JP6288663B2 - Method for producing porous carbon material - Google Patents
Method for producing porous carbon material Download PDFInfo
- Publication number
- JP6288663B2 JP6288663B2 JP2013140432A JP2013140432A JP6288663B2 JP 6288663 B2 JP6288663 B2 JP 6288663B2 JP 2013140432 A JP2013140432 A JP 2013140432A JP 2013140432 A JP2013140432 A JP 2013140432A JP 6288663 B2 JP6288663 B2 JP 6288663B2
- Authority
- JP
- Japan
- Prior art keywords
- porous carbon
- lignin
- carbon material
- plant
- producing
- 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.)
- Active
Links
- 239000003575 carbonaceous material Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 229920005610 lignin Polymers 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 241000196324 Embryophyta Species 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 16
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 16
- 241001330002 Bambuseae Species 0.000 claims description 16
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 16
- 239000011425 bamboo Substances 0.000 claims description 16
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LWFBRHSTNWMMGN-UHFFFAOYSA-N 4-phenylpyrrolidin-1-ium-2-carboxylic acid;chloride Chemical compound Cl.C1NC(C(=O)O)CC1C1=CC=CC=C1 LWFBRHSTNWMMGN-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 239000001913 cellulose Substances 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001720 carbohydrates Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007833 carbon precursor Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Description
本発明は、多孔質炭素材料の製造方法に関する。 The present invention relates to a method for producing a porous carbon material.
多孔質炭素材料の代表例として活性炭が挙げられる。活性炭として一般的なヤシ殻活性炭は、比表面積が1200 m2 /g程度である。 A typical example of the porous carbon material is activated carbon. Coconut shell activated carbon, which is common as activated carbon, has a specific surface area of about 1200 m 2 / g.
1800 m2 /g程度以上の大きな比表面積を有する高性能な活性炭を作製する場合、一般に、水酸化カリウムや炭酸カリウムを使用した薬品賦活が行われる。これらの薬品の添加量は原料と同程度かそれ以上の質量の比率で混合した状態で加熱処理される。
しかし、これらの薬品を用いた賦活は、賦活のための加熱処理において金属カリウムが生成してしまう可能性があり、取り扱いには十分な配慮が必要となる。
When producing a high-performance activated carbon having a large specific surface area of about 1800 m 2 / g or more, chemical activation using potassium hydroxide or potassium carbonate is generally performed. The amount of these chemicals added is heat-treated in the state of being mixed at a mass ratio equal to or higher than that of the raw material.
However, activation using these chemicals may generate metal potassium in the heat treatment for activation, and sufficient consideration is required for handling.
多孔質炭素材料に関し、本発明者は、先に、糖類を主成分とする炭素前駆体にリンおよび窒素のうちのいずれか一方または双方を含有する化合物を配合し、炭化することで電気二重層キャパシタ分極性電極用炭素材料を得る技術を開示している（特許文献１参照）。この技術によれば、静電容量が大きい電気二重層キャパシタを得ることができる。 Regarding the porous carbon material, the present inventor previously blended and carbonized a compound containing either one or both of phosphorus and nitrogen into a carbon precursor mainly composed of saccharide, and carbonized the electric double layer. A technique for obtaining a carbon material for capacitor polarizable electrodes is disclosed (see Patent Document 1). According to this technique, an electric double layer capacitor having a large capacitance can be obtained.
ところで、活性炭の製造技術として、リグニンを原料とする比表面積が大きな活性炭が開示されている（特許文献２参照）。また、バイオマスを蒸煮してリグニンを可溶化し、熱可塑性を発現して成形したものを炭素前駆体として用いて活性炭を得る技術が開示されている（特許文献３参照）。また、特許文献３と同様の狙いで、リグニンが細胞壁中に内包されている木質系原料を加圧して細胞壁から放出させたリグニンをバインダの代わりとして利用して成形したものを炭素前駆体として用いて活性炭を得る技術が開示されている（特許文献４参照）。
一方、リグニンを原料として利用し、あるいはリグニンの特性を利用するこれらの技術とは逆に、リグニンを除去した草木をゲル状の糖質材料に調整し、これに金属化合物を添加して賦活して活性炭を得る技術が開示されている（特許文献５参照）。この場合、例えば硫酸に草木質を投入し、リグニン質を固体として析出させるとともにセルロース等の糖質を水溶液中に溶解し、糖質を酸により炭化処理した後に酸を除去し、ゲルに調製する。この技術によれば、活性炭を賦活処理する際にリグニンが細孔を閉塞する不具合を防止できるとされている。
By the way, activated carbon with a large specific surface area using lignin as a raw material has been disclosed as a technique for producing activated carbon (see Patent Document 2). In addition, a technique is disclosed in which activated carbon is obtained using steamed biomass to solubilize lignin and develop thermoplasticity as a carbon precursor (see Patent Document 3). Further, for the same purpose as that of Patent Document 3, a material obtained by molding a lignin released from a cell wall by pressurizing a wooden material in which lignin is encapsulated in the cell wall is used as a carbon precursor. A technique for obtaining activated carbon is disclosed (see Patent Document 4).
