JPH03106443A - Globular porous carbon particle and preparation thereof - Google Patents
Globular porous carbon particle and preparation thereofInfo
- Publication number
- JPH03106443A JPH03106443A JP1240564A JP24056489A JPH03106443A JP H03106443 A JPH03106443 A JP H03106443A JP 1240564 A JP1240564 A JP 1240564A JP 24056489 A JP24056489 A JP 24056489A JP H03106443 A JPH03106443 A JP H03106443A
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- particle
- globular
- particles
- porous carbon
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 229920002678 cellulose Polymers 0.000 claims abstract description 31
- 239000001913 cellulose Substances 0.000 claims abstract description 30
- 238000011282 treatment Methods 0.000 claims abstract description 10
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 21
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 238000012856 packing Methods 0.000 abstract description 7
- 238000010000 carbonizing Methods 0.000 abstract description 4
- 238000004587 chromatography analysis Methods 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 4
- 238000005899 aromatization reaction Methods 0.000 abstract description 2
- 238000005087 graphitization Methods 0.000 abstract description 2
- 208000005156 Dehydration Diseases 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012798 spherical particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- -1 and fired Substances 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- RLDQYSHDFVSAPL-UHFFFAOYSA-L calcium;dithiocyanate Chemical compound [Ca+2].[S-]C#N.[S-]C#N RLDQYSHDFVSAPL-UHFFFAOYSA-L 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、球状多孔性炭素粒子に関する。更に詳しくは
、気体や有機物質の吸着剤、機能性物質の固定化用担体
あるいは、液体クロマトグラフィー川充填剤として有用
な球状多孔性炭素粒子に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to spherical porous carbon particles. More specifically, the present invention relates to spherical porous carbon particles useful as adsorbents for gases or organic substances, carriers for immobilizing functional substances, or fillers for liquid chromatography.
〔従来の技術及び発明が解決しようとする課題〕従来よ
り多孔性炭素粒子は触媒用担体、吸着剤などの用途に用
いられている。又、最近では医療用として人工肝臓や人
工腎臓などの人工臓器、更には多孔性炭素粒子の次の特
性によって液体クロマトグラフィー用充填剤として注目
され検討が始められている。[Prior Art and Problems to be Solved by the Invention] Porous carbon particles have heretofore been used as catalyst carriers, adsorbents, and the like. In addition, recently, porous carbon particles have been attracting attention and investigation as a packing material for artificial organs such as artificial livers and artificial kidneys, and for liquid chromatography due to the following characteristics.
以下に多孔性炭素粒子の一般的特性を示す。General characteristics of porous carbon particles are shown below.
(1)機械的強度が大きい。(1) High mechanical strength.
(2)比表面積は、50〜5 0 0 rd / tで
相応の保持に適当である。(2) The specific surface area is 50 to 500 rd/t, which is suitable for appropriate retention.
(3)5nm以上の微細孔をもち、物質移動しやすい。(3) Possesses micropores of 5 nm or more for easy mass transfer.
(4)相互作用部位が粒子表面に均一に分布する。(4) Interaction sites are uniformly distributed on the particle surface.
(5)広いpH領域の緩衝液が使用でき、化学的安定性
が良い。(5) Buffer solutions with a wide pH range can be used, and chemical stability is good.
(6)理論的に無極性不活性である。(6) Theoretically non-polar and inert.
(7〉耐熱性が良い。(7> Good heat resistance.
(8)形態安定性がある。(8) It has morphological stability.
以上の特長は、液体クロマトグラフィー川充填剤等の上
記用途に要請される条件をほとんど満たしている。本発
明はこの液体クロマトグラフィー用充填剤等に用いる事
の出来る炭素粒子を提供するものである。The above features almost satisfy the requirements for the above-mentioned applications such as liquid chromatography packing material. The present invention provides carbon particles that can be used as packing materials for liquid chromatography.
多孔性炭素粒子の製造方法は、一般的には、カーボンブ
ラックと樹脂バインダーとを押圧成形した後炭化焼成し
、焼威後得られた戊形体を破砕して所望の粒径の粒子と
する。The method for producing porous carbon particles generally involves press-molding carbon black and a resin binder, then carbonizing and firing, and crushing the oval bodies obtained after firing to obtain particles with a desired particle size.
