JPH01308818A - Production of activated carbon - Google Patents
Production of activated carbonInfo
- Publication number
- JPH01308818A JPH01308818A JP1030873A JP3087389A JPH01308818A JP H01308818 A JPH01308818 A JP H01308818A JP 1030873 A JP1030873 A JP 1030873A JP 3087389 A JP3087389 A JP 3087389A JP H01308818 A JPH01308818 A JP H01308818A
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- lignin
- alkali
- derivative
- followed
- 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 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920005610 lignin Polymers 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002655 kraft paper Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000010411 cooking Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 11
- 230000004913 activation Effects 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical compound COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- -1 sawdust Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
Landscapes
- 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、各種物質の吸着剤として多くの用途がある高
性能の活性炭を容易に製造する方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for easily producing high-performance activated carbon, which has many uses as an adsorbent for various substances.
（従来の技術）
活性炭は、工業用吸着剤として古くから利用されている
が、近年、公害防止などの技術の開発と共に、その需要
が著しく増大している。現在実際に市販されている活性
炭は、やしから、おがくず、石炭などを原料として製造
され、賦活方法によって、水蒸気賦活炭と塩化亜鉛賦活
炭の二種類に大別されている。(Prior Art) Activated carbon has been used as an industrial adsorbent for a long time, but its demand has increased significantly in recent years with the development of technologies for preventing pollution. Activated carbon that is currently on the market is manufactured using raw materials such as palm, sawdust, and coal, and is roughly divided into two types depending on the activation method: steam activated carbon and zinc chloride activated carbon.
（発明が解決しようとする課題）
上記の二種類の活性炭に関しては、製造上前者は９００
〜１２００℃の高温を必要とし、後者は薬品による腐蝕
・汚染などが問題となっている。(Problem to be solved by the invention) Regarding the above two types of activated carbon, the former has a 900%
It requires high temperatures of ~1200°C, and the latter poses problems such as corrosion and contamination due to chemicals.
いずれも製造の際に高度の技術を必要とするため、かな
り高価なことが問題点として指摘されている。The problem with both of these is that they require advanced technology to manufacture, so they are quite expensive.
また、現在主流の一つをしめているやしがら炭は、原料
のやしからを輸入にたよっているため、その供給に不安
があることも指摘されている。In addition, it has been pointed out that there are concerns about the supply of coconut shell charcoal, which is currently one of the mainstream products, as the raw material for the raw material is imported.
一方、石炭を原料とする場合には、副生ずるタール状物
質、廃ガスの処理に難があることが指摘されている。On the other hand, it has been pointed out that when coal is used as a raw material, there are difficulties in processing the by-product tar-like substances and waste gas.
さらに、これらの市販活性炭の比表面積は最高１６００
ｎ（／ｇ程度であるが、これよりも比表面積の大きい活
性炭が得られれば、吸着性能が向上するばかりでなく、
従来になかった用途が開発されるものと期待される。Furthermore, the specific surface area of these commercially available activated carbons is up to 1600
n(/g), but if activated carbon with a larger specific surface area than this can be obtained, not only will the adsorption performance improve,
It is expected that new uses will be developed.
一方、活性炭の製造に際し、原料としてリグニン又はそ
の誘導体を用いる検討もなされてきた。On the other hand, studies have also been made to use lignin or its derivatives as a raw material in the production of activated carbon.
たとえば、塩化亜鉛や塩化カルシウムで賦活する方法（
洋本ら、祇パ技術誌、２３，８ Ｑ、１９９゜２０１
（１９７９））、濃硫酸で炭化してから空気賦活する
方法ＣＢ、に、Ｐａ ｒｋら、Ｊ。For example, activation with zinc chloride or calcium chloride (
Yomoto et al., Gipa Technical Magazine, 23, 8 Q, 199°201
(1979)), Method CB of carbonization with concentrated sulfuric acid followed by air activation, Park et al., J.