On the other hand, in contrast to these technologies that use lignin as a raw material or use the characteristics of lignin, the lignin-free vegetation is prepared into a gel-like saccharide material, which is then activated by adding a metal compound. A technique for obtaining activated carbon is disclosed (see Patent Document 5). In this case, for example, vegetation is added to sulfuric acid, lignin is precipitated as a solid, and saccharides such as cellulose are dissolved in an aqueous solution. The saccharide is carbonized with an acid, and then the acid is removed to prepare a gel. . According to this technique, it is said that the problem that lignin blocks pores when activated carbon is activated.
解決しようとする課題は、特許文献１の技術を改良して、より比表面積の大きな多孔質炭素材料を得ることができる多孔質炭素材料の製造方法を提供することである。 The problem to be solved is to provide a method for producing a porous carbon material capable of improving the technique of Patent Document 1 and obtaining a porous carbon material having a larger specific surface area.
本発明に係る多孔質炭素材料の製造方法は、植物からリグニンを溶出する工程と、リグニンを溶出した植物にリンおよび窒素のうちのいずれか一方または双方を含有する化合物を加えて炭化する工程を有することを特徴とする。 The method for producing a porous carbon material according to the present invention includes a step of eluting lignin from a plant, and a step of adding a compound containing either one or both of phosphorus and nitrogen to a plant eluting lignin and carbonizing it. It is characterized by having.
また、本発明に係る多孔質炭素材料の製造方法は、好ましくは、過酸化水素水と酢酸の混液を用いて植物からリグニンを溶出することを特徴とする。 Moreover, the method for producing a porous carbon material according to the present invention is preferably characterized in that lignin is eluted from a plant using a mixed solution of hydrogen peroxide and acetic acid.
また、本発明に係る多孔質炭素材料の製造方法は、好ましくは、リンおよび窒素のうちのいずれか一方または双方を含有する化合物がリン酸グアニジンであることを特徴とする。 Moreover, the method for producing a porous carbon material according to the present invention is preferably characterized in that the compound containing one or both of phosphorus and nitrogen is guanidine phosphate.
また、本発明に係る多孔質炭素材料の製造方法は、好ましくは、炭化する工程の後に、二酸化炭素ガスにより賦活する工程をさらに有することを特徴とする。 In addition, the method for producing a porous carbon material according to the present invention preferably further includes a step of activating with carbon dioxide gas after the step of carbonizing.
本発明に係る多孔質炭素材料の製造方法は、植物からリグニンを溶出する工程と、リグニンを溶出した植物にリンおよび窒素のうちのいずれか一方または双方を含有する化合物を加えて炭化する工程を有するため、比表面積の大きな多孔質炭素材料を得ることができる。 The method for producing a porous carbon material according to the present invention includes a step of eluting lignin from a plant, and a step of adding a compound containing either one or both of phosphorus and nitrogen to a plant eluting lignin and carbonizing it. Therefore, a porous carbon material having a large specific surface area can be obtained.
本発明の実施の形態（以下、本実施の形態例という。）について、以下に説明する。 An embodiment of the present invention (hereinafter referred to as this embodiment) will be described below.
本実施の形態例に係る多孔質炭素材料の製造方法は、植物からリグニンを溶出する工程と、リグニンを溶出した植物にリンおよび窒素のうちのいずれか一方または双方を含有する化合物を加えて炭化する工程を有する。 The method for producing a porous carbon material according to the present embodiment includes a step of eluting lignin from a plant, and adding a compound containing either or both of phosphorus and nitrogen to the plant from which lignin has been eluted. The process of carrying out.
植物は、天然資源として大量に賦存する。植物は、セルロース、ヘミセルロースおよびリグニンを大量に含む。
本実施の形態例において、植物として、竹粉末を好適に用いることができるが、これに限定するものではない。
Plants exist in large quantities as natural resources. Plants contain large amounts of cellulose, hemicellulose and lignin.
