JP2001226111A - Activated carbon and its manufacturing method - Google Patents
Activated carbon and its manufacturing methodInfo
- Publication number
- JP2001226111A JP2001226111A JP2000226836A JP2000226836A JP2001226111A JP 2001226111 A JP2001226111 A JP 2001226111A JP 2000226836 A JP2000226836 A JP 2000226836A JP 2000226836 A JP2000226836 A JP 2000226836A JP 2001226111 A JP2001226111 A JP 2001226111A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- carbon
- temperature
- inorganic compound
- specific gravity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 22
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 230000005484 gravity Effects 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims description 17
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 10
- 244000060011 Cocos nucifera Species 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 239000003610 charcoal Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000000630 rising effect Effects 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 24
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- 238000005192 partition Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WUNUDQFLPACRKI-UHFFFAOYSA-N OB(O)O.F.F.F.F Chemical compound OB(O)O.F.F.F.F WUNUDQFLPACRKI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- -1 calcium carbonate Chemical compound 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/10—Energy storage using batteries
Landscapes
- Inert Electrodes (AREA)
- Secondary Cells (AREA)
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、比表面積が大きい
高機能活性炭およびその製法に関し、特に電気二重層コ
ンデンサ、リチウムイオン電池、亜鉛空気電池、溶剤回
収用等々に有用な活性炭に関するものである。The present invention relates to a high-performance activated carbon having a large specific surface area and a method for producing the same, and more particularly to an activated carbon useful for electric double layer capacitors, lithium ion batteries, zinc air batteries, solvent recovery, and the like.
【０００２】[0002]
【従来の技術】活性炭は、従来から吸着用、触媒用等に
使用されているが、近年、エレクトロニクス関係の製品
の小型化、携帯化に伴い、電池用途に大きく利用され、
今後も需要の増大が期待されている。その中でも、電気
二重層コンデンサの電極を主として、その他各種電池関
連用途での高機能活性炭の需要が急増している。電気二
重層コンデンサに使用される分極性電極の構成材料とな
る活性炭は、単位体積、単位重量あたりの静電容量が大
きいことが電池の軽量化、短小化、性能向上にあたって
必須である。このため、活性炭の具備すべき条件とし
て、細孔径が容量に寄与する２ｎｍ程度以下のミクロ孔
を主体とし、その分布がシャープであること、高比表面
積で充填密度が高く且つ不純物が少ないことが要求され
ている。2. Description of the Related Art Activated carbon has conventionally been used for adsorption, catalysis, and the like. However, recently, with the miniaturization and portability of electronics-related products, activated carbon has been widely used for batteries.
Demand is expected to increase in the future. Among them, demand for high-performance activated carbon mainly for electrodes of electric double-layer capacitors and other various battery-related applications has been rapidly increasing. Activated carbon, which is a constituent material of a polarizable electrode used in an electric double layer capacitor, must have a large capacitance per unit volume and unit weight in order to reduce the weight, size, and performance of a battery. For this reason, the activated carbon should have the following conditions: micropores having a pore diameter of about 2 nm or less, which contribute to capacity, having a sharp distribution, a high specific surface area, a high packing density, and a small amount of impurities. Has been requested.