Ｋｏｒｅａｎ ｃｈｅｍ、Ｓｏｃ、、２０＋１５３（
１９７６）等が知られている。Korean chem, Soc, 20+153(
1976) etc. are known.
しかしながら、これまでの方法は、重金属、腐食性物質
を使用したり、あるいは１０００℃近（に加熱する工程
を含んでいたり、さらに加熱工程が炭化、賦活と二段階
であったりして、上記の目的が達成されているとはいえ
ない。However, conventional methods use heavy metals and corrosive substances, or include a heating process to nearly 1000°C, and the heating process consists of two stages: carbonization and activation. It cannot be said that the purpose has been achieved.
そこで、本発明者は、リグニン又はその誘導体を原料と
し、比表面積が大きい活性炭を収率良く得る方法を見出
すべく、種々検討を行ない、本発明に到達した。Therefore, the present inventor conducted various studies in order to find a method for obtaining activated carbon with a large specific surface area in good yield using lignin or its derivatives as a raw material, and arrived at the present invention.
（課題を解決するための手段）
すなわち、本発明の要旨は、リグニン又はその誘導体に
、アルカリを添加し、ついで加熱処理して活性炭を得る
ことを特徴とする活性炭の製造方法にある。(Means for Solving the Problems) That is, the gist of the present invention resides in a method for producing activated carbon, which is characterized in that an alkali is added to lignin or a derivative thereof, and then heat-treated to obtain activated carbon.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
まず、本発明方法においては、活性炭を製造するために
、原料としてリグニン又はリグニン誘導体が用いられる
。First, in the method of the present invention, lignin or a lignin derivative is used as a raw material to produce activated carbon.
リグニンはセルロースおよびヘミセルロースとともに植
物体の骨格を形成する主要成分であり、木質化した植物
組織から二次的成分である樹脂、タンニン、灰分などを
除いた非炭水化物である。Lignin, along with cellulose and hemicellulose, is a major component that forms the skeleton of plants, and is a non-carbohydrate obtained by removing secondary components such as resin, tannin, and ash from lignified plant tissue.
このリグニンは、木材ではその含有量が２０〜３０−ｔ
％に達するが、未変化の状態では単離しに＜＜、単離法
としては、（ｉ）リグニンを不溶解残金として得る方法
、（ｉｉ ）リグニンを溶解して分離する方法に大別さ
れる常法を採用しうる。This lignin content is 20-30-t in wood.
%, but cannot be isolated in an unchanged state.Isolation methods are broadly divided into (i) methods to obtain lignin as an undissolved residue, and (ii) methods to dissolve and separate lignin. Conventional methods may be adopted.
工業的には、クラフト法（硫酸塩法）によるパルプ製造
廃液を中和して得られるチオリグニン、サルファイド法
パルプ蒸解液を濃縮乾燥して得られるリグニンスルホン
酸、等の誘導体が入手しやすく、好適に使用される。Industrially, derivatives such as thiolignin obtained by neutralizing pulp manufacturing waste liquid by the Kraft method (sulfate method) and lignin sulfonic acid obtained by concentrating and drying pulp cooking liquor by the sulfide method are easily available and suitable. used for.
たとえば、チオリグニンを得る方法としては、クラフト
法パルプ廃液であるＫＰ黒液を硫酸で中和してｐＨ２程
度でチオリグニンを析出せさる方法、又はＣ０ｆｆ１を
吹込んでｐＨ９程度で大部分のチオリグニンを析出させ
る方法等が採用される。For example, thiolignin can be obtained by neutralizing KP black liquor, which is waste liquid from Kraft process pulp, with sulfuric acid to precipitate thiolignin at a pH of about 2, or by blowing COff1 to precipitate most of the thiolignin at a pH of about 9. method etc. will be adopted.