In the present embodiment, bamboo powder can be suitably used as the plant, but is not limited thereto.
植物からリグニンを溶出する方法は、例えばパルプ業界等において種々の技術が広く知られており、これらの技術のなかから適宜選択して用いることができる。過酸化水素水と酢酸の混液を用いて植物からリグニンを溶出することは、好適な実施態様である。
過酸化水素水と酢酸の混液を用いて植物からリグニンを溶出する場合、植物１００質量部に対して、過酸化水素水および酢酸をそれぞれ純物質基準で３００〜８００質量部用いることが好ましい。過酸化水素水および酢酸は、ほぼ等量用いることがより好ましい。温度６０〜１１０℃で４〜２４時間攪拌しながら処理することが好ましい。植物からリグニンを溶出した後は、例えば、濾過等によりリグニンを含む混液を植物から分離除去し、植物を洗浄した後、乾燥する。
Various techniques for eluting lignin from plants are widely known, for example, in the pulp industry and the like, and can be appropriately selected and used from these techniques. It is a preferred embodiment to elute lignin from plants using a mixture of hydrogen peroxide and acetic acid.
When lignin is eluted from a plant using a mixed solution of hydrogen peroxide and acetic acid, it is preferable to use 300 to 800 parts by mass of hydrogen peroxide and acetic acid, respectively, on a pure substance basis with respect to 100 parts by mass of the plant. It is more preferable to use approximately equal amounts of hydrogen peroxide solution and acetic acid. The treatment is preferably performed at a temperature of 60 to 110 ° C. with stirring for 4 to 24 hours. After the lignin is eluted from the plant, for example, the mixed solution containing lignin is separated and removed from the plant by filtration or the like, and the plant is washed and dried.
リンおよび窒素のうちのいずれか一方または双方を含有する化合物は、リンおよび窒素双方を含有するものとして、リン酸グアニジン、リン酸メラミン、リン酸グアニル尿素等を挙げることができる。このうち、リン酸グアニジンを用いることは好適な実施の形態である。また、リンおよび窒素のうちのいずれか一方を含有するものとしては、周知の適宜の化合物、例えばリン酸や炭酸グアニジン等を用いることができる。
リン酸グアニジンを用いる場合、植物からリグニンを溶出した後の乾燥植物１００質量部に対して、リン酸グアニジンを純物質基準で１〜２０質量部加えることが好ましい。
リグニンを溶出した後の乾燥植物にリン酸グアニジンを含浸法等によって加えて加熱して炭化する条件は、６００〜１０００℃の加熱温度で０．５〜２時間の加熱時間とすることが好ましい。このとき、窒素等の不活性ガス雰囲気下で処理することが好ましい。
リグニンを溶出した後の乾燥植物を炭化した後、好ましくは、６００〜１０００℃の加熱温度で、二酸化炭素ガスで１〜５時間処理し、その後不活性ガス雰囲気下で室温まで冷却して賦活することが好ましい。加熱温度は、７００〜９００℃であると、より好ましい。処理時間は、２〜４時間であると、より好ましい。
Examples of the compound containing either or both of phosphorus and nitrogen include guanidine phosphate, melamine phosphate, guanylurea phosphate and the like as those containing both phosphorus and nitrogen. Of these, the use of guanidine phosphate is a preferred embodiment. Moreover, as what contains any one of phosphorus and nitrogen, a well-known appropriate compound, for example, phosphoric acid, a guanidine carbonate, etc. can be used.
When using guanidine phosphate, it is preferable to add 1 to 20 parts by mass of guanidine phosphate on a pure substance basis with respect to 100 parts by mass of the dried plant after eluting lignin from the plant.
The conditions for adding guanidine phosphate to the dried plant after elution of lignin by the impregnation method, etc., and heating and carbonizing are preferably set at a heating temperature of 600 to 1000 ° C. for a heating time of 0.5 to 2 hours. At this time, it is preferable to process in inert gas atmosphere, such as nitrogen.
After carbonizing the dried plant after eluting lignin, it is preferably treated with carbon dioxide gas at a heating temperature of 600 to 1000 ° C. for 1 to 5 hours, and then cooled to room temperature in an inert gas atmosphere to activate. It is preferable. The heating temperature is more preferably 700 to 900 ° C. The treatment time is more preferably 2 to 4 hours.
