CN101125650A - 用竹子制作的电容器专用活性炭及方法 - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 18
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 18
- 241001330002 Bambuseae Species 0.000 title claims abstract description 18
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 18
- 239000011425 bamboo Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003990 capacitor Substances 0.000 title claims description 15
- 229910052799 carbon Inorganic materials 0.000 title description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 38
- 230000004913 activation Effects 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005539 carbonized material Substances 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000006210 lotion Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 abstract description 11
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000012190 activator Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Organic Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明是用竹子制作电容器专用活性炭及方法,是以竹子为原料,经炭化、活化、水洗、烘干处理而得到,原料经筛选截锯至5~10mm,于400~550℃炭化处理1~2小时;将炭化料与氢氧化钠和氢氧化钾按1∶1.0~2.0∶0.5~1.3重量配比混合,于700~800℃活化处理2~3小时;将活化物料加入水中冷却,滤出物料水洗并加酸中和,水洗液pH值至6~7,烘干后即可得到成品。利用该方法制备的活性炭,比表面积大,吸附能力优良,孔隙分布合理,综合理化指标优于目前世界同类产品,制作成本为11~16万元/吨(人民币),该产品最适合应用于双电层电容器电极的制作。
Description
技术领域
本发明涉及一种高比表面专用活性炭及制备方法,特别是主分类为CO1B31/12用竹子制作的超级电容器电极专用活性炭及方法。
发明背景
超级电容器是二十世纪八十年代开始在世界上出现的物理电源储存新技术,超级电容器电极的核心材料是高性能、高比表面积、指定孔隙大小的高性能专用活性炭(简称电极炭)。电极炭在上世纪80年代由美国AMOCO公司开发,但只能少量商业化生产,随后日本也开始少量商业化生产,中国自1993年开始研究,至今未能真正实现工业化生产。美国、日本生产电极炭是以树脂和同性沥青为原料,专利号为01123095.9,名称“活性炭及其生产方法、可极化电极、以及双电层电容器”,该技术由日本一家企业研制发明,是由颗粒状各向同性的沥青经热处理和活化制作静电容大的活性炭;专利号为00118967.0。名称“制作超级电容器电极的活性炭制备方法”由天津大学公开了一种制作超级电容器电极的活性炭制作方法,该方法是以酚醛树脂为原料,主要经过焦化、炭化、活化处理,再经水洗、烘干制得所需活性炭。以树脂、沥青、石油焦类为原料生产的电极炭其最大不足是成本高,原料成本比本发明至少高出3~5倍,生产的电极炭价格昂贵,一般在80~160万元/吨(人民币),这也是难以实现大量商业化生产的主要原因;该原料生产的产品含杂质高,尤其是金属离子和重金属离子指标含量高;对工作环境的污染和设备腐蚀严重,据试验证明:当活化温度超过800℃时,NaOH和KOH快速气化,对工作环境造成严重污染和设备腐蚀,该工艺目前仍停留在试验阶段,未能进行工艺放大,用于连续工业化生产。以树脂为原料生产的电极炭价格一般在80~160万元/吨(人民币),这也是难以实现大量商业化生产的主要原因。
发明内容
本发明的目的是提供一种用竹子为原料制作的电容器专用活性炭及其方法,利用该方法制备的活性炭,比表面积大,吸附能力优良,孔隙分布合理;制作成本平均只有11~16万元/吨(人民币),该活性炭适合应用于双电层电容器制造,是超级电容器电极的核心材料。