しかしながら、戊形体を破砕することにより得られる粒
子は破砕品の為球状とは言えず、また粒度分布も広範囲
であり液体クロマトグラフィー用充填剤としては不充分
であった。これらの欠点を補う為カーボンブラックを予
め球状化し、バインダーを含浸させ焼成する方法あるい
は炭素源として、ポリアクリル系樹脂、ボリスチレン系
樹脂、フェノール樹脂、ポリ塩化ビニル等の合成重合物
の球状粒子を用い加熱処理し炭素化する方法が提案され
ている(特開昭53−48989号公報、特開昭54−
4 1 296号公報)。However, the particles obtained by crushing the cylindrical body cannot be said to be spherical because they are crushed, and the particle size distribution is also wide, making them insufficient as a filler for liquid chromatography. To compensate for these drawbacks, carbon black is spheroidized in advance, impregnated with a binder, and fired, or spherical particles of synthetic polymers such as polyacrylic resin, polystyrene resin, phenol resin, polyvinyl chloride, etc. are used as the carbon source. A method of heat treatment and carbonization has been proposed (JP-A-53-48989, JP-A-54-
4 1 296).
しかし、いずれの方法においても焼成加熱処理する際バ
インダーあるいは合成重合物の融角ダによる粒子間の固
着、壊化、凝集化が起こり、均一な球状粒子を得ること
は困難であった。However, in any of these methods, during the calcination heat treatment, interparticle fixation, breakage, and agglomeration occur due to the fusion angle of the binder or synthetic polymer, making it difficult to obtain uniform spherical particles.
加熱処理における融解を防止するためには、たとえば特
開If?{ 5 3 − 4 8 9 8 9号公報に
記載されているように、スルホン化、ニトロ化などの処
理が行なわれているが、効果が充分とはいえなかった。In order to prevent melting during heat treatment, for example, JP-A If? {As described in Japanese Patent No. 53-48989, treatments such as sulfonation and nitration have been carried out, but the effects were not sufficient.
本発明者等はセルロースが加熱によって溶融あるいは軟
化することがない物質であることに着[iし、セルロー
スを炭素源として用いれば加熱処理における粒子の変形
、固着等の問題が角ll決できると考えた。本発明者等
はこの考えに従って研究し、セルロース球状粒子を脱水
縮合処理し、ついで加熱処理することにより均一な球状
炭素粒子が容易に得られること、また使用する球状セル
ロースの性状によって、得られた球状炭素粒子の多孔性
をコントロールできること、を知見した。この知見に基
づいて更に検討の粘果、本発明に到達した。The present inventors found that cellulose is a substance that does not melt or soften when heated, and that problems such as particle deformation and sticking during heat treatment can be resolved by using cellulose as a carbon source. Thought. The present inventors conducted research in accordance with this idea, and found that uniform spherical carbon particles can be easily obtained by subjecting cellulose spherical particles to dehydration condensation treatment and then heat treatment, and that the properties of the spherical cellulose used We discovered that the porosity of spherical carbon particles can be controlled. Based on this knowledge, we further investigated and arrived at the present invention.
本発明は下記のものを包含する。The present invention includes the following.
(1)平均粒径が1〜300μmであり、比表面積が5
0〜1000rrr/gである球状多孔性炭素粒子。(1) Average particle size is 1 to 300 μm and specific surface area is 5
Spherical porous carbon particles having a particle size of 0 to 1000 rrr/g.
(2)球状セルロースを脱水重合処理し、次いで炭化焼
成することを特徴とする球状多孔性炭素粒子の製造方法
。(2) A method for producing spherical porous carbon particles, which comprises dehydrating and polymerizing spherical cellulose and then carbonizing it.
本発明に用いられる球状セルロース粒子は、真球状であ
りその製造方法としては、次の様な例があるが特に限定
されるものではない。The spherical cellulose particles used in the present invention are truly spherical, and methods for producing them include the following examples, but are not particularly limited.
■ 特開11r{ 5 3 − 8 6 7 4 9号
公報に記載の方法で、セルロース酢酸エステルを有機溶
媒中に溶角?し、この溶液を水性溶媒中に懸濁させて球
状化し、有機溶媒を蒸発させてセルロースエステル粒子
ヲ得、これをケン化後セルロース粒子とする方法。■ By the method described in JP-A No. 11r{53-86749, cellulose acetate is dissolved in an organic solvent. A method in which this solution is suspended in an aqueous solvent and spheroidized, the organic solvent is evaporated to obtain cellulose ester particles, which are then saponified to become cellulose particles.