【０００３】活性炭は、出発原料の炭素材料として一般
的に椰子殻、大鋸屑、石炭等の天然物系、フェノール樹
脂、ポリ塩化ビニリデン樹脂等の合成樹脂系、あるいは
これらの混合物が使用され、これらの原料を加熱し炭化
する工程と多孔質とする賦活工程の２つの工程で製造さ
れる。一般的には、原料として合成樹脂系原料を使用し
た方が高機能の活性炭が得られると言われている。賦活
工程については、工業的には約７００℃以上の高温下で
数十分から数時間の範囲で炭化物と高温の水蒸気を反応
させることによる水蒸気賦活法が簡易的でありるため主
として行われている。この賦活炉としては、ロータリー
キルン等の連続炉が、連続的に効率的に原料を賦活でき
るため主に用いられている。しかし、この水蒸気賦活方
法では、高機能を発揮するとされる合成樹脂原料を用い
ても細孔径分布がシャープでなく容量に寄与する細孔の
割合が減少し体積あたりのコンデンサ容量（Ｆ／ｃ
ｍ3）が小さく、電気二重層コンデンサの用途として十
分でない。Activated carbon is generally used as a starting material as a carbon material such as coconut husks, sawdust, natural materials such as coal, synthetic resins such as phenolic resins and polyvinylidene chloride resins, or mixtures thereof. It is manufactured in two steps, a step of heating and carbonizing the raw material and an activation step of making the material porous. It is generally said that a highly functional activated carbon can be obtained by using a synthetic resin-based material as a material. The activation step is mainly performed industrially because the steam activation method by reacting carbide and high-temperature steam in a range of tens of minutes to several hours under a high temperature of about 700 ° C. or higher is simple, I have. As the activation furnace, a continuous furnace such as a rotary kiln is mainly used because the raw material can be continuously and efficiently activated. However, in this water vapor activation method, even when a synthetic resin material which is considered to exhibit high performance is used, the pore size distribution is not sharp and the ratio of pores contributing to the capacity is reduced, and the capacitor capacity per volume (F / c
m 3 ) is small and not sufficient for use in electric double layer capacitors.
【０００４】また、他の方法としてＫＯＨ等の薬品を炭
素材料と混合し高温加熱する薬品賦活方法がある。この
方法は、腐食環境で賦活を行うため容器、装置が特殊な
合金を使用する必要があり、高価あるいは交換が頻繁で
あること、あるいは残留するＫＯＨの水洗工程による手
間、賦活により発生した金属カリウムの発火の危険性等
で量産上問題が多い。また、活性炭中に残留するカリウ
ム等の金属が充放電特性に悪影響を与えることも考えら
れる。As another method, there is a chemical activation method in which a chemical such as KOH is mixed with a carbon material and heated at a high temperature. In this method, the activation is performed in a corrosive environment. Therefore, it is necessary to use a special alloy for the container and the apparatus, and it is expensive or frequently exchanged. There are many problems in mass production due to the danger of fire. It is also conceivable that a metal such as potassium remaining in the activated carbon has an adverse effect on the charge / discharge characteristics.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、主として電
気二重層コンデンサ用途等に要求される高性能を持った
活性炭を効率的に簡易に製造することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to efficiently and simply produce activated carbon having high performance required mainly for use in electric double layer capacitors.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記状況
に鑑み鋭意検討した結果、炭化物、またはそれを水蒸気
賦活して得られた炭化物を、７５０℃以下で熱分解し炭
酸ガスを発生し始める無機化合物とともに加熱し、該無
機化合物の炭酸ガス発生温度から上を昇温速度１０℃／
ｈｒ以下で７５０℃〜１４００℃間の温度まで焼成する
ことにより所望の活性炭を効率良く容易に製造できるこ
とがわかった。これに使用される炭化物の出発原料は、
椰子殻が安価で入手容易であるので好ましい。この焼成
時に炭化物と共に入れる無機化合物は、炭酸カルシウム
またはその化合物を使用することが入手、反応の安定性
から良い。このような製造法により、電気二重層コンデ
ンサとして最適である真比重が２．０以上かつ比表面積
が８００ｍ2／ｇ以上である活性炭が得られるととも
に、これを電極として使用した電気二重層コンデンサ
は、従来製法によるものよりはるかに高容量を示した。
なお、ここでの真比重は浸漬液にエタノールを使用しＪ
ＩＳ Ｒ７２２２に準拠した比重ビンによる測定方法で
ある。Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above situation, and as a result, have been found to thermally decompose a carbide or a carbide obtained by activating the same at 750 ° C. or less to generate carbon dioxide gas. With the inorganic compound that starts to grow, and the temperature is raised from the carbon dioxide generation temperature of the inorganic compound by 10 ° C. /
It has been found that the desired activated carbon can be efficiently and easily produced by calcining at a temperature of 750 ° C. to 1400 ° C. at not more than hr. The starting material of the carbide used for this is
Coconut shells are preferred because they are inexpensive and readily available. As the inorganic compound to be added together with the carbide at the time of this calcination, use of calcium carbonate or a compound thereof is available, which is good in terms of the stability of the reaction. By such a manufacturing method, an activated carbon having a true specific gravity of 2.0 or more and a specific surface area of 800 m 2 / g or more, which is optimal as an electric double layer capacitor, can be obtained. And showed much higher capacity than that of the conventional manufacturing method.
The true specific gravity here is determined by using ethanol as the immersion liquid.
This is a measurement method using a specific gravity bin based on IS R7222.
【０００７】[0007]
【発明の実施の形態】以下本発明を詳細に説明する。本
発明の製法に用いる出発原料の炭素粉体又は粒体は、椰
子殻系、石炭系、フェノール樹脂、ポリ塩化ビニリデン
樹脂等の合成樹脂系、あるいはこれらの混合物を原料と
することができるが、椰子殻は安価で入手し易いととも
に活性炭にした時、コンデンサ容量に寄与するに適当な
１〜３ｎｍ程度の大きさの細孔ができやすいので好まし
い。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The carbon powder or granular material of the starting material used in the production method of the present invention may be a coconut shell type, a coal type, a phenol resin, a synthetic resin type such as a polyvinylidene chloride resin, or a mixture thereof. Coconut shells are preferred because they are inexpensive and easily available, and when activated carbon is used, pores having a size of about 1 to 3 nm suitable for contributing to the capacitor capacity are easily formed.
【０００８】椰子殻を炭化したものが本発明の出発原料
として好ましい。また、あらかじめ水蒸気賦活した炭素
粉体又は粒体を本発明の賦活に使用するとより好適であ
る。これは水蒸気により既に生成した細孔と本発明によ
る炭酸ガス賦活により生成した細孔とが異なった部位に
生成されるからではないかと考えられる。結果としてコ
ンデンサ電極に使用した時の容量が増し好ましい。[0008] The carbonized coconut shell is preferred as the starting material of the present invention. Further, it is more preferable to use carbon powder or granules activated in advance with steam in the activation of the present invention. This may be because the pores already generated by the water vapor and the pores generated by the activation of carbon dioxide gas according to the present invention are formed in different portions. As a result, the capacity when used for the capacitor electrode increases, which is preferable.
【０００９】本発明では、加熱により炭素粉体又は粒体
を炭化するとともに同時に炭酸ガスによる賦活を行おう
とするものである。その炭酸ガスの発生源として無機化
合物を利用する。本無機化合物は、低温でガスを発生す
る必要はなく、賦活の効果的な温度近傍になってガスを
発生するものが好ましい。特に、常温から徐々に加熱温
度を上げていく場合には、賦活温度近傍までの発生ガス
は、無駄となるからである。本発明では、７５０℃近傍
から炭酸ガス賦活が効果的に働くため、７５０℃以下で
炭酸ガスを発生し始める無機化合物が適当である。７５
０℃以下で熱分解し炭酸ガスを発生し始める無機化合物
には、各種炭酸塩があるが、炭酸カルシウムを主成分と
する化合物が安価であるとともに、賦活温度に近い領域
の約７００℃近傍で炭酸ガスを発生するため昇温時から
の無駄なガスの放出が少ないため好ましい。炭酸カルシ
ウムは、単体でもよいが、ドロマイトのような炭酸カル
シウムと他の無機化合物の化合物でも可能である。In the present invention, the carbon powder or granules are carbonized by heating, and at the same time, activation by carbon dioxide gas is performed. An inorganic compound is used as a source of the carbon dioxide gas. It is not necessary for the present inorganic compound to generate gas at a low temperature, and it is preferable that the inorganic compound generates a gas at a temperature near the effective activation temperature. In particular, when the heating temperature is gradually increased from room temperature, the generated gas up to the vicinity of the activation temperature is wasted. In the present invention, since the activation of carbon dioxide gas works effectively at around 750 ° C., an inorganic compound which starts generating carbon dioxide gas at 750 ° C. or lower is suitable. 75
Inorganic compounds that begin to decompose at 0 ° C. or lower and generate carbon dioxide gas include various carbonates. Compounds containing calcium carbonate as a main component are inexpensive and have a temperature near the activation temperature of about 700 ° C. Since carbon dioxide gas is generated, wasteful release of gas from the time of temperature rise is small, which is preferable. Calcium carbonate may be a simple substance, or a compound of calcium carbonate and other inorganic compounds such as dolomite.
【００１０】更に製造法についての詳細な説明を行う。
活性炭の出発原料と炭酸カルシウム等の炭酸ガス発生用
無機化合物を耐熱材料で作製された蓋付き容器に入れ
て、非酸化性雰囲気中で焼成する。容器内には原料と炭
酸カルシウム粉末が混合しないよう、簡単な仕切りを設
けておくか、混合して焼成後に分離する方法でもよい。
予め混合してから焼成した場合、焼成後に無機化合物の
残材を活性炭と分離する必要があり、このため例えば風
力分級、洗浄等を使用した分離作業が後で必要となる。
従って、同一容器内で上下に炭素材料と無機化合物を分
け、仕切板で例えば発生ガスのみ通過するようなものを
設けておくことにより、焼成賦活後の分離作業が簡単に
なり楽である。この場合、容器の下方に無機化合物を入
れ、上方にガスが流れ炭素材料中を通過するようにする
ことが好ましい。なお，容器は使用温度を考慮し、黒
鉛、ステンレス等が使用できる。炭酸カルシウムは原料
に対して重量比０．２〜１０倍程度使用するのが良い。
目標とする高性能活性炭を得るために昇温速度、容器の
材質、形状、寸法等によってこの量を調整する。重量比
１０を超えると、賦活が早く進み、賦活収率が下がる。
重量比０．２未満では賦活に要するガス発生が十分に得
られず、賦活が進まない。[0010] The production method will be described in detail.
A starting material of activated carbon and an inorganic compound for generating carbon dioxide, such as calcium carbonate, are placed in a lidded container made of a heat-resistant material and fired in a non-oxidizing atmosphere. A simple partition may be provided in the container so that the raw material and the calcium carbonate powder are not mixed, or a method of mixing and separating after firing.
In the case of firing after mixing in advance, it is necessary to separate the residual material of the inorganic compound from the activated carbon after firing, so that a separation operation using, for example, air classification, washing, or the like is required later.
Therefore, by separating the carbon material and the inorganic compound vertically in the same container and providing a partition plate that allows only the generated gas to pass through, for example, the separation operation after firing activation becomes simple and easy. In this case, it is preferable that the inorganic compound is put in the lower part of the container and the gas flows upward and passes through the carbon material. In addition, graphite, stainless steel, etc. can be used for the container in consideration of the operating temperature. Calcium carbonate is preferably used in a weight ratio of about 0.2 to 10 times the raw material.
In order to obtain the desired high-performance activated carbon, the amount is adjusted depending on the temperature rising rate, the material, the shape, and the dimensions of the container. When the weight ratio is more than 10, the activation proceeds quickly, and the activation yield decreases.
If the weight ratio is less than 0.2, sufficient gas generation for activation cannot be obtained, and the activation does not proceed.
【００１１】賦活時の最終取出し温度は、炭酸ガスによ
る賦活が好適に進行する温度で７５０〜１４００℃、好
ましくは８５０〜１２００℃である。７５０℃未満では
賦活反応が進行しにくく、また１４００℃をこえると炭
材の結晶化が進み、得られた活性炭の細孔が再び閉塞し
てしまう。また、この時の昇温速度は遅いほうがより高
性能な活性炭が得られる。特に、ガス発生してから取出
し温度までの昇温速度は、遅いほうがよい。好適なの
は、１０℃／ｈｒ以下である。これより早いと細孔径分
布がシャープでなく、また真比重も低くなる。なお、こ
のような昇温速度が得られれば、加熱炉は、ヒーター形
式のものでも誘導炉形式のものでも、特に炉の形式は問
わない。The final removal temperature at the time of activation is a temperature at which activation with carbon dioxide gas proceeds suitably, and is 750 to 1400 ° C., preferably 850 to 1200 ° C. If the temperature is lower than 750 ° C., the activation reaction hardly proceeds. If the temperature exceeds 1400 ° C., crystallization of the carbon material proceeds, and the pores of the obtained activated carbon are closed again. In this case, the higher the heating rate, the higher the performance of the activated carbon. In particular, the rate of temperature rise from the generation of gas to the removal temperature is preferably low. Suitable is 10 ° C./hr or less. If it is earlier than this, the pore size distribution is not sharp and the true specific gravity is low. If the heating rate can be obtained, the heating furnace may be of a heater type or an induction furnace type, and the type of the furnace is not particularly limited.
【００１２】得られた活性炭は、真比重が高い。ここで
いう真比重は、ＪＩＳ Ｒ７２２２に記載されているよ
うに試料を標準ふるい１４９μｍを通過するまで砕いた
ものを、該ＪＩＳに従い、乾燥、冷却した後、比重ビン
にて浸漬液として１−ブタノールの代わりにエタノール
を使用し、測定したものである。ここで１−ブタノール
の代わりにエタノールを使うのは、入手し易いためであ
り、１−ブタノールでも問題なく類似の値が得られる
が、本発明ではエタノールにて測定したものである。得
られた活性炭は、真比重が高く、電気二重層コンデンサ
用電極用として最適な細孔を有している。[0012] The obtained activated carbon has a high true specific gravity. The true specific gravity as used herein refers to a value obtained by crushing a sample through a standard sieve of 149 μm as described in JIS R7222, drying and cooling it according to the JIS, and then using a specific gravity bottle as an immersion liquid in 1-butanol. Was measured using ethanol instead of. Here, ethanol is used in place of 1-butanol because it is easily available. Similar values can be obtained without any problem even with 1-butanol, but in the present invention, ethanol was measured. The obtained activated carbon has a high true specific gravity and has pores most suitable for electrodes for electric double layer capacitors.
【００１３】すなわち真比重が高い結果、同体積で重量
の大きな電極が作成され、この結果、電極にした場合の
同体積あたりの表面積（ｍ2／ｃｍ3）を高めることがで
き、結局コンデンサとしての単位体積あたりの容量の向
上が図れる。That is, as a result of a high true specific gravity, an electrode having the same volume and a large weight is produced, and as a result, the surface area per unit volume (m 2 / cm 3 ) when the electrode is formed can be increased. Can be improved per unit volume.
【００１４】[0014]
【実施例】以下、実施例に従い本発明を説明する。 （実施例１〜３、比較例１）賦活の原料として市販の活
性化前の椰子殻炭および市販の水蒸気賦活した椰子殻活
性炭（比表面積 １０００ｍ2／ｇ）を用いた。これを
表１に示す条件で原料と石灰石を図１のようなステンレ
ス製の容器（３０×３０×５０ｃｍ）に入れ蓋をして電
気炉を用いて焼成した。石灰石を容器の下側に入れ穴の
開いた仕切り板をはさんで、上側に原料の炭素材料を置
き下方から発生した炭酸ガスが上方の炭素材料を通じて
上方へ逃げるようにした。 （比較例２〜５）実施例１と同様の椰子殻炭とフェノー
ル樹脂（ＢＲＬ−１２０Ｚ：昭和高分子（株）製）を１
５０℃で硬化後、Ｎ２雰囲気下５０℃／ｈｒで８００℃
まで昇温、炭化したものを一定温度に保った加熱炉に入
れ、Ｎ２ガスをキャリヤーとして常温水換算１０ｃｃ／
ｍｉｎの水蒸気を導入し、表２に示す条件で水蒸気賦活
を行った。得られた活性炭については、ＢＥＴ（Ｎ2）
法による比表面積および前記の測定法による真比重の測
定を行った。この結果を表３に示す。The present invention will be described below with reference to examples. (Examples 1 to 3, Comparative Example 1) Commercially available coconut shell charcoal before activation and commercially available coconut shell activated carbon activated with steam (specific surface area: 1000 m 2 / g) were used as starting materials. Under the conditions shown in Table 1, the raw material and limestone were placed in a stainless steel container (30 × 30 × 50 cm) as shown in FIG. The limestone was placed under the container and sandwiched by a perforated partition plate. The raw carbon material was placed on the upper side so that carbon dioxide gas generated from below escaped upward through the upper carbon material. (Comparative Examples 2 to 5) The same coconut shell charcoal and phenol resin (BRL-120Z: manufactured by Showa Polymer Co., Ltd.)
After curing at 50 ° C, 800 ° C at 50 ° C / hr in N2 atmosphere
Into a heating furnace maintained at a constant temperature, and using N2 gas as a carrier, 10 cc /
min, and steam activation was performed under the conditions shown in Table 2. About the obtained activated carbon, BET (N 2 )
The specific surface area by the method and the true specific gravity by the measurement method described above were measured. Table 3 shows the results.
【００１５】[0015]
【表１】 [Table 1]
【表２】 [Table 2]
【表３】 次にこの得られた各活性炭を用いて電気二重層用コンデ
ンサ電極を作成し、電気二重層コンデンサを組み充放電
容量を測定した。まず、活性炭を平均粒径２０μｍに粉
砕し、テフロン樹脂粉末（三井デユポンフルオロケミカ
ル（株）製：Ｊ６）、カーボンブラック（電気化学工業
（株）製：デンカブラック）を、各々８０：１０：１０
に配合し、金型を用いて５００ｋｇ／ｃｍ2で加圧成形
して２ｃｍ角、厚み約０．５ｍｍの電極とした。電解液
としてテトラエチルメチルアンモニウム４フッ化ボレー
ト塩をプロピレンカーボネイト溶媒に３０％溶かした液
を使用し、この電解液を電極に真空含浸した後に単セル
を作成した。市販充放電測定装置により、２ｍＡ／ｃｍ
2の電流密度で電圧２．５Ｖの条件にて充放電を行い、
コンデンサ容量性能を測定した。容量値は、1対の電極
の合計体積で割った単位体積あたりの容量（Ｆ／ｃ
ｍ3）で示した。この結果を表３に示す。なお、参考と
して電気二重層コンデンサ用と称して市販されている活
性炭についての測定値も表３に示した。[Table 3] Next, a capacitor electrode for an electric double layer was prepared using each of the obtained activated carbons, and an electric double layer capacitor was assembled to measure the charge / discharge capacity. First, activated carbon was pulverized to an average particle size of 20 μm, and Teflon resin powder (manufactured by Mitsui DuPont Fluorochemicals Co., Ltd .: J6) and carbon black (manufactured by Denki Kagaku Kogyo Co., Ltd .: Denka Black) were each 80:10:10.
And press-molded at 500 kg / cm 2 using a mold to form an electrode having a 2 cm square and a thickness of about 0.5 mm. As an electrolyte, a solution prepared by dissolving tetraethylmethylammonium tetrafluoride borate in a propylene carbonate solvent at 30% was used, and the electrolyte was vacuum impregnated into the electrodes to form a single cell. 2 mA / cm using a commercially available charge / discharge measuring device
Charge and discharge at a current density of 2 and a voltage of 2.5 V,
The capacitor capacity performance was measured. The capacitance value is the capacitance per unit volume (F / c) divided by the total volume of a pair of electrodes.
m 3 ). Table 3 shows the results. For reference, Table 3 also shows measured values of commercially available activated carbon for electric double layer capacitors.
【００１６】[0016]
【発明の効果】本発明によれば、安価で入手し易い椰子
殻等の原料から電気二重層コンデンサ用途等に要求され
る比表面積を保ちつつ、真比重の高い活性炭が得られ、
これを用いた電極は、コンデンサとしての体積あたりの
容量が高い高性能のものが得られる。According to the present invention, activated carbon having a high true specific gravity can be obtained from raw materials such as coconut shells, which are inexpensive and easily available, while maintaining the specific surface area required for electric double layer capacitor applications and the like.
An electrode using this is a high-performance electrode having a high capacity per volume as a capacitor.
【００１７】[0017]
【図１】本発明の方法にて使用される容器の断面図の一
例である。FIG. 1 is an example of a sectional view of a container used in the method of the present invention.
【００１８】[0018]
１ ステンレス製蓋 ２ ステンレス製箱 ３ 目皿（黒鉛板） ４ 原料 ５ 炭酸カルシウム 1 Stainless steel lid 2 Stainless steel box 3 Plate (graphite plate) 4 Raw material 5 Calcium carbonate
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 12/06 Ｈ０１Ｇ 9/00 ３０１Ａ Ｆターム(参考） 4G046 HA01 HA08 HB00 HB02 HB05 HC09 HC10 5H018 AA10 AS03 BB00 BB01 EE07 HH02 HH05 HH08 5H029 AJ01 AL08 AM01 CJ21 DJ16 HJ07 HJ08 HJ14 5H032 AA01 AS03 BB00 BB02 EE01 EE15 HH02 HH04 HH06 5H050 AA01 BA17 BA20 CA16 CB09 FA17 GA21 HA07 HA08 HA14 HA20 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H01M 12/06 H01G 9/00 301A F-term (Reference) 4G046 HA01 HA08 HB00 HB02 HB05 HC09 HC10 5H018 AA10 AS03 BB00 BB01 EE07 HH02 HH05 HH08 5H029 AJ01 AL08 AM01 CJ21 DJ16 HJ07 HJ08 HJ14 5H032 AA01 AS03 BB00 BB02 EE01 EE15 HH02 HH04 HH06 5H050 AA01 BA17 BA20 CA16 CB09 FA17 GA21 HA07 HA08 HA14 HA20
Claims (7)
２２２の比重ビンによる真比重測定方法での真比重値が
２．０以上であり、比表面積が８００ｍ2／ｇ以上であ
る活性炭。(1) JIS R7 using ethanol as an immersion liquid
Activated carbon having a true specific gravity value of 2.0 or more and a specific surface area of 800 m 2 / g or more in a true specific gravity measurement method using a specific gravity bin 222.
し炭酸ガスを発生し始める無機化合物とを同一容器にて
昇温し、該無機化合物の炭酸ガス発生温度から上を昇温
速度１０℃／ｈｒ以下の昇温速度で加熱し、７５０℃〜
１４００℃の範囲内の温度まで焼成することを特徴とす
る活性炭の製造方法。2. The temperature of the carbon powder or granules and the inorganic compound which is thermally decomposed at 750 ° C. or lower and starts generating carbon dioxide gas are raised in the same vessel, and the temperature is raised from the carbon dioxide generation temperature of the inorganic compound. Heat at a heating rate of 10 ° C / hr or less,
A method for producing activated carbon, comprising firing to a temperature in the range of 1400 ° C.
水蒸気賦活されたものである請求項２記載の活性炭の製
造方法。3. The method for producing activated carbon according to claim 2, wherein the carbon powder or granules to be heated have been activated in advance by steam.
合物を混合しないよう容器内で分けて入れることを特徴
とする請求項２又は３記載の活性炭の製造方法。4. The method for producing activated carbon according to claim 2, wherein the heated carbon powder or granules and the inorganic compound are separately placed in a container so as not to be mixed.
が椰子殻である請求項２〜４いずれか記載の活性炭の製
造方法。5. The method for producing activated carbon according to claim 2, wherein the carbon powder or granules used as a starting material for the activated carbon are coconut shells.
始める無機化合物が炭酸カルシウムまたは炭酸カルシウ
ムを含む化合物である請求項２〜５いずれか記載の活性
炭の製造方法。6. The method for producing activated carbon according to claim 2, wherein the inorganic compound which starts to decompose at a temperature of 750 ° C. or lower and generates carbon dioxide gas is calcium carbonate or a compound containing calcium carbonate.
した電気二重層コンデンサ。7. An electric double layer capacitor using the activated carbon of claim 1 as a material for an electrode.
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|---|---|---|---|
| JP2000226836A JP2001226111A (en) | 1999-12-07 | 2000-07-27 | Activated carbon and its manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-347092 | 1999-12-07 | ||
| JP34709299 | 1999-12-07 | ||
| JP2000226836A JP2001226111A (en) | 1999-12-07 | 2000-07-27 | Activated carbon and its manufacturing method |
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|---|---|
| JP2001226111A true JP2001226111A (en) | 2001-08-21 |
Family
ID=26578420
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004275091A (en) * | 2003-03-17 | 2004-10-07 | Asahi Breweries Ltd | Method for producing fermented malt beverage and activated carbon for purine removal of fermented malt beverage |
| WO2004091020A1 (en) * | 2003-04-08 | 2004-10-21 | Matsushita Electric Industrial Co. Ltd. | Electrode for oxygen reduction and electrochemical device using the same |
| JP2004321004A (en) * | 2003-04-21 | 2004-11-18 | Asahi Breweries Ltd | Production method of fermented malt beverage |
| US8283139B2 (en) * | 2007-02-09 | 2012-10-09 | Cj Cheiljedang Corporation | Method of producing xylitol using hydrolysate containing xylose and arabinose prepared from byproduct of tropical fruit biomass |
| US9133229B2 (en) | 2009-10-30 | 2015-09-15 | Cj Cheiljedang Corporation | Economic process for producing xylose from hydrolysate using electrodialysis and direct recovery method |
| JP2017127806A (en) * | 2016-01-19 | 2017-07-27 | トヨタ自動車株式会社 | Thermal barrier film forming method and thermal barrier film forming apparatus |
| CN109264715A (en) * | 2018-09-28 | 2019-01-25 | 中国石油大学(华东) | A kind of method that step heating prepares active carbon |
-
2000
- 2000-07-27 JP JP2000226836A patent/JP2001226111A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004275091A (en) * | 2003-03-17 | 2004-10-07 | Asahi Breweries Ltd | Method for producing fermented malt beverage and activated carbon for purine removal of fermented malt beverage |
| WO2004091020A1 (en) * | 2003-04-08 | 2004-10-21 | Matsushita Electric Industrial Co. Ltd. | Electrode for oxygen reduction and electrochemical device using the same |
| CN100365855C (en) * | 2003-04-08 | 2008-01-30 | 松下电器产业株式会社 | Electrode for oxygen reduction, electrochemical device using same, and manufacturing method thereof |
| JP2004321004A (en) * | 2003-04-21 | 2004-11-18 | Asahi Breweries Ltd | Production method of fermented malt beverage |
| US8283139B2 (en) * | 2007-02-09 | 2012-10-09 | Cj Cheiljedang Corporation | Method of producing xylitol using hydrolysate containing xylose and arabinose prepared from byproduct of tropical fruit biomass |
| US9133229B2 (en) | 2009-10-30 | 2015-09-15 | Cj Cheiljedang Corporation | Economic process for producing xylose from hydrolysate using electrodialysis and direct recovery method |
| JP2017127806A (en) * | 2016-01-19 | 2017-07-27 | トヨタ自動車株式会社 | Thermal barrier film forming method and thermal barrier film forming apparatus |
| CN109264715A (en) * | 2018-09-28 | 2019-01-25 | 中国石油大学(华东) | A kind of method that step heating prepares active carbon |
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