为了达到上述目的,本发明产品是通过以下技术方案来实现的:是采用竹子为原料,经炭化、活化、水洗、烘干处理来制取电容器电极专用活性炭,其技术特征是:炭化料与氢氧化钠和氢氧化钾的重量配比为1∶1.0~2.0∶0.5~1.3。
本发明用竹子制作电容器专用活性炭的方法,是以竹子为原料,经炭化、活化、水洗、烘干处理而得到,其特征是:
a)原料截至5~10Cm,于400~550℃炭化处理1~2小时;
b)将炭化料与氢氧化钠和氢氧化钾按1∶1.0~2.0∶0.5~1.3重量配比混合,于700~800℃活化处理2~3小时;
c)将活化物料加入水中冷却,滤出物料水洗并加酸中和,水洗液PH值至6~7,烘干后即可得到成品。
本发明还可以通过以下技术方案来实现:
经实验本发明炭化温度适宜于450~500℃。采用化学活化工艺,在活化剂KOH、NaOH、ZnCL、CaCL2当中选用NaOH和KOH为本方法的组合活化剂,炭化料与氢氧化钠和氢氧化钾的较佳重量配比选择为1∶1.5~2.0∶0.6~1.0,活化温度选择为750~800℃,时间为2~3小时较适宜,当活化温度继续升高、活化时间越长,活性炭的综合理化性能不是提高,而是降低,炭碱配比将影响活性炭孔隙的形成,冷却后的滤出物料水洗加入盐酸中和。
本发明实施例以下面列表形式来表达
原料 | 炭化温度℃ | 活化温度℃ | 加碱量(g)KOH+NaOH | 活化时间(小时) | 碘吸附值mg/g | 比表面积M2/g |
竹子1000克水洗液PH=6~7 | 500 | 780 | 800+1700 | 2 | 1300~1400 | 2000~2400 |
500 | 750 | 700+1600 | 2 | 1200~1300 | 1800~2000 | |
500 | 700 | 850+1600 | 2 | 1300~1400 | 2000~2400 | |
500 | 780 | 850+1600 | 3 | 1400~1600 | 2300~2600 | |
500 | 750 | 700+2000 | 3 | 1300~1400 | 2200~2400 | |
500 | 700 | 1000+1500 | 3 | 1500~1600 | 2500~2600 |
取锯截破碎的竹子1000g,长度在5~10Cm,于500℃±5温度下炭化2小时,再将炭化料与90%氢氧化钠1890g和85%氢氧化钾942g(工业品含量80~90%)混合均匀,于780±5℃温度下在转式活化炉内活化处理2小时,将活化物料迅速放入水中冷却,滤出物料水洗加盐酸中和,使水洗液PH值达6~7,将物料烘干研磨至需要颗粒细度即可。
本发明产品与树脂法产品对比表
生产国 | 美国、日本 | 本发明企业 |
原料工艺 | 树脂法 | 竹子炭化活化法 |
所用活化剂与配比 | 树脂:KOH=1∶3.5~8 | 竹子炭化料:NaOH∶KOH=1∶1.0~2.0∶0.5~1.0 |
孔隙分布的吸附指标 | 比表面积:2500~3000m2/g孔径分布:1~3nm碘吸附值:1600~2000mg/g亚甲兰吸附:20~35ml比重:0.3~0.4g/ml | 比表面积:2000~2600m2/g孔径分布:0.8~2.2n m碘吸附值:1300~1600mg/g亚甲兰吸附:20~30ml比重:0.4~0.5g/ml |
平均价格(人民币) | 80~160万元/吨 | 11~16万元/吨 |
主要技术性能 | 放电时间:2分20秒 | 放电时间:2分40秒 |
用本发明制备的活性炭,由上表列出的放电时间可以看出,放电时间越长,说明活性炭孔隙分布越合理;在选定一适宜的活化温度区间同时,组合活化剂以及适宜的配比量也是提高活性炭综合理化指标的关键因素。本发明产品经近年来为国内有关能源企业试用证明,该产品极适用于双电层超级电容器电极的制作,品质和综合技术指标优于目前世界同类产品,产品价格极具竞争力,是用于航空航天、防化事业等高科技领域的前沿产品。
Claims (6)
1.用竹子制作的电容器专用活性炭,是以竹子为原料,经炭化、活化、水洗、烘干处理得到,其特征是:炭化料与氢氧化钠和氢氧化钾的重量配比为1∶1.0~2.0∶0.5~1.3。
2.按照权利要求1所述的用竹子制作的电容器专用活性炭,其特征是炭化料与氢氧化钠和氢氧化钾的重量配比选择为1∶1.5~2.0∶0.6~1.0。
3.用竹子制作电容器专用活性炭的方法,是以竹子为原料,经炭化、活化、水洗、烘干处理而得到,其特征是:
a)原料截至5~10Cm,于400~550℃炭化处理1~2小时;
b)将炭化料与氢氧化钠和氢氧化钾按1∶1.0~2.0∶0.5~1.3重量配比混合,于700~800℃活化处理2~3小时;
c)将活化物料加入水中冷却,滤出物料水洗并加酸中和,水洗液PH值至6~7,烘干后即可得到成品。