■ ■の方法の応用でセルロース酢酸エステルの溶液に
脂肪族高級アルコール等を加えて、多孔性を調節する特
開昭56−24429号公報の方法。(2) A method disclosed in JP-A-56-24429, in which the porosity is adjusted by adding an aliphatic higher alcohol or the like to a solution of cellulose acetate as an application of the method (2).
■ セルロースをバラホルムアルデヒドとジメチルスル
ホキシドの混合溶媒にとかして造粒する特開11fl
5 7 − 1 5 9 8 0 1号公報、特公IM
{ 5 7 −1 59802号公報の方法。■ Unexamined patent publication 11fl in which cellulose is granulated by dissolving it in a mixed solvent of rose formaldehyde and dimethyl sulfoxide.
57-159801 Publication, Special Publication IM
{The method disclosed in 57-1 59802.
■ セルロースを水酸化第2銅、塩化第1銅の濃アンモ
ニア水に溶解して造粒する特開11r{ 5 2 −1
1237号公報の方法。■ JP-A 11r { 5 2 -1 in which cellulose is dissolved in concentrated ammonia water containing cupric hydroxide and cuprous chloride and granulated
The method of Publication No. 1237.
■ ビスコースを変圧器浦中に分散させて逍粒する特開
昭51−5361号公報の方法。■ A method disclosed in Japanese Patent Application Laid-Open No. 51-5361, in which viscose is dispersed and granulated in a transformer well.
■ セルロースをチオシアン酸カルシウム塩溶液に溶解
させて造粒する特開nr4 5 5 − 4 4 3
1 2号公報の方法。■ JP-A No. 4,555-443, in which cellulose is dissolved in a calcium thiocyanate salt solution and granulated.
1 Method of Publication No. 2.
■ 梢製リンターを銅アンモニア溶液に溶解させて造粒
する特開昭48−60754号公報の方法。(2) A method disclosed in Japanese Patent Application Laid-open No. 48-60754, in which Kozue-made linter is dissolved in a copper ammonia solution and granulated.
■ ビスコースと水溶性アニオン性高分子化合物とを混
合してビスコースの分散液を生成せしめ加熱し凝固させ
る特開昭61−241337号公flJの方法。(2) The method disclosed in JP-A-61-241337 flJ, in which viscose and a water-soluble anionic polymer compound are mixed to form a viscose dispersion, which is then heated and coagulated.
用いる球状セルロース粒子は平均粒子径が3〜300μ
mのものを用いるのがよい。The spherical cellulose particles used have an average particle diameter of 3 to 300μ.
It is better to use m.
球状セルロース粒子は水等を含む場合は通常は乾燥して
使用する。乾燥方法は特に限定されないが、例えば炉過
して大部分の液体を除去した後加熱乾燥する方法、アル
コール、エーテル、アセトン等の溶媒に置換後減圧乾燥
する方法等がある。If the spherical cellulose particles contain water or the like, they are usually used dry. The drying method is not particularly limited, but includes, for example, a method in which most of the liquid is removed through an oven and then dried by heating, a method in which the material is substituted with a solvent such as alcohol, ether, or acetone, and then dried under reduced pressure.
セルロース粒子はまず加熱脱水縮合処理(予備炭化)に
付する。この処理は100〜400℃、好ましくは20
0〜300℃で3〜6時間行なわれ、真空あるいは不活
性ガス雰囲気で可能であるが、酸性ガス、例えば乾燥塩
化水素ガスの存在下に実施することも反応の促進に有効
である。The cellulose particles are first subjected to a heating dehydration condensation treatment (preliminary carbonization). This treatment is carried out at 100-400°C, preferably at 20°C.
The reaction is carried out at 0 to 300°C for 3 to 6 hours, and can be carried out in vacuum or in an inert gas atmosphere, but it is also effective to carry out the reaction in the presence of an acidic gas, such as dry hydrogen chloride gas, to accelerate the reaction.
セルロース粒子を炭化焼成するには、電気炉またはロー
タリーキルン等を用い窒素、アルゴンなどの不活性ガス
雰囲気下で加熱焼成するのがよい。In order to carbonize and fire the cellulose particles, it is preferable to heat and fire them in an atmosphere of an inert gas such as nitrogen or argon using an electric furnace or a rotary kiln.
