度达到数mm~数十m,得到成型物。成型时的含水率和成型物的堆比重、成型物的状态见表1。
此外,成型时的含水率通过使用喷雾器对原材料喷水、以及当时的喷雾量来调整。
[表1]
含水率(质量%)是指原材料中所含的水分量,使用加热干燥式水分计来测定。具体而言,使用A&D公司的ML-50,将1g样品在150℃下干燥20分钟,根据干燥前后的重量变化测定含水率。例如,1.0g样品在干燥后变为0.9g时,含水率为10质量%。
接下来,将所制作的含水率为16质量%的成型物在氮气流下、在600℃下加热3小时,得到碳化物。
接下来,将碳化物粗粉碎成2mm左右的大小,之后将其浸在1mol%的氢氧化钠水溶液中,除去灰分后进行清洗。
接下来,在水蒸气环境下、在950℃下加热3.5小时进行活化化,得到多孔质碳材料。
使用磨碎混合机(raikai mixer)粉碎所得的多孔质碳材料,用筛进行分级。
对于分级后的多孔质碳材料,求出粒径与堆比重的关系,见图1。
另外,分级后的多孔质碳材料的比表面积、中孔容积见表2。
[表2]
尚需说明的是,图1中作图的各粒径的所有样品的比表面积和中孔容积均相同。
(比较例1)
使用稻壳作为原材料。
接下来,在氮气流下、在600℃加热稻壳3小时,得到碳化物。
接下来,将碳化物浸在1mol%的氢氧化钠水溶液中,除去灰分,之后进行清洗。
接下来,在水蒸气环境下、在950℃加热3小时,进行活化化,得到多孔质碳材料。
使用磨碎混合机粉碎所得的多孔质碳材料,使用筛进行分级。
对于分级后的多孔质碳材料,求出粒径与堆比重的关系,见图1。
另外,分级后的多孔质碳材料的比表面积、中孔容积见表3。
[表3]
尚需说明的是,图1中作图的各粒径的所有样品的比表面积和中孔容积均相同。
由图1可知:比较例1的多孔质碳材料(现有的多孔质碳材料),其堆比重为0.10g/cm3,与粒径无关,相对于此,实施例1的多孔质碳材料的粒径在10μm以上的范围,堆比重明显大于现有的多孔质碳材料。
特别是在粒径为100μm以上的范围,堆比重为比较例的约3倍。由于堆比重变为约3倍,所以同一容器内的填充重量也增加,例如,将其用于净水用过滤器时,净水性能大幅提高。
另外,按照上述方法研究同一体积下的残留氯除去性能,结果见图2。
通过改善堆比重,吸附容量增加。因此,例如除去率下降至80%以下的材料,其单位体积的通水量在比较例1中为27L/mL。相对于此,实施例1中,即使材料单位体积的通水量超过100L/mL,除去率也会超过80%。这显示作为残留氯除去过滤器的寿命延长4倍左右。
(实施例2)
在实施例1中,除了将活化化的时间由3.5小时变更为3小时以外,进行与实施例1相同的操作,制作了多孔质碳材料。所得的多孔质碳材料的比表面积和中孔容积见表4。
尚需说明的是,实施例2中的粒径与堆比重的值与实施例1(图1)相同。
(比较例2)
在比较例1中,除了将活化化的时间由3.5小时变更为2.5小时以外,进行与比较例1相同的操作,制作了多孔质碳材料。所得的多孔质碳材料的比表面积和中孔容积见表4。
尚需说明的是,比较例2中的粒径和堆比重的值与比较例1(图1)相同。
另外,对于实施例2和比较例2中得到的多孔质碳材料,按照上述方法研究同一体积下的残留氯除去性能,结果见图3。
在比表面积和中孔容积不同的实施例2和比较例2中,也得到了与实施例1和比较例1相同的结果。
[表4]
产业实用性
本发明的多孔质碳材料,由于中孔发达、同时堆比重大,因此可用于过滤器、电容器的电极材料、各种吸附剂、面具、吸附片材、催化剂用载体等。
Claims (12)
1.一种多孔质碳材料,其特征在于,
粒径为10μm以上且1cm以下,
堆比重为0.20g/cm3以上,并且
中孔容积为0.10cm3/g以上。
2.根据权利要求1所述的多孔质碳材料,其中,
包含来自植物的材料。
3.根据权利要求2所述的多孔质碳材料,其中,
所述来自植物的材料为稻壳。
4.一种过滤器,其特征在于,
具有权利要求1~3中任一项所述的多孔质碳材料。
5.根据权利要求4所述的过滤器,其中,
所述过滤器为净水用过滤器。
6.根据权利要求4所述的过滤器,其中,
所述过滤器为空气净化用过滤器。
7.一种滤芯,其特征在于,
具有权利要求4~6中任一项所述的过滤器。
8.一种片材,其特征在于,
具有权利要求1~3中任一项所述的多孔质碳材料。
9.一种催化剂用载体,其特征在于,
具有权利要求1~3中任一项所述的多孔质碳材料。
10.一种多孔质碳材料的制造方法,其特征在于,
所述制造方法是权利要求1~3中任一项所述的多孔质碳材料的制造方法,包括以下工序:
将来自植物的材料加压成型,得到成型物;
将所述成型物碳化,得到碳化物;以及
将所述碳化物活化。
11.根据权利要求10所述的多孔质碳材料的制造方法,其中,
所述来自植物的材料为稻壳。
12.根据权利要求10或11所述的多孔质碳材料的制造方法,其中,
所述得到成型物的工序是指将含水率为3质量%以上且30质量%以下的所述来自植物的材料加压成型的工序。
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