また本発明においては、原料としてリグニン又はその誘
導体を含有する廃液類も使用しうる。たとえば、上記の
ＫＰ黒液が挙げられるが、得られる活性炭の特性を向上
させるために好適には酸化カルシウム、酸化バリウム等
を、好適には水溶液として添加して、無機塩類を沈澱さ
せた上澄液を用い得る。Furthermore, in the present invention, waste liquids containing lignin or its derivatives can also be used as raw materials. An example is the above-mentioned KP black liquor, but in order to improve the properties of the obtained activated carbon, calcium oxide, barium oxide, etc. are preferably added, preferably as an aqueous solution, and the supernatant is prepared by precipitating inorganic salts. liquid can be used.
次に、本発明方法においては、リグニン又はその誘導体
に、アルカリが添加される。アルカリとしては、ナトリ
ウム、カリウム等のアルカリ金属の水酸化物もしくは炭
酸塩、カルシウム、マグネシウム、バリウム等のアルカ
リ土類金属の水酸化物もしくは炭酸塩、等が挙げられる
が、得られる効果等の点から水酸化ナトリウム、水酸化
カリウムが最適である。これらのアルカリは、固体、水
溶液のいずれも使用しうる。Next, in the method of the present invention, an alkali is added to lignin or its derivative. Examples of the alkali include hydroxides or carbonates of alkali metals such as sodium and potassium, hydroxides or carbonates of alkaline earth metals such as calcium, magnesium, and barium, etc. However, in terms of the effects obtained, etc. Sodium hydroxide and potassium hydroxide are most suitable. These alkalis can be used either in solid form or in aqueous solution.
その使用量は、リグニン又はその誘導体１重量部に対し
、通常０．１〜１０重量部程度、好ましくは１〜５重量
重量部外ら選択される。The amount used is usually selected from about 0.1 to 10 parts by weight, preferably from 1 to 5 parts by weight, per 1 part by weight of lignin or its derivative.
上記アルカリを添加した後、リグニン又はその誘導体は
、加熱処理され、活性炭が得られる。たとえば、乾留炉
中でリグニン又はその誘導体に対して所定量のアルカリ
水溶液を加えてよく攪拌した後、加熱して水を留去し、
さらに温度を上昇させて炭化・賦活を一度に完成し、内
容物を取り出して水を加えてアルカリを回収し、残った
炭化物を十分に水洗・乾燥すると高性能の活性炭を得る
ことができる。After adding the alkali, the lignin or its derivative is heat treated to obtain activated carbon. For example, a predetermined amount of alkaline aqueous solution is added to lignin or its derivative in a carbonization furnace, the mixture is thoroughly stirred, and then water is distilled off by heating.
High-performance activated carbon can be obtained by raising the temperature further to complete carbonization and activation at once, removing the contents, adding water to recover the alkali, and thoroughly washing and drying the remaining char.
上記加熱は、３００〜９００℃程度、好適には４００〜
６５０℃程度の温度で、通常０．５〜４８時間程度、好
適には１〜５時間程度行なわれ、炭化・賦活が同時にな
される。The above heating is performed at a temperature of about 300 to 900°C, preferably 400 to 900°C.
Carbonization and activation are carried out at a temperature of about 650°C for usually about 0.5 to 48 hours, preferably about 1 to 5 hours, and carbonization and activation are carried out simultaneously.
上記加熱処理に際しては、乾留炉（焼成炉）、たとえば
ロータリーキルン等を用いることができ、大気圧下で、
そのままもしくは窒素のような不活性ガスの気流中で昇
温する。昇温の過程で留去してくる水分・分解油は出口
にとりつけた凝縮器によってトラップして回収する。ま
た、メタンを主成分とする廃ガスも別途回収することが
できる。For the above heat treatment, a carbonization furnace (calcination furnace), such as a rotary kiln, can be used, and under atmospheric pressure,
Either as is or heated in a stream of inert gas such as nitrogen. The water and cracked oil that distill off during the temperature rising process are trapped and recovered by a condenser installed at the outlet. Additionally, waste gas whose main component is methane can also be recovered separately.
なお、工業的にはこれらの副生物を燃焼廃棄することも
できる。In addition, industrially, these by-products can also be disposed of by combustion.
上記加熱処理が終了すると、放冷後、アルカリを含む炭
化物を炉より取して粉砕し、まず水を加えて加熱洗浄し
、洗液からアルカリが回収される。When the heat treatment is completed, the carbide containing the alkali is taken out from the furnace and pulverized after being allowed to cool. First, water is added thereto and heated and washed, and the alkali is recovered from the washing liquid.
さらに、希酸によって再度加熱洗浄をし、洗液のｐＨが
７前後になるまでくり返すのが好適である。Furthermore, it is preferable to perform heat washing again with a dilute acid and repeat the process until the pH of the washing liquid becomes around 7.
（実施例） 以下、実施例によりさらに本発明の詳細な説明する。(Example) Hereinafter, the present invention will be further explained in detail with reference to Examples.
実施例１〜１０
リグニンスルホン酸く山陽国際パルプ■製、“サンエキ
スｐ−２５２”、リグニンスルホン酸６０％、多Ｉｌ！
類３６％を含有する）を、表１記載の所定量の水酸化ナ
トリウム又は炭酸ソーダを混合した後、ステンレス製ビ
ーカーに入れ、それを鉄製レトルト中におき、電気炉に
て所定温度まで、昇温速度２〜３℃／１Ｉｉｎで加熱を
続け、所定温度に達した後、所定時間その温度に保持し
た。昇温の途中では水分が留去され、またガス発生が認
められた。そのガスの主成分は、メタンであった。Examples 1 to 10 Lignosulfonic acid "Sunextract p-252" manufactured by Sanyo Kokusai Pulp ■, 60% ligninsulfonic acid, multi-Il!
After mixing the predetermined amount of sodium hydroxide or soda carbonate listed in Table 1, the mixture was placed in a stainless steel beaker, placed in an iron retort, and heated to a predetermined temperature in an electric furnace. Heating was continued at a temperature rate of 2 to 3° C./1 inch, and after reaching a predetermined temperature, the temperature was maintained for a predetermined time. During the temperature rise, water was distilled off and gas generation was observed. The main component of the gas was methane.
ついで放冷し、得られた炭化物を水洗して、アルカリを
回収し活性炭を得た。結果を第１表に示す。The mixture was then allowed to cool, and the resulting carbide was washed with water to recover the alkali and obtain activated carbon. The results are shown in Table 1.
なお、比表面積は、ＢＥＴ比表面積であり、“カンタソ
ーブ表面測定装置” （Ｑｕ ａ ｎ ｊａ ｃｈ ｒ
ｏｍｅ社製）を用いる１点法（窒素ガス）によって測
定した。Note that the specific surface area is the BET specific surface area, which is measured by the "Cantasorb surface measuring device" (Qua nja ch r
Measurement was performed by a one-point method (nitrogen gas) using a microcomputer (manufactured by OME Inc.).
実施例１）
リグニンの純度を特に高めたいわゆる変成りゲニンスル
ホン酸（重陽国際パルプ■製、“バニレソクスＲＮ″）
に対してカセイソーダを重量比で１加え、上述のように
して４５０℃で１時間加熱（すなわち、炭化・賦活して
得られた活性炭の比表面積をＢＥＴ法で測定すると１８
５０％／ｇとなり、このもののヨウ素吸着能（ＪＩＳ
Ｋ−１４７４）１３００■／ｇとなった。Example 1) So-called modified geninsulfonic acid with particularly high purity of lignin (manufactured by Chongyang International Pulp ■, “Vaniresox RN”)
1 part by weight of caustic soda was added to the carbon and heated at 450°C for 1 hour as described above (i.e., when the specific surface area of the activated carbon obtained by carbonization and activation was measured by the BET method, it was 18
50%/g, which is the iodine adsorption capacity of this material (JIS
K-1474) was 1300 ■/g.
実施例１２
クラフト法によるリグニンであるいわゆるチオリグニン
（Ｗｅｓｔｖａｃｏ社製、”Ｉｎｄｕｌｉ ｎＡＴ”）
を原料として実施例１）と同様に製造した活性炭の性能
は、比表面積２７５０％／ｇで、ヨウ素吸着能２０９０
■／ｇとなった。Example 12 So-called thiolignin (manufactured by Westvaco, "Induli inAT"), which is a lignin produced by the Kraft method.
The performance of the activated carbon produced in the same manner as in Example 1) using as a raw material is that the specific surface area is 2750%/g, and the iodine adsorption capacity is 2090%.
■/g.
また、この活性炭の細孔分布をＮ！吸着法により測定（
測定装置としてＣａｒｂｏ−Ｅｒｂａ社製、“Ｓｏｒｐ
ｔｏｍａｔｉｃ″を用いた）した結果を第１図に示す。Also, the pore distribution of this activated carbon is N! Measured by adsorption method (
As a measuring device, “Sorp” manufactured by Carbo-Erba was used.
FIG.
すなわち、細孔径１５〜１００人にわたる範囲が非常に
発達していることがわかる。That is, it can be seen that the range of pore diameters from 15 to 100 is highly developed.
実施例１３
ＫＰ黒液に半量の酸化カルシウムを添加し、硫酸カルシ
ウムなどの無機塩類を沈殿させた上澄液を原料として実
施例１）と同様にして活性炭を得た。得られた活性炭の
比表面積は７１０ｍ／ｇであった。Example 13 Activated carbon was obtained in the same manner as in Example 1) using the supernatant obtained by adding half the amount of calcium oxide to KP black liquor and precipitating inorganic salts such as calcium sulfate as a raw material. The specific surface area of the obtained activated carbon was 710 m/g.
実施例１４
実施例１２において、カセイソーダに代えて、水酸カリ
ウムを用い、５５０℃で３時間、加熱して活性炭を得た
。得られた活性炭のヨウ素吸着能は次のとおりであった
。Example 14 In Example 12, potassium hydroxide was used instead of caustic soda, and activated carbon was obtained by heating at 550° C. for 3 hours. The iodine adsorption capacity of the obtained activated carbon was as follows.
すなわち、チオリグニンに対する水酸化カリウム重量比
が１．２及び３のとき、それぞれヨウ素吸着能は６２２
．１）００及び１７４０■／ｇであった。That is, when the weight ratio of potassium hydroxide to thiolignin is 1.2 and 3, the iodine adsorption capacity is 622.
．． 1) 00 and 1740 μ/g.
（発明の効果）
本発明によれば、木材蒸解によるパルプ製造の際の副産
物として多量に排出するリグニンあるいはその誘導体を
原料として、アルカリを賦活剤として用い、従来法にく
らべて低温で、しかも−段階の加熱プロセスで収率よく
高性能の活性炭を得ることができる。(Effects of the Invention) According to the present invention, lignin or its derivatives, which are discharged in large quantities as by-products during pulp production by wood digestion, are used as raw materials, and alkali is used as an activator, and the process is performed at a lower temperature than that of conventional methods. High yield and high performance activated carbon can be obtained through a stepwise heating process.
また、得られる活性炭は、きわめて高比表面積のものま
で可能であり、さらに細孔特性も、たとえば、特に細孔
径１５〜１００人にわたる範囲が非常に発達しているの
が特徴である。Furthermore, the activated carbon obtained can have an extremely high specific surface area, and is also characterized by extremely well-developed pore characteristics, particularly in the range of pore diameters from 15 to 100 pores.
第１図は実施例１２で得られた活性炭の細孔分布および
細孔容積累積曲線を示す。FIG. 1 shows the pore distribution and pore volume cumulative curve of the activated carbon obtained in Example 12.
Claims (7)
ついで加熱処理して活性炭を得ることを特徴とする活性
炭の製造方法。(1) Adding an alkali to lignin or its derivative,
A method for producing activated carbon, which is characterized in that activated carbon is then obtained by heat treatment.