均一に炭化焼成するためにはロータリーキルン、流動床
炉等の非固定式炉が望ましい。焼成温度は、低すぎては
炭化が進まないし、高すぎても炭化の進行を促進するこ
とはない為、通常500〜3000℃が望ましい。特に
2000〜3000℃で行うとグラファイト化が起こる
事により得られる球状炭素粒子の硬度が上がり、炭素化
工程中におこるセルロースの芳香族化が消失しクロマト
グラフィー操作において、不要な非特異吸着が減少する
という利点がある。For uniform carbonization and firing, a non-fixed furnace such as a rotary kiln or a fluidized bed furnace is preferable. If the firing temperature is too low, carbonization will not proceed, and if it is too high, the carbonization will not proceed, so it is usually desirable to set the firing temperature to 500 to 3000°C. In particular, when carried out at 2,000 to 3,000°C, graphitization occurs, increasing the hardness of the resulting spherical carbon particles, eliminating the aromatization of cellulose that occurs during the carbonization process, and reducing unnecessary non-specific adsorption during chromatography operations. There is an advantage to doing so.
昇温速度については、速すぎると球状粒子の形状が保て
ない為、5℃〜1000℃/時間、望ましくは、50℃
〜500℃/時間が好適である。Regarding the heating rate, if it is too fast, the shape of the spherical particles cannot be maintained, so the heating rate should be 5°C to 1000°C/hour, preferably 50°C.
~500°C/hour is preferred.
焼成時間は、昇温速度に依存する。50℃〜500℃/
時間の昇温速度であれば希望する温度に達したのち0.
1〜24時間あれば炭化焼成は達成される。The firing time depends on the temperature increase rate. 50℃~500℃/
If the heating rate is 1 hour, the desired temperature will be reached and then 0.
Carbonization and firing can be achieved in 1 to 24 hours.
このようにして平均粒径が1〜300μmであり、比表
面積が50〜1000rrl”/gである球状多孔性炭
素粒子をうろことができる。In this way, spherical porous carbon particles having an average particle diameter of 1 to 300 μm and a specific surface area of 50 to 1000 rrl''/g can be obtained.
以下に実施例として、球状セルロース粒子を出発原料と
した球状炭素粒子の製造方法と得られた粒子の使川例を
示すが本発明はかかる実施例のみに限定されるものでは
ない。As an example, a method for producing spherical carbon particles using spherical cellulose particles as a starting material and an example of the use of the obtained particles will be shown below, but the present invention is not limited to these examples.
以下の例で、平均粒径の測定はコールカウンター(モデ
ルTAII 仲日科機製)で測定した。又、比表面積
は比表面積測定装置(モデル2205島律製作所■製)
を用いアルゴンを使用してBET低温吸着法にて測定し
た。In the following examples, the average particle diameter was measured using a coal counter (model TAII, manufactured by Nakanikaki Ki). In addition, the specific surface area is measured using a specific surface area measuring device (Model 2205 manufactured by Shima Ritsu Seisakusho ■)
It was measured by the BET low temperature adsorption method using argon.
実施例1
特開11n5 5 − 4 4 3 1 2号公報の実
施例1の方法で製造したセルロース粒子のサクションド
ライ品100gをメタノール、エタノール、エーテルを
各々240ml用いて順次洗浄し溶媒置換を行った後ろ
過しロータリーエバボレーターで真空乾燥を行った。得
られた乾燥セルロース粒子を更に、乾燥塩化水素ガス雰
囲気下300℃で3時間加熱処理し、脱水縮合処理を行
った。Example 1 100g of suction-dried cellulose particles produced by the method of Example 1 of JP-A-11N55-44312 was washed sequentially with 240ml each of methanol, ethanol, and ether to perform solvent replacement. After filtering, vacuum drying was performed using a rotary evaporator. The obtained dried cellulose particles were further heat-treated at 300° C. for 3 hours in a dry hydrogen chloride gas atmosphere to perform a dehydration condensation treatment.
得られた粒子をロータリーキルンを用い窒素気流中30
0℃まで4時間、300℃からiooo℃まで14時間
で昇温し、この温度で4nq間炭化焼成して球状炭素粒
子81rを得た。The obtained particles were heated in a nitrogen stream for 30 minutes using a rotary kiln.
The temperature was raised to 0° C. for 4 hours and from 300° C. to iooo° C. in 14 hours, and carbonized and fired at this temperature for 4 nq to obtain spherical carbon particles 81r.
得られた炭素粒子の平均粒径は13μm1比表而積は6
8 0 rd / gであった。The average particle size of the obtained carbon particles was 13 μm, and the specific surface area was 6.
It was 80rd/g.
実施例2
特開11fl 5 6 − 2 4 4 2 9号公報
の実施例1の方法で製造したセルロース粒子のサクショ
ンドライ品 200Kをジオキサン及びエーテル各40
0m!で洗浄し、溶媒置換を行った後ロータリーエバボ
レーターで真空乾燥した。得られた乾燥セルロース粒子
を更に乾燥塩化水素雰囲気中で350℃、4時間加熱処
理し、脱水縮合処理を行った。Example 2 A suction-dried product of cellulose particles produced by the method of Example 1 of JP-A No. 11fl56-24429. 200K was mixed with 40% each of dioxane and ether.
0m! After washing with and replacing the solvent, vacuum drying was performed using a rotary evaporator. The obtained dried cellulose particles were further heat-treated at 350° C. for 4 hours in a dry hydrogen chloride atmosphere to perform a dehydration condensation treatment.
得られた粒子を流動床炉に入れアルゴンガス雰囲気中1
000℃まで20時間、更に2800℃まで21時間か
け昇温し、2800℃で0.5時間炭化焼成して球状多
孔性炭素粒子15.を得た。The obtained particles were placed in a fluidized bed furnace in an argon gas atmosphere.
The temperature was raised to 000°C for 20 hours, then to 2800°C for 21 hours, and carbonized and fired at 2800°C for 0.5 hours to obtain spherical porous carbon particles 15. I got it.
得られた炭素粒子の平均粒径は25μm1比表面積は5
2rrr/srであった。The average particle size of the obtained carbon particles was 25 μm, and the specific surface area was 5.
It was 2rrr/sr.
実施例3
市販されているセルロースビーズ(セルロファイン(商
標)GCタイプ チッソ■製)のサクションドライ50
0gをメタノール21,エタノール1Iで各々洗浄し、
溶媒置換を行った後、ろ過しロータリーエバボレーター
で真空乾燥を行った。Example 3 Suction drying of commercially available cellulose beads (Cellulofine (trademark) GC type manufactured by Chisso ■) 50
Wash 0g with 21 methanol and 1I ethanol,
After the solvent was replaced, it was filtered and vacuum dried using a rotary evaporator.
得られたセルロース粒子を更に乾燥塩化水素ガス雰囲気
下300℃で6時間加熱処理し、脱水縮合処理を行った
後粒子をアセ1・ン2gで洗浄しろ過しロータリーエバ
ボレータで真空乾燥した。The obtained cellulose particles were further heat-treated at 300° C. for 6 hours in a dry hydrogen chloride gas atmosphere to perform a dehydration condensation treatment, and then the particles were washed with 1.2 g of acetic acid, filtered, and vacuum-dried in a rotary evaporator.
得られた粒子をロータリーキルンを用いアルゴンガス雰
囲気中で300℃まで4時間、300℃から1000℃
まで14時間、1000℃から2200℃まで5時間で
昇温し、2200℃で2時III炭化焼成して、球状炭
素粒子42.を得た。The obtained particles were heated in a rotary kiln at 300°C to 1000°C for 4 hours in an argon gas atmosphere.
The temperature was raised from 1,000°C to 2,200°C in 5 hours, and carbonized and fired at 2,200°C for 2 hours to form spherical carbon particles. I got it.
得られた炭素粒子は平均粒径が6μm1比表面積が3
7 5 td / gであった。The obtained carbon particles have an average particle size of 6 μm and a specific surface area of 3
It was 75 td/g.
比較例1
実施例3において、セルロースビーズに代えて市販され
ているポリアクリルビーズ(オイバーギフト(商標)
Roha Pbarsa社製)を使用し、他を全く同様
な条件で行い、炭素粒子28gを得た。Comparative Example 1 In Example 3, commercially available polyacrylic beads (Oibergift (trademark)) were used instead of cellulose beads.
(manufactured by Roha Pbarsa) under the same conditions except that 28 g of carbon particles were obtained.
得られた炭素粒子は塊状のため平均粒径は測定不能であ
り、比表面積は0.3rrr/gであった。The average particle size of the obtained carbon particles was unmeasurable because they were in the form of agglomerates, and the specific surface area was 0.3 rrr/g.
比較試験1
実施例3及び比較例1で得られた粒子を比較する為に各
粒子を走査型電子顕微鏡写真で観察した。Comparative Test 1 In order to compare the particles obtained in Example 3 and Comparative Example 1, each particle was observed using a scanning electron microscope photograph.
これを、第1図及び第2図.に示す。This is shown in Figures 1 and 2. Shown below.
セルロースビーズを出発原料とした多孔性炭素粒子は、
1個1個がきれいな球状を保っているのに比べ、ポリア
クリルビーズのそれは、融角ダ、固着、凝集しているの
が判る。Porous carbon particles using cellulose beads as starting material are
It can be seen that each individual bead maintains a beautiful spherical shape, whereas the polyacrylic beads have a poor fusion angle, stick together, and aggregate.
この粘果により、本発明の炭素粒子は均一な球状粒子で
ある串が判る。This viscosity reveals that the carbon particles of the present invention are uniform spherical particles.
使用例1
実施例1〜3で得られた球状炭素粒子を内径8關×長さ
100m−の液体クロマトグラフィー用ステンレス力ラ
ムに充填し、溶は液としてMeOH/ H 20 −
6 0 / 4 0 ( v / v )を用い安息香
酸エステル類をクロマトグラフィー操作した時の溶出挙
動を第3図に示した。Usage Example 1 The spherical carbon particles obtained in Examples 1 to 3 were packed into a stainless steel ram for liquid chromatography with an inner diameter of 8 mm and a length of 100 m, and the solution was MeOH/H20- as a liquid.
FIG. 3 shows the elution behavior when benzoic acid esters were subjected to chromatography using 60/40 (v/v).
横軸に溶出させた安息香酸エステル類のカーボン数を示
している。実施vq1〜3の各球状炭素粒子は、カーボ
ン数の増加とともにK′が増加しており、有機化合物の
分離が可能なすぐれた液体クロマトグラフィー用充填剤
である事が判る。The horizontal axis shows the number of carbon atoms in the eluted benzoic acid esters. In each of the spherical carbon particles of Examples vq1 to 3, K' increases as the number of carbon atoms increases, and it can be seen that they are excellent packing materials for liquid chromatography capable of separating organic compounds.
以上、詳細に説明した様に本発明によれば固着、塊化、
凝集することなく均一な球状炭素粒子を高収率で製造す
る市ができる。この様にして得られた球状炭素粒子は機
械的強度が大きく、比表面積は50〜1000rd”/
gに達し、化学的安定性が高い等、充填剤の特性を全て
備えており、高分子物質の吸着剤、クロマトグラフィー
用充填剤等に有用である。As explained above in detail, according to the present invention, fixation, clumping,
It is possible to produce uniform spherical carbon particles in high yield without agglomeration. The spherical carbon particles obtained in this way have high mechanical strength and a specific surface area of 50 to 1000rd”/
It has all the characteristics of a packing material, such as a high chemical stability, and is useful as an adsorbent for polymeric substances, a packing material for chromatography, etc.
第1、2図は各々実施例3及び比較例1で得られた各粒
子の走査!2rr1子顕微鎮写真である。
第3図は実施例1〜3で得られた球状炭素粒子を用いた
液体クロマトグラフィー操作により、安息!酸エステル
類を分離した時のキャパシティファクターK′と安息香
酸エステル類のカーボン数の関係を表した図である。
第1図
B℃!j””)7.t l 1θ,,第2
図
門晶Bo,Figures 1 and 2 are scans of each particle obtained in Example 3 and Comparative Example 1, respectively! This is a micrograph of a 2rr single child. Figure 3 shows the result of liquid chromatography using the spherical carbon particles obtained in Examples 1 to 3. FIG. 2 is a diagram showing the relationship between the capacity factor K' and the carbon number of benzoate esters when acid esters are separated. Figure 1 B℃! j””)7. t l 1θ,, second
Zumon Akira Bo,
Claims (1)
〜1000m^2/gである球状多孔性炭素粒子。 2、球状セルロースを脱水縮合処理し次いで、炭化焼成
することを特徴とする球状多孔性炭素粒子の製造方法。[Claims] 1. The average particle size is 1 to 300 μm and the specific surface area is 50 μm.