以上説明した本実施の形態例に係る多孔質炭素材料の製造方法により得られる多孔質炭素材料は、特許文献１の発明の製造方法により得られる炭素材料よりも大きく、かつ市販の電気二重層キャパシタと同程度の比表面積を有する。 The porous carbon material obtained by the method for producing a porous carbon material according to this embodiment described above is larger than the carbon material obtained by the production method of the invention of Patent Document 1 and is a commercially available electric double layer capacitor. Specific surface area of the same level.
本実施の形態例に係る多孔質炭素材料の製造方法により得られる多孔質炭素材料は、活性炭や電気二重層キャパシタ電極等の用途に好適に使用できる。
活性炭としては、揮発性ガスに対する吸着剤、メタンガスの運搬や貯蔵材料、色素含有廃液の脱色剤、バイオエタノールの回収材、脱臭剤として使用できる。また、電気二重層キャパシタ電極としては、回路部品、レーザープリンタ、コピー機等の大容量蓄電や急速加熱用途やハイブリッド自動車に使用できる。
The porous carbon material obtained by the method for producing a porous carbon material according to this embodiment can be suitably used for applications such as activated carbon and electric double layer capacitor electrodes.
As activated carbon, it can be used as an adsorbent for volatile gases, a material for transporting and storing methane gas, a decolorizer for dye-containing waste liquid, a bioethanol recovery material, and a deodorizer. Moreover, as an electric double layer capacitor electrode, it can be used for high capacity | capacitance electrical storage, rapid heating uses, such as a circuit component, a laser printer, a copy machine, and a hybrid vehicle.
本発明の実施例を説明する。なお、本発明は、以下に説明する実施例に限定されるものではない。 Examples of the present invention will be described. In addition, this invention is not limited to the Example demonstrated below.
（多孔質炭素材料の調製：実施例）
原料として500μm以下の竹粉末（バンブーケミカル社製自動竹粉作製装置で製造）を用いた。
得られた竹粉末２０ｇを容器に入れて、30w/v％過酸化水素水100ｍｌおよび酢酸100ｍｌをそれぞれ含浸し、８５℃の温度で８時間攪拌した。ついで、吸引濾過、蒸留水による洗浄および恒量となるまでの乾燥処理を行い、リグニンを溶出した竹粉末（以下、これを脱リグニン竹粉末という。）を得た。なお、脱リグニン処理前後の竹粉末のリグニン量を硫酸法で測定したところ、処理前の竹粉末が２１．４ｗｔ％、処理後の竹粉末が０ｗｔ％であった。
得られた脱リグニン竹粉末に、リン酸グアニジン（東京化成工業株式会社製、製品名リン酸グアニジン 主成分：リン酸グアニジン95.0容量％ リン含有量14.33質量％ 窒素有量6.48質量％）を、質量比で脱リグニン竹粉末：リン酸グアニジン＝２０：１の割合で混合し、１日放置して乾燥した。
管状炉（アズワン社製、ARF-50K）に乾燥後のリン酸グアニジン添着脱リグニン竹粉末を配置し、窒素ガスを９リットル／ｈｒの流速で流通して加熱炉内を窒素ガス雰囲気として８００℃の温度で１時間加熱、焼成して、リン酸グアニジン添着脱リグニン竹粉末を炭化した。さらに、８００℃の温度を保持しながら加熱炉に二酸化炭素ガスを９リットル／ｈｒの流速で流通し、炭化物を賦活した。賦活時間は、０時間（実施例１）、１時間（実施例２）、２時間（実施例３）、３時間（実施例４）および４時間（実施例５）の５水準とした。その後、窒素ガス雰囲気に戻し、室温まで冷却して多孔質炭素材料を得た。
(Preparation of porous carbon material: Examples)
As a raw material, bamboo powder of 500 μm or less (manufactured by an automatic bamboo powder production apparatus manufactured by Bamboo Chemical Co., Ltd.) was used.
20 g of the obtained bamboo powder was put in a container, impregnated with 100 ml of 30 w / v% hydrogen peroxide water and 100 ml of acetic acid, and stirred at a temperature of 85 ° C. for 8 hours. Subsequently, suction filtration, washing with distilled water, and drying to a constant weight were performed to obtain bamboo powder eluting lignin (hereinafter referred to as delignified bamboo powder). In addition, when the amount of lignin of the bamboo powder before and after the delignification treatment was measured by the sulfuric acid method, the bamboo powder before the treatment was 21.4 wt% and the bamboo powder after the treatment was 0 wt%.