ルホン酸である請求項１記載の方法。(2) The method according to claim 1, wherein the lignin derivative is thiolignin or lignin sulfonic acid.
求項１記載の方法。(3) The method according to claim 1, wherein pulp manufacturing waste liquid is used as the lignin derivative.
１記載の方法。(4) The method according to claim 1, wherein the alkali is an alkali metal hydroxide.
ムである請求項１記載の方法。(5) The method according to claim 1, wherein the alkali is sodium hydroxide or potassium hydroxide.
項１記載の方法。(6) The method according to claim 1, wherein the heat treatment is performed at a temperature of 300 to 900°C.
請求項１記載の方法。(7) The method according to claim 1, wherein the activated carbon has a specific surface area of 500 m^3/g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1030873A JPH01308818A (en) | 1988-02-10 | 1989-02-09 | Production of activated carbon |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-27736 | 1988-02-10 | ||
| JP2773688 | 1988-02-10 | ||
| JP1030873A JPH01308818A (en) | 1988-02-10 | 1989-02-09 | Production of activated carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01308818A true JPH01308818A (en) | 1989-12-13 |
Family
ID=26365703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1030873A Pending JPH01308818A (en) | 1988-02-10 | 1989-02-09 | Production of activated carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01308818A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001122608A (en) * | 1999-10-26 | 2001-05-08 | Tokyo Gas Co Ltd | Activated carbon controlled in fine pore structure and method of manufacturing the same |
| KR100387990B1 (en) * | 2000-10-27 | 2003-06-18 | 김철갑 | Method of making activated carbons using pulp sludges containing lignin produced as by products when making corncob pulp |
| WO2005053846A1 (en) * | 2003-12-05 | 2005-06-16 | Nisshoku Corporation | Anion-adsorbing carbon material, and method and apparatus for producing same |
| WO2008090938A1 (en) * | 2007-01-24 | 2008-07-31 | Fujifilm Corporation | Method for producing activated carbon and recycle system of waste film |
| JP2011162369A (en) * | 2010-02-05 | 2011-08-25 | Univ Of Miyazaki | Activated carbon with high-specific surface area using lignin as raw material, and adsorbent for lower alcohol containing the same |
| JP2015197515A (en) * | 2014-03-31 | 2015-11-09 | 大王製紙株式会社 | Manufacturing method of carbon fine particles for electrophotographic toner |
-
1989
- 1989-02-09 JP JP1030873A patent/JPH01308818A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001122608A (en) * | 1999-10-26 | 2001-05-08 | Tokyo Gas Co Ltd | Activated carbon controlled in fine pore structure and method of manufacturing the same |
| KR100387990B1 (en) * | 2000-10-27 | 2003-06-18 | 김철갑 | Method of making activated carbons using pulp sludges containing lignin produced as by products when making corncob pulp |
| WO2005053846A1 (en) * | 2003-12-05 | 2005-06-16 | Nisshoku Corporation | Anion-adsorbing carbon material, and method and apparatus for producing same |
| KR100795118B1 (en) * | 2003-12-05 | 2008-01-17 | 니혼쇼꾸세이가부시끼가이샤 | Anion-adsorbing carbon material, and method for producing same |
| US8222182B2 (en) | 2003-12-05 | 2012-07-17 | Nisshoku Corporation | Anion adsorbing carbon material, as well as manufacturing method and manufacturing facilities for same |
| WO2008090938A1 (en) * | 2007-01-24 | 2008-07-31 | Fujifilm Corporation | Method for producing activated carbon and recycle system of waste film |
| JP2011162369A (en) * | 2010-02-05 | 2011-08-25 | Univ Of Miyazaki | Activated carbon with high-specific surface area using lignin as raw material, and adsorbent for lower alcohol containing the same |
| JP2015197515A (en) * | 2014-03-31 | 2015-11-09 | 大王製紙株式会社 | Manufacturing method of carbon fine particles for electrophotographic toner |
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