Spherical porous carbon particles with ~1000 m^2/g. 2. A method for producing spherical porous carbon particles, which comprises subjecting spherical cellulose to dehydration condensation treatment, followed by carbonization and firing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1240564A JP2989201B2 (en) | 1989-09-19 | 1989-09-19 | Spherical porous carbon particles and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1240564A JP2989201B2 (en) | 1989-09-19 | 1989-09-19 | Spherical porous carbon particles and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03106443A true JPH03106443A (en) | 1991-05-07 |
JP2989201B2 JP2989201B2 (en) | 1999-12-13 |
Family
ID=17061403
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1240564A Expired - Fee Related JP2989201B2 (en) | 1989-09-19 | 1989-09-19 | Spherical porous carbon particles and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2989201B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03164416A (en) * | 1989-11-20 | 1991-07-16 | Showa Denko Kk | Vitreous carbon powder and its production |
US6787029B2 (en) | 2001-08-31 | 2004-09-07 | Cabot Corporation | Material for chromatography |
US8555896B2 (en) | 2007-12-19 | 2013-10-15 | Philip Morris Usa Inc. | Activated carbon from microcrystalline cellulose |
-
1989
- 1989-09-19 JP JP1240564A patent/JP2989201B2/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03164416A (en) * | 1989-11-20 | 1991-07-16 | Showa Denko Kk | Vitreous carbon powder and its production |
US6787029B2 (en) | 2001-08-31 | 2004-09-07 | Cabot Corporation | Material for chromatography |
US7008534B2 (en) | 2001-08-31 | 2006-03-07 | Cabot Corporation | Material for chromatography |
US7195713B2 (en) | 2001-08-31 | 2007-03-27 | Cabot Corporation | Material for chromatography |
US7951297B2 (en) | 2001-08-31 | 2011-05-31 | Cabot Corporation | Material for chromatography |
US8555896B2 (en) | 2007-12-19 | 2013-10-15 | Philip Morris Usa Inc. | Activated carbon from microcrystalline cellulose |
Also Published As
Publication number | Publication date |
---|---|
JP2989201B2 (en) | 1999-12-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4820681A (en) | Preparation of hydrophobic carbon molecular sieves | |
EP0401285B1 (en) | Carbon dioxide removal using aminated carbon molecular sieves | |
JPH09328308A (en) | Activated carbon, its production and capacitor using the same | |
WO2001098209A1 (en) | Pyrolyzed hard carbon material, preparation and its applications | |
KR20140005245A (en) | Method of preparing porous carbon | |
CN111453724B (en) | Preparation method and application of three-dimensional porous carbon material | |
US4076651A (en) | Agglomerated siliceous bodies | |
CN114146679A (en) | Millimeter-grade nitrogen-doped porous carbon sphere and preparation and application thereof | |
JP3642532B2 (en) | Production method of high-performance activated carbon | |
KR101728098B1 (en) | Process method for the making micropore in the pellet | |
JP2902032B2 (en) | Spherical porous carbon particles and method for producing the same | |
JP3629743B2 (en) | Method for producing activated carbon | |
CN113861600A (en) | Bio-based porous material and preparation method and application thereof | |
JPH03106443A (en) | Globular porous carbon particle and preparation thereof | |
CN108946722A (en) | The preparation method and its product and purposes of the controllable spherical activated charcoal in aperture | |
JP6997299B2 (en) | Metahalloysite powder and its manufacturing method | |
JP2595296B2 (en) | Vapor-grown carbon fiber granulated material | |
JP4868326B2 (en) | Titanium oxide / carbon composite particles and production method thereof | |
JPH0692611A (en) | Production of carbonaceous particle | |
JPH03151041A (en) | Molded adsorbent | |
JPH0445445B2 (en) | ||
JPS6320762B2 (en) | ||
JPH02122828A (en) | Manufacture of adsorbent | |
JPH03275139A (en) | Globular fiber lump-activated carbon and its production | |
JP2799187B2 (en) | Porous graphitic carbon granules and support materials for chromatography using the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071008 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081008 Year of fee payment: 9 |
|
LAPS | Cancellation because of no payment of annual fees |