To the resulting delignified bamboo powder, guanidine phosphate (manufactured by Tokyo Chemical Industry Co., Ltd., product name: guanidine phosphate, main component: guanidine phosphate 95.0% by volume, phosphorus content 14.33% by mass, nitrogen content 6.48% by mass), mass The ratio of delignified bamboo powder: guanidine phosphate was mixed at a ratio of 20: 1 and left to dry for one day.
Arranged lignin bamboo powder with guanidine phosphate attached and dried in a tubular furnace (ARF-50K, manufactured by ASONE Co., Ltd.), nitrogen gas was circulated at a flow rate of 9 liters / hr, and the inside of the heating furnace was set to a nitrogen gas atmosphere at 800 ° C. The lignin bamboo powder added and detached with guanidine phosphate was carbonized by heating and firing at a temperature of 1 hour. Furthermore, carbon dioxide gas was circulated through the heating furnace at a flow rate of 9 liter / hr while maintaining a temperature of 800 ° C. to activate the carbide. The activation time was set to 5 levels of 0 hour (Example 1), 1 hour (Example 2), 2 hours (Example 3), 3 hours (Example 4) and 4 hours (Example 5). Then, it returned to nitrogen gas atmosphere and cooled to room temperature, and obtained the porous carbon material.
（多孔質炭素材料の調製：比較例１）
脱リグニン処理および賦活処理を行わなかったほかは実施例１と同様の加熱条件で竹粉末を炭化して多孔質炭素材料（比較例１）を得た。
(Preparation of porous carbon material: Comparative Example 1)
Bamboo powder was carbonized under the same heating conditions as in Example 1 except that delignification treatment and activation treatment were not performed to obtain a porous carbon material (Comparative Example 1).
（多孔質炭素材料の調製：比較例２）
蒸留水を入れた容器に、球状セルロース(大東化成工業株式会社製 CELLULOBEADS D-100直径（粒度分布における中位径 100μm以下)にリン酸グアニジン（東京化成工業株式会社製 製品名リン酸グアニジン 主成分：リン酸グアニジン95.0容量％ リン含有量14.33質量％ 窒素有量6.48質量％）を球状セルロースに対して質量比で球状セルロース：リン酸グアニジン =２０:１の割合で加え、１日放置して乾燥した。
管状炉に乾燥後のリン酸グアニジン添着球状セルロースを配置し、窒素ガスを９リットル／ｈｒの流速で流通して加熱炉内を窒素ガス雰囲気として８５０℃の温度で１時間加熱、焼成して、リン酸グアニジン添着球状セルロースを炭化した後、室温まで冷却して多孔質炭素材料（比較例２）を得た。
(Preparation of porous carbon material: Comparative Example 2)
In a container containing distilled water, spherical cellulose (CELLULOBEADS D-100 diameter manufactured by Daito Kasei Kogyo Co., Ltd.) (Guanidine phosphate manufactured by Tokyo Chemical Industry Co., Ltd.) ： Guanidine phosphate 95.0% by volume Phosphorus content 14.33% by mass Nitrogen content 6.48% by mass) Spherical cellulose by mass ratio with respect to spherical cellulose: guanidine phosphate = 20: 1 did.
Place the dried guanidine phosphate-impregnated spherical cellulose in a tubular furnace, circulate nitrogen gas at a flow rate of 9 liters / hr and heat and calcinate at 850 ° C. for 1 hour in a nitrogen gas atmosphere, After carbonizing the guanidine phosphate-impregnated spherical cellulose, it was cooled to room temperature to obtain a porous carbon material (Comparative Example 2).
（多孔質炭素材料の物性等評価）
実施例および各比較例について、比表面積等の物性を測定、評価した結果をまとめて表１に示す。
(Evaluation of physical properties of porous carbon materials)
Table 1 summarizes the results of measurement and evaluation of physical properties such as specific surface area for the examples and comparative examples.