4.按照权利要求3所述的方法,其特征是所述的炭化温度为450~500℃。
5.按照权利要求3所述的方法,其特征是所述活化温度为750~800℃。
6.按照权利要求3所述的方法,其特征是中和酸为盐酸。
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CNA2007100123054A CN101125650A (zh) | 2007-07-27 | 2007-07-27 | 用竹子制作的电容器专用活性炭及方法 |
PCT/CN2007/003679 WO2009015533A1 (fr) | 2007-07-27 | 2007-12-19 | Charbon actif pour condensateur et son procédé de préparation |
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Cited By (2)
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CN109607534A (zh) * | 2019-01-28 | 2019-04-12 | 广西农垦糖业集团昌菱制糖有限公司 | 一种利用蔗渣生产活性炭的加工工艺 |
CN113307266A (zh) * | 2021-06-04 | 2021-08-27 | 国际竹藤中心 | 改性活性炭及其制备方法和超级电容器 |
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KR101300162B1 (ko) | 2011-04-15 | 2013-08-26 | 재단법인 포항산업과학연구원 | 천연섬유 기반의 다공성 섬유상 탄소재 및 그 제조방법 |
KR102191650B1 (ko) * | 2019-06-14 | 2020-12-28 | 전주대학교 산학협력단 | 슈퍼캐패시터 전극용 활성탄소종이 제조방법, 이를 이용한 활성탄소종이 및 이를 포함하는 슈퍼캐패시터 전극 |
CN111634910A (zh) * | 2020-06-22 | 2020-09-08 | 桂林理工大学 | 一种超级电容器电极材料及其制备方法 |
CN113314353B (zh) * | 2021-03-12 | 2022-06-14 | 浙江省林业科学研究院 | 基于毛竹生物活性炭电极的可降解超级电容器 |
CN114105137A (zh) * | 2021-11-04 | 2022-03-01 | 中欣环保科技有限公司 | 一种复合型超级电容炭的制备方法 |
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CN1128100C (zh) * | 2001-09-04 | 2003-11-19 | 郑兴福 | 由竹质原料制备活性炭的方法 |
CN1406867A (zh) * | 2001-09-06 | 2003-04-02 | 何弘鑫 | 以竹子制备活性碳的方法 |
CN1382625A (zh) * | 2002-06-09 | 2002-12-04 | 陈文照 | 一种竹质活性炭生产工艺 |
US20060281633A1 (en) * | 2005-06-08 | 2006-12-14 | Chi-Hsiang Wang | Method of making bamboo charcoal adsorbents |
CN1318295C (zh) * | 2005-09-19 | 2007-05-30 | 朝阳森塬活性炭有限公司 | 用硬质果壳制作电容器专用活性炭的方法 |
CN1830772A (zh) * | 2006-03-17 | 2006-09-13 | 华南理工大学 | 一种高比表面积竹活性炭的制备方法 |
CN101117219A (zh) * | 2007-07-27 | 2008-02-06 | 朝阳森塬活性炭有限公司 | 用竹子制作电容器专用活性炭的方法 |
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CN109607534A (zh) * | 2019-01-28 | 2019-04-12 | 广西农垦糖业集团昌菱制糖有限公司 | 一种利用蔗渣生产活性炭的加工工艺 |
CN113307266A (zh) * | 2021-06-04 | 2021-08-27 | 国际竹藤中心 | 改性活性炭及其制备方法和超级电容器 |
CN113307266B (zh) * | 2021-06-04 | 2022-10-14 | 国际竹藤中心 | 改性活性炭及其制备方法和超级电容器 |
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