Claims (4)
The method for producing a porous carbon material according to claim 1, wherein the plant is bamboo powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013140432A JP6288663B2 (en) | 2013-07-04 | 2013-07-04 | Method for producing porous carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013140432A JP6288663B2 (en) | 2013-07-04 | 2013-07-04 | Method for producing porous carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015013767A JP2015013767A (en) | 2015-01-22 |
| JP6288663B2 true JP6288663B2 (en) | 2018-03-07 |
Family
ID=52435827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013140432A Active JP6288663B2 (en) | 2013-07-04 | 2013-07-04 | Method for producing porous carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6288663B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744789A (en) * | 2016-11-14 | 2017-05-31 | 天津工业大学 | A kind of utilization lignin prepares porous charcoal and the application in ultracapacitor |
| KR20210089643A (en) * | 2018-11-09 | 2021-07-16 | 주식회사 쿠라레 | Carbonaceous material, its manufacturing method, electrode active material for electrochemical device, electrode for electrochemical device, and electrochemical device |
| CN112794324B (en) * | 2019-11-14 | 2022-10-25 | 华南理工大学 | High-mesoporosity lignin hierarchical pore carbon material and preparation method and application thereof |
| CN114804100B (en) * | 2022-05-13 | 2023-10-27 | 中南大学 | Porous carbon with ultrahigh specific surface area and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005047724A (en) * | 2003-07-30 | 2005-02-24 | Araco Corp | Production method for molded active carbon |
| JP2005126292A (en) * | 2003-10-24 | 2005-05-19 | Araco Corp | Manufacturing method of active carbon |
| JP2007269555A (en) * | 2006-03-31 | 2007-10-18 | Kitakyushu Foundation For The Advancement Of Industry Science & Technology | Activated carbon molded product and method for manufacturing the same |
| JP5652636B2 (en) * | 2010-05-16 | 2015-01-14 | 国立大学法人九州工業大学 | Method for producing carbon material for electric double layer capacitor polarizable electrode |
| JP5846575B2 (en) * | 2011-09-16 | 2016-01-20 | 国立大学法人九州工業大学 | Manufacturing method of electric double layer capacitor |
| JP2013087132A (en) * | 2011-10-13 | 2013-05-13 | Oji Holdings Corp | Method for producing fine fibrous cellulose |
-
2013
- 2013-07-04 JP JP2013140432A patent/JP6288663B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2015013767A (en) | 2015-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101648707B (en) | Preparation method of activated carbon with high pore volume | |
| CN107108232B (en) | Activated carbon, hydrothermal carbon and preparation method thereof | |
| Sevilla et al. | A green approach to high‐performance supercapacitor electrodes: the chemical activation of hydrochar with potassium bicarbonate | |
| JP5400892B2 (en) | Method for producing porous activated carbon | |
| JP6513401B2 (en) | Active carbon fiber having high active surface area | |
| JP6288663B2 (en) | Method for producing porous carbon material | |
| RU2562285C2 (en) | Method for production of filter for tobacco smoke filtering | |
| Mueller et al. | Influence of the nanofiber dimensions on the properties of nanocellulose/poly (vinyl alcohol) aerogels | |
| JP5781992B2 (en) | Parenteral adsorbent provided with basic functional group and method for producing the same | |
| JP6760583B2 (en) | How to make activated carbon | |
| JP2012507470A5 (en) | ||
| Shen et al. | Hollow porous carbon fiber from cotton with nitrogen doping | |
| Khan et al. | Developments in activated functionalized carbons and their applications in water decontamination: a review | |
| Kang et al. | Hierarchically Porous Carbons Derived from Cotton Stalks for High‐Performance Supercapacitors | |
| Ding et al. | Novel Biomass‐Derived Adsorbents Grafted Sodium Titanium Silicate with High Adsorption Capacity for Rb+ and Cs+ in the Brine | |
| Wang et al. | Activated carbon preparation from cassava residue using a two-step KOH activation: preparation, micropore structure and adsorption capacity | |
| JP5231294B2 (en) | Volatile organic compound adsorbent and method for producing the same | |
| JP2006225231A (en) | Activated carbon from chitinous matter as raw material and its manufacturing method | |
| CN107051383A (en) | A kind of preparation method of carbon material for sewage disposal | |
| JP2009226401A (en) | Adsorbent for adsorbing volatile organic compound, its producing method and method for utilizing bark or its molding | |
| RU2620404C1 (en) | Method of obtaining mesoporous carbon | |
| JP2005126292A (en) | Manufacturing method of active carbon | |
| JP6624993B2 (en) | Activated carbon production method | |
| JP2016026985A (en) | Method for producing activated carbon | |
| JP7097683B2 (en) | Method for manufacturing chemically activated carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20150629 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20150629 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160607 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170214 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170216 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170407 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170829 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171030 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180109 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180131 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6288663 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |