JPS6360009B2 - - Google Patents
Info
- Publication number
- JPS6360009B2 JPS6360009B2 JP62012799A JP1279987A JPS6360009B2 JP S6360009 B2 JPS6360009 B2 JP S6360009B2 JP 62012799 A JP62012799 A JP 62012799A JP 1279987 A JP1279987 A JP 1279987A JP S6360009 B2 JPS6360009 B2 JP S6360009B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- spherical
- spherical activated
- present
- ammonia
- 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.)
- Expired
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 176
- 239000011148 porous material Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 239000000729 antidote Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 239000000523 sample Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000002550 fecal effect Effects 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 230000004913 activation Effects 0.000 description 8
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 8
- 230000028327 secretion Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000001784 detoxification Methods 0.000 description 6
- 201000010099 disease Diseases 0.000 description 6
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 210000000936 intestine Anatomy 0.000 description 5
- 229940109239 creatinine Drugs 0.000 description 4
- 210000002249 digestive system Anatomy 0.000 description 4
- 239000011295 pitch Substances 0.000 description 4
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000037396 body weight Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008991 intestinal motility Effects 0.000 description 3
- 230000006371 metabolic abnormality Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 241000699670 Mus sp. Species 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 231100000215 acute (single dose) toxicity testing Toxicity 0.000 description 2
- 238000011047 acute toxicity test Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000968 intestinal effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003053 toxin Substances 0.000 description 2
- 231100000765 toxin Toxicity 0.000 description 2
- 108700012359 toxins Proteins 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 208000007882 Gastritis Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000700157 Rattus norvegicus Species 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 206010070863 Toxicity to various agents Diseases 0.000 description 1
- 208000037386 Typhoid Diseases 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000010171 animal model Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 238000011888 autopsy Methods 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 210000002318 cardia Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 208000023652 chronic gastritis Diseases 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 208000001848 dysentery Diseases 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 208000028774 intestinal disease Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000004526 pharmaceutical effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- -1 pitch Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 210000000664 rectum Anatomy 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 201000008297 typhoid fever Diseases 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Description
本発明は、活性炭の少なくとも85%が真球であ
る球形活性炭から成る、消化器系から毒物あるい
は有害物質を除去、解毒するのに適した球形活性
炭およびその製造法に関する。
更に詳しくは、本発明は胃、腸のような消化器
系内に存在あるいは生成される有害物質を、活性
炭の服用によつて解毒する際に、従来から問題と
されていた便泌性副作用を示さない、活性炭の少
くとも85%が真球である解毒剤に適した球形活性
炭およびその製造法に関する。
活性炭は、これを服用することにより腸疾患等
の治療に効果的であるということは古くから知ら
れており、多くの病気治療の目的に用いられてい
る。活性炭を服用することにより、赤痢、コレ
ラ、腸チフス、食中毒等の細菌性感染性、消化不
良、腸の張り、慢性胃炎、てんかん、めまい、萎
黄病及び炭疸病等に対して、特に優れた治療効果
を示すということが報告されている。また、薬
物、毒物の摂取に際して、救急的に活性炭を服用
することにより解毒効果が得られている。更に、
活性炭の服用は、その他各種の疾患に伴う代謝異
常により生成する消化器系内の有毒物質の除去に
対しても効果的である。
これらの効果は、消化器系内の毒素、異常代謝
物又は毒素を生成する或いは代謝異常をひきおこ
す物質が生体に対して全く毒性のない活性炭に吸
着され、活性炭と共に体外に排出されるためと考
えられている。
従来、この解毒作用を目的としては全て粉末活
性炭が用いられており、この粉末活性炭を水と一
緒に服用するか、適当な錠剤として服用されてい
た。
錠剤として服用しても体内で解錠された粉末状
となり水と一緒に服用した場合と同等の吸着能力
を発現する。しかしながら、粉末活性炭の使用は
副作用として便泌現象を起せしめ、これが大きな
欠点でもあつた。特に活性炭は通常、各種疾患に
際して服用するものであるから、患者の体力が消
耗している場合が多く、この時、副作用として起
る便泌は患者にとつて著しい苦痛であるばかりで
なく、患者が充分な排泄力を有していない場合に
は、機械的にこれを除去しなければ、生命に関す
る場合も生じ得るという欠点を従来の活性炭は有
していた。
このような状況に鑑み、本発明者は、前述した
欠点を解決すべく、鋭意研究の結果、活性炭の少
なくとも85%、好ましくは90%が真球である特定
な球形活性炭が、優れた解毒作用を有しかつ便泌
性副作用を示さないことを見出し、本発明に到達
した。
本発明による解毒剤は、2工程からなる次に記
載の方法によつて高分子量炭化水素、例えばピツ
チから製造される。
第一工程では、ピツチを熔融状態で小粒球形と
し冷却の後、酸化して不融化し、その後不活性雰
囲気中800〜1000℃の温度で炭化し、次いで水蒸
気雰囲気中で900〜1000℃の温度で賦活して、直
径0.05〜2mm、表面積500〜2000m2/g、細孔半
径100〜75000Åの範囲での細孔容積0.05〜1.0
ml/g、PH=8〜10の微小球形活性炭を製造す
る。
第二工程では、これらの球形活性炭をNH3を
1〜1000ppm好ましくは5〜100ppm含有する希
アンモニア水溶液で接触処理し乾燥して、アンモ
ニア処理を行なう前の球形活性炭と同一直径、表
面積及び細孔容積を有し、アンモニア処理する前
の球形活性炭に比較してPH=6〜8の微小球形活
性炭を製造する。
この生成物は、活性炭の少なくとも85%が真球
である微小球形活性炭からなつており、この活性
炭は、めだつたかどのない、滑らかな凸表面を有
しており、最大直径と最小直径の割合が1.0〜1.3
である。
球形活性炭の粒径(直径)が0.05mm以下では解
毒作用はあつても便泌性副作用除去には充分効果
的でない。また球形活性炭の粒径が2mm以上にな
ると、服用し難いだけでなく、目的とする解毒効
果も迅速に発現しない。
活性炭の形状は本発明の満足すべき医薬上の効
果を得る上でのひとつの重要な因子であり、実質
に球形であることが必要である。更に、詳しく
は、活性炭の少なくとも85%が真球であることが
必要である。
形状と同様に、活性炭の表面積及び細孔容積
も、充分な解毒作用と便泌性副作用の除去という
効果を同時に発現させる上で重要な要因となる。
即ち、活性炭の表面積、細孔容積が小さすぎると
吸着力が弱くなり実用上充分な解毒効果は得られ
ず、また表面積、細孔容積が大きすぎると解毒作
用はあつても便泌現象を伴うことになる。また活
性炭の表面積、細孔容積が本発明の範囲より大き
くなると、強度が低下して服用時又は服用後に形
状が崩れ粉化を伴うことも便泌性副作用を生ずる
原因と考えられる。
本発明の微小球形活性炭の表面積は、市販の表
面積測定装置を用いて測定すると、500〜2000
m2/g、ましくは700〜1500m2/gである。細孔
容積は、市販の水銀圧入ボロシメーターで測定す
ると、細孔半径100〜75000Åの領域で0.05〜1.0
ml/g、好ましくは0.1〜0.8ml/gである。
このような特性を有する活性炭の製造に用いる
原料として、オガ屑、石炭、ヤシ殻、ピツチ類、
有機合成高分子等の公知の原料のいずれでもよ
く、これらの物質から球形活性炭を製造すること
ができる。
例えば、初期の球形活性炭を製造する方法とし
ては、粉末原料をピツチ等のバインダーを用いて
小粒球形に造粒し、次いで不活性雰囲気中で800
〜1000℃に加熱焼成して炭化し、水蒸気雰囲気中
で900〜1000℃で賦活する方法がある。
一方、例えば特公昭50―18879に開示されてい
る方法により、ピツチ類を熔融状態で小粒球形と
し次いで酸化により不融化した後、不活性雰囲気
中で800〜1000℃で加熱焼成して炭化し、水蒸気
雰囲気中で900〜1000℃賦活する方法により球形
活性炭を製造することができる。
特に、後者の方法では真球度の高い、高強度の
表面の滑らかな球形活性炭が得られるので、本発
明の活性炭の製造方法として好適である。
本発明の微小球形活性炭の製造方法の第二工程
は、特に重要なプロセスである。球形活性炭のPH
は、通常PH=8〜10であるが、これをPH=6〜8
に変える。この第二工程の処理をすることによつ
て球形活性炭は優れた性質をもつようになる。
アンモニア水溶液による処理の条件は、水蒸気
処理をした球形活性炭の状態に依つて異なるが、
通常は、アンモニア水溶液のNH3の濃度は1〜
1000ppm、好ましくは5〜100ppm、アンモニア
水溶液と球形活性炭の容量割合は1〜50、好まし
くは2〜10で、処理温度は10〜50℃で、処理時間
は0.5〜5時間である。アンモニア水溶液中の
NH3の濃度が上述した範囲より高くなると生成
物のPHも高くなつて、アルカリ領域となり、また
NH3の濃度が低くなると生成物のPHはアルカリ
領域に残る。
アルカリ性を示す球形活性炭が、アルカリ試
薬、すなわち、アンモニア水溶液と接触させるこ
とによつて酸性―中性の球形活性炭に変わる理由
は明らかではなく、更にこのようなPHの変化は全
く予期せぬことであつた。次に、このようにアン
モニア水溶液によつて処理された球形活性炭を通
常100〜150℃の温度で乾燥し、服用に適するサイ
ズにふるいわけをする。一様なサイズの生成物に
調整すること、すなわち一定の範囲のサイズに篩
分けすることは服用する際に好ましいことであ
る。ふるいわけは、最大粒子と最小粒子の直径の
比が1〜1.3であるような球形活性炭を得るため
に、アンモニア水溶液処理を行う前に、行われ
る。
何れの場合においても球形活性炭は服用するも
のであるから、安全上充分な純度のものでなけれ
ばならないのは勿論であつて例えば、日本薬局法
第九改正、“薬用炭”の項に示されている純度試
験に適合するものでなければならない。
本発明による球形活性炭の服用方法は、通常の
活性炭と同様の公知の方法でよい。飲料水に本発
明による微小球形活性炭を懸濁させて服用するの
が最も簡単であるが、常法に従い球形活性炭を適
当な形の錠剤として服用してもよい。但し、この
場合は勿論本発明の球形活性炭としての効果を示
す様、体内で元の球形活性炭粒子に解錠される必
要がある。
又常法に従い通常の円筒形カプセルに包含させ
て服用してもよい。
球形活性炭の服用量は、疾患の程度、緊急解毒
の必要性等によつても異なるが通常1回0.5〜10
g、1日3回程度である。又、食間服用が好まし
いが、緊急を要する場合は勿論この限りでない。
本発明の球形活性炭が解毒作用を維持しかつ便
泌性副作用の除去に著しい効果を示すことは全く
予期し得なかつたことで、未だその原因は明らか
でないが、本発明の球形活性炭はアンモニア処理
によつて表面が特殊な状態になつているため、外
因性及び内因性有害物質の吸着能力を保有してい
る。即ち、本発明の球形活性炭は摂取した植物、
消化した植物やその消化物の存在下においても、
従来の粉末活性炭、或いは単に粉末活性炭から球
形あるいは塊状化した活性炭と比較して、優れた
吸着能力を有する。従来の粉末炭又は、該粉末炭
の球状化あるいは塊状化物は腸運動の刺激物質も
吸着し、腸の運動を弱めると同時に便によく混合
して便の凝集力を増して便泌をきたすのに対し、
本発明の球形活性炭は表面性質の異なる滑らかな
球体であるため、便の凝集力上昇効果をもたらさ
ないと同時に、腸運動の刺激物質の吸着が少な
く、又、球形活性炭が腸に適度な刺激を与える等
の複合効果により便泌をきたさないとも推定され
る。
以下、実施例によつて本発明の効果を説明する
が、何等本発明の範囲を限定するものではない。
実施例 1
(球形活性炭の製造)
原油の高温分解により得られたピツチ(軟化点
175℃、ニトロベンゼン不溶分25%、H/C元素
比0.63)750部、ナフタレン250部を撹拌機付ステ
ンレス製オートクレーブに仕込み、170℃で混合
溶解し、これに「ゴーセノールGH―17」(日本
合成社製ポリビニルアルコール系懸濁剤)0.5%
水溶液3000部を加えて130℃で60分間激しく撹拌
した後、撹拌下に室温まで冷却し、真球状の球形
粒子を得た。大部分の水を別した後、粒子重量
の5倍量のメタノールに浸漬、振盪してナフタレ
ンを抽出除去した後通風乾燥し、次いで、小型ロ
ータリー・キルン中で空気を送入しながら25℃/
Hrで300℃まで昇温して不触性の球形粒子を得
た。次いで空気送入を停止し、代りに水蒸気を送
入しながら900℃まで昇温することによつて炭化
し、更にこの温度に保つことによつて賦活を進め
て、粒径0.1〜1.5mmの真球性の高い球形活性炭を
得た。
賦活時間を変えることによつて賦活の程度が異
なつた2種の球形活性炭を製造した。
比較試料No.1は賦活度の低いものであり、比較
試料No.2は賦活度の高いものであり、共に球形サ
イズをふるいわけにて整えたものである。
次に、比較試料No.1及び比較試料No.2の球形活
性炭のそれぞれ一部を、NH3の濃度が10ppmで
あるアンモニア水溶液に、アンモニア水溶液と球
形活性炭の容積/重量比が10ml/1gで、室温下
3時間浸漬した。続いて、溶液から球形活性炭を
取り出し、110℃の温度で16時間乾燥して、球形
活性炭を生成した。
賦活度の低い度合の活性炭からの生成物を試料
No.1とし、賦活度の高い度合の活性炭からの生成
物を試料No.2とする。
これら4つの活性炭の特性を表―1に示す。
尚、吸着能力は試験管内試験によつて、クレア
チニン及び尿酸に対する吸着能力をそれぞれ測定
した。前述の2つの物質は、賢疾患等の代謝異常
で体内に生成する有害物質としてよく知られてい
るものである。
The present invention relates to spherical activated carbon, which is made of spherical activated carbon in which at least 85% of the activated carbon is true spheres, and is suitable for removing and detoxifying poisons or harmful substances from the digestive system, and a method for producing the same. More specifically, the present invention eliminates the fecal secretion side effects that have traditionally been a problem when taking activated charcoal to detoxify harmful substances that exist or are produced within the digestive system such as the stomach and intestines. The present invention relates to a spherical activated carbon suitable for an antidote, in which at least 85% of the activated carbon is true spheres, and a method for producing the same. Activated charcoal has long been known to be effective in treating intestinal diseases and the like when ingested, and is used to treat many diseases. By taking activated charcoal, it has a particularly excellent therapeutic effect on dysentery, cholera, typhoid fever, bacterial infections such as food poisoning, indigestion, intestinal tension, chronic gastritis, epilepsy, dizziness, yellowing disease, anthrax, etc. It has been reported that it shows. In addition, detoxifying effects have been obtained by taking activated charcoal as an emergency when ingesting drugs or poisonous substances. Furthermore,
Taking activated charcoal is also effective in removing toxic substances in the digestive system that are produced due to metabolic abnormalities associated with various other diseases. These effects are thought to be due to the fact that toxins, abnormal metabolites, or substances that produce toxins or cause metabolic abnormalities in the digestive system are adsorbed by activated carbon, which is completely non-toxic to living organisms, and are excreted from the body along with the activated carbon. It is being Conventionally, powdered activated carbon has been used for this detoxification purpose, and this powdered activated carbon has been taken with water or in the form of a suitable tablet. Even when taken as a tablet, it becomes a powder that is unlocked within the body and exhibits the same adsorption capacity as when taken with water. However, the use of powdered activated carbon caused fecal secretion as a side effect, which was a major drawback. In particular, since activated charcoal is usually taken for various diseases, the patient's physical strength is often exhausted, and the fecal discharge that occurs as a side effect is not only extremely painful for the patient, but also Conventional activated carbon has the disadvantage that if it does not have sufficient excretion power, it may be life-threatening unless it is removed mechanically. In view of this situation, in order to solve the above-mentioned drawbacks, the inventor of the present invention has conducted extensive research and found that a specific spherical activated carbon in which at least 85%, preferably 90% of the activated carbon is true spheres has an excellent detoxifying effect. The present invention has been achieved based on the discovery that the drug has the following properties and exhibits no fecal secretion side effects. The antidote according to the invention is prepared from a high molecular weight hydrocarbon, such as pitch, by the following two-step process. In the first step, pitch is made into small spherical particles in a molten state, cooled, oxidized to make it infusible, then carbonized at a temperature of 800 to 1000°C in an inert atmosphere, and then carbonized at a temperature of 900 to 1000°C in a steam atmosphere. The pore volume is 0.05 to 1.0 with a diameter of 0.05 to 2 mm, a surface area of 500 to 2000 m 2 /g, and a pore radius of 100 to 75000 Å.
Produce microspherical activated carbon with ml/g and pH=8-10. In the second step, these spherical activated carbons are contacted with a dilute ammonia aqueous solution containing 1 to 1000 ppm of NH 3 , preferably 5 to 100 ppm, and dried to give the same diameter, surface area, and pores as the spherical activated carbon before the ammonia treatment. Microspherical activated carbon having a volume and pH=6 to 8 compared to the spherical activated carbon before ammonia treatment is produced. The product consists of microspherical activated carbon in which at least 85% of the activated carbon is true spheres, the activated carbon has a smooth convex surface with no noticeable edges, and the ratio of maximum diameter to minimum diameter is 1.0~1.3
It is. If the particle size (diameter) of spherical activated carbon is less than 0.05 mm, it will not be sufficiently effective in eliminating fecal side effects, even if it has a detoxifying effect. Furthermore, if the particle size of the spherical activated carbon exceeds 2 mm, it will not only be difficult to take, but also the desired detoxifying effect will not be achieved quickly. The shape of the activated carbon is one important factor in obtaining the satisfactory pharmaceutical effect of the present invention, and it is necessary that it be substantially spherical. More specifically, at least 85% of the activated carbon needs to be true spheres. Similar to the shape, the surface area and pore volume of activated carbon are also important factors in achieving sufficient detoxification and elimination of fecal side effects at the same time.
In other words, if the surface area and pore volume of activated carbon are too small, the adsorption power will be weak and a practically sufficient detoxification effect will not be obtained, and if the surface area and pore volume are too large, even if the activated carbon has a detoxifying effect, it will cause fecal secretion. It turns out. Furthermore, when the surface area and pore volume of the activated carbon are larger than the ranges of the present invention, the strength decreases, the shape collapses during or after ingestion, and powdering occurs, which is also considered to be a cause of fecal secretion side effects. The surface area of the microspherical activated carbon of the present invention is 500 to 2000 when measured using a commercially available surface area measuring device.
m 2 /g, preferably 700 to 1500 m 2 /g. The pore volume is 0.05 to 1.0 in the region of pore radius 100 to 75000 Å when measured with a commercially available mercury intrusion borosimeter.
ml/g, preferably 0.1-0.8 ml/g. Raw materials used to produce activated carbon with such characteristics include sawdust, coal, coconut shells, pithus,
Any known raw materials such as organic synthetic polymers may be used, and spherical activated carbon can be produced from these materials. For example, the initial method for producing spherical activated carbon was to granulate powdered raw materials into small spherical shapes using a binder such as Pitz, and then to
There is a method of carbonizing by heating to ~1000°C and activating at 900~1000°C in a steam atmosphere. On the other hand, for example, according to the method disclosed in Japanese Patent Publication No. 50-18879, pitches are made into small spherical shapes in a molten state, and then made infusible by oxidation, and then carbonized by heating and baking at 800 to 1000°C in an inert atmosphere. Spherical activated carbon can be produced by a method of activation at 900 to 1000°C in a steam atmosphere. In particular, the latter method is suitable as the method for producing activated carbon of the present invention because it yields spherical activated carbon with high sphericity, high strength, and a smooth surface. The second step of the method for producing microspherical activated carbon of the present invention is a particularly important process. PH of spherical activated carbon
is usually PH=8~10, but this is PH=6~8
Change to By performing this second step, the spherical activated carbon has excellent properties. The conditions for treatment with aqueous ammonia solution vary depending on the state of the spherical activated carbon that has been treated with steam, but
Usually, the concentration of NH 3 in ammonia aqueous solution is 1 to
1000 ppm, preferably 5-100 ppm, the volume ratio of ammonia aqueous solution and spherical activated carbon is 1-50, preferably 2-10, the treatment temperature is 10-50°C, and the treatment time is 0.5-5 hours. in ammonia aqueous solution
When the concentration of NH 3 is higher than the range mentioned above, the PH of the product also increases and becomes alkaline region.
When the concentration of NH 3 decreases, the PH of the product remains in the alkaline region. It is not clear why spherical activated carbon, which exhibits alkalinity, changes to acidic-neutral spherical activated carbon when it comes into contact with an alkaline reagent, that is, an aqueous ammonia solution, and furthermore, such a change in PH is completely unexpected. It was hot. Next, the spherical activated carbon thus treated with the aqueous ammonia solution is dried at a temperature of usually 100 to 150°C and sieved into sizes suitable for administration. Adjusting the product to a uniform size, ie sieving to a range of sizes, is preferred for dosing. Sieving is carried out before the ammonia aqueous solution treatment in order to obtain spherical activated carbon with a diameter ratio of the largest particles to the smallest particles of 1 to 1.3. In any case, since the spherical activated carbon is to be taken, it must of course be of sufficient purity for safety. The purity test must be passed. The method for taking the spherical activated carbon according to the present invention may be the same known method as for ordinary activated carbon. Although it is easiest to take the microspherical activated carbon according to the present invention by suspending it in drinking water, it is also possible to take the spherical activated carbon in the form of an appropriately shaped tablet according to a conventional method. However, in this case, of course, it is necessary to unlock the original spherical activated carbon particles within the body so that the spherical activated carbon of the present invention can exhibit its effects. It may also be taken in a conventional cylindrical capsule according to a conventional method. The dose of spherical activated charcoal varies depending on the severity of the disease, the need for emergency detoxification, etc., but it is usually 0.5 to 10 g per dose.
g, about 3 times a day. Also, it is preferable to take the drug between meals, but of course this does not apply if there is an emergency. It was completely unexpected that the spherical activated carbon of the present invention would maintain the detoxification effect and show a remarkable effect on eliminating fecal side effects, and although the cause is still unclear, the spherical activated carbon of the present invention was treated with ammonia. Due to the special condition of the surface, it has the ability to adsorb exogenous and endogenous harmful substances. That is, the spherical activated carbon of the present invention can be used for ingested plants,
Even in the presence of digested plants and their digested products,
It has superior adsorption capacity compared to conventional powdered activated carbon or activated carbon made from powdered activated carbon into spheres or lumps. Conventional powdered charcoal or spheroidized or agglomerated powdered charcoal also adsorbs substances that stimulate intestinal motility, weakening intestinal motility, and at the same time mixes well with stool, increasing the cohesive force of stool and causing fecal secretion. For,
Since the spherical activated carbon of the present invention is a smooth sphere with different surface properties, it does not have the effect of increasing the cohesive force of stool, and at the same time adsorbs few substances that stimulate intestinal motility, and the spherical activated carbon provides moderate stimulation to the intestines. It is also presumed that the combined effect of feeding does not cause fecal secretion. EXAMPLES Hereinafter, the effects of the present invention will be explained with reference to Examples, but the scope of the present invention is not limited in any way. Example 1 (Production of spherical activated carbon) Pitch obtained by high-temperature decomposition of crude oil (softening point
175℃, nitrobenzene insoluble content 25%, H/C element ratio 0.63), 750 parts of naphthalene and 250 parts of naphthalene were placed in a stainless steel autoclave equipped with a stirrer, mixed and dissolved at 170℃. polyvinyl alcohol suspension agent) 0.5%
After adding 3000 parts of an aqueous solution and stirring vigorously at 130°C for 60 minutes, the mixture was cooled to room temperature while stirring to obtain true spherical particles. After removing most of the water, the particles were immersed in methanol in an amount 5 times the weight of the particles, shaken to extract and remove naphthalene, and then dried in a small rotary kiln at 25°C while blowing air.
Inaccessible spherical particles were obtained by heating to 300°C with Hr. Next, the supply of air is stopped, and the temperature is raised to 900°C while steam is supplied instead to carbonize, and the activation is continued by maintaining this temperature to form particles with a particle size of 0.1 to 1.5 mm. Spherical activated carbon with high sphericity was obtained. Two types of spherical activated carbon with different degrees of activation were produced by changing the activation time. Comparative Sample No. 1 has a low degree of activation, and Comparative Sample No. 2 has a high degree of activation, both of which have been sieved to have a spherical size. Next, a portion of each of the spherical activated carbons of Comparative Sample No. 1 and Comparative Sample No. 2 was added to an ammonia aqueous solution with an NH 3 concentration of 10 ppm at a volume/weight ratio of 10 ml/1 g of the ammonia aqueous solution and the spherical activated carbon. , and immersed at room temperature for 3 hours. Subsequently, the spherical activated carbon was taken out from the solution and dried at a temperature of 110° C. for 16 hours to produce spherical activated carbon. Sample product from activated carbon with low degree of activation
Sample No. 1 and the product from activated carbon with a high degree of activation are Sample No. 2. Table 1 shows the properties of these four activated carbons. In addition, the adsorption ability for creatinine and uric acid was measured by an in vitro test. The above-mentioned two substances are well known as harmful substances that are produced in the body due to metabolic abnormalities such as diseases.
第1表に示した試料につて、マウスを用いた急
性毒性試験を実施した。結果は以下に示す通りで
あり、本発明の球形活性炭を多量に投与しても極
めて安全性の高いものであることを確認した。
実験動物として、市販ICR―JCL系雌マウス
(体重22±1g)を用い、第1表の4つの試料を
胃ゾンデを用いて強制経口投与した。1週間後の
生死の判定により、Litchfield―Wilcoxon法から
LD50を求めた。結果を第2表に示す。1週間後、
解剖したが、外観的及び内蔵観察においても特記
すべき異常所見を認めず又特記すべき中毒症状も
認められなかつた。
Acute toxicity tests using mice were conducted on the samples shown in Table 1. The results are shown below, and it was confirmed that the spherical activated carbon of the present invention is extremely safe even when administered in large amounts. Commercially available ICR-JCL female mice (body weight 22±1 g) were used as experimental animals, and the four samples shown in Table 1 were orally administered by force using a gastric probe. After one week, the Litchfield-Wilcoxon method was used to determine whether the animal was alive or dead.
Asked for LD50 . The results are shown in Table 2. 1 week later,
An autopsy was performed, but no notable abnormal findings were found in the external appearance or internal organ observation, nor were any notable toxic symptoms observed.
【表】
実施例 2
(動物実験)
体重130〜140gのウイスター(Wistar)系雌
ラツトを用い、ベントバルビタール―Naを20
mg/Kg体重になるように水溶液として経口投与し
た。次いで直ちに第1表に示した試料を水懸濁液
として200mg/Kg体重になるように経口投与した。
同時に活性炭を投与しない比較試験を実施した。
検体は、各活性炭試料投与群及び非投与群毎に10
匹ずつ使用した。次いで血中のベントバルビター
ルNaの最大濃度の平均値を求め比較試験群での
濃度に対する割合を除去率として算出した結果は
第3表の通りである。
第3表から明らかなとうり、何れの球形活性炭
試料投与群においても解毒効果が観察された。し
かしながら、試料No.1及びNo.2(アンモニア処理
したもの)は、比較試料No.1及びNo.2(アンモニ
ア処理しないもの)に比較して特に顕著な解毒効
果を有していた。[Table] Example 2 (Animal experiment) Using female Wistar rats weighing 130 to 140 g, bentobarbital-Na was administered at 20%
It was orally administered as an aqueous solution at mg/Kg body weight. Immediately thereafter, the samples shown in Table 1 were orally administered as an aqueous suspension at a concentration of 200 mg/Kg body weight.
At the same time, a comparative test was conducted in which activated charcoal was not administered.
Ten samples were prepared for each activated carbon sample administration group and non-administration group.
One by one was used. Next, the average value of the maximum concentration of bentobarbital Na in the blood was determined, and the ratio to the concentration in the comparison test group was calculated as the removal rate. The results are shown in Table 3. As is clear from Table 3, detoxification effects were observed in all groups administered with the spherical activated carbon samples. However, Samples No. 1 and No. 2 (treated with ammonia) had a particularly remarkable detoxifying effect compared to Comparative Samples No. 1 and No. 2 (not treated with ammonia).
【表】
次いで、活性炭の投与から90分後にこれ等の検
体群を麻酔死させ消化管を摘出して活性炭の腸内
移送の程度を比較した。即ち、噴門から直腸末端
までの全長に対する活性炭到達部までの移送距離
の割合を移送率として判定した。結果は第4表に
示す様に、第1表に示す本発明の活性炭試料を用
いた検体群では、その移送率が大きく、便泌作用
の少ないことが示された。[Table] Next, 90 minutes after the administration of activated charcoal, these sample groups were anesthetized, the gastrointestinal tract was removed, and the degree of intestinal transport of activated charcoal was compared. That is, the ratio of the transfer distance to the activated carbon reaching part to the total length from the cardia to the end of the rectum was determined as the transfer rate. As shown in Table 4, the results showed that in the sample group using the activated carbon samples of the present invention shown in Table 1, the transport rate was high and the fecal secretion effect was small.
【表】
実施例 3
(吸着能)
本発明の球形活性炭の実際の吸着能力をみるた
めに、腸内で活性炭による有害物質の吸着を妨げ
るステアリン酸ナトリウムの存在下で次の実験を
おこなつた。
ステアリン酸ナトリウムをPH7.4のリン酸緩衝
液中に、腸内のステアリン酸ナトリウムの概算濃
度である。2%の濃度に分散させ、更にクレアチ
ニンを前述の溶液に15ml/dlの濃度になるように
溶解した。次いで第1表の各試料を前述の溶液に
加え、3時間振り、その後混合物を5ml毎に分け
た。ステアリン酸を沈澱させる為に硫酸アルミニ
ウムの10%水溶液を3滴混合物に加えた後、表層
のクレアチニンの濃度を比色定量法によつて測定
した。比色定量法による測定工程以外はすべて37
℃の温度にて実験をおこなつた。
測定の結果を第5表に示す。
第5表から明らかな如く、本発明の球形活性炭
は比較試料(アンモニア処理をしていないもの)
に比べて優れた吸着能力を有している。この結
果、本発明の球形活性炭は、腸内で活性炭による
有害物質の吸着を妨げるステアリン酸ナトリウム
のような物質の存在下においても、クレアチニン
のような有害物質に対する吸収能力が優れている
ことが明らかである。[Table] Example 3 (Adsorption capacity) In order to examine the actual adsorption capacity of the spherical activated carbon of the present invention, the following experiment was conducted in the presence of sodium stearate, which prevents the adsorption of harmful substances by activated carbon in the intestines. . Sodium stearate in phosphate buffer at pH 7.4 is the approximate concentration of sodium stearate in the intestine. The solution was dispersed at a concentration of 2%, and creatinine was further dissolved in the above solution at a concentration of 15 ml/dl. Each sample from Table 1 was then added to the above solution and shaken for 3 hours, after which time the mixture was divided into 5 ml portions. After adding 3 drops of a 10% aqueous solution of aluminum sulfate to the mixture to precipitate the stearic acid, the concentration of creatinine in the surface layer was determined by colorimetric method. All except the measurement process using colorimetric method are 37
The experiment was conducted at a temperature of ℃. The results of the measurements are shown in Table 5. As is clear from Table 5, the spherical activated carbon of the present invention is a comparative sample (not subjected to ammonia treatment).
It has superior adsorption ability compared to As a result, it is clear that the spherical activated carbon of the present invention has an excellent ability to absorb harmful substances such as creatinine even in the presence of substances such as sodium stearate that prevent activated carbon from adsorbing harmful substances in the intestine. It is.
【表】
ニンのmgの量
[Table] Amount of garlic in mg
Claims (1)
て、粒子の最大径と最小径の比が1.0〜1.3、直径
0.05〜2.0mm、表面積500〜2000m2/g、細孔半径
100〜75000Åにおける細孔容積0.05〜1.0ml/g、
PH=6〜8の特性を有する、アンモニア処理され
た径口解毒剤。1 At least 85% of the spherical activated carbon is a true sphere, the ratio of the maximum diameter to the minimum diameter of the particles is 1.0 to 1.3, and the diameter
0.05~2.0mm, surface area 500~2000m2 / g, pore radius
Pore volume 0.05-1.0ml/g at 100-75000Å,
Ammoniated pore antidote with properties of PH=6-8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62012799A JPS62223125A (en) | 1979-06-26 | 1987-01-22 | Antidote for oral administration |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8053779A JPS565313A (en) | 1979-06-26 | 1979-06-26 | Detoxificating spherical active carbon and preparing the same |
JP62012799A JPS62223125A (en) | 1979-06-26 | 1987-01-22 | Antidote for oral administration |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8053779A Division JPS565313A (en) | 1977-12-27 | 1979-06-26 | Detoxificating spherical active carbon and preparing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62223125A JPS62223125A (en) | 1987-10-01 |
JPS6360009B2 true JPS6360009B2 (en) | 1988-11-22 |
Family
ID=26348471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62012799A Granted JPS62223125A (en) | 1979-06-26 | 1987-01-22 | Antidote for oral administration |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62223125A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005094844A1 (en) * | 2004-04-02 | 2005-10-13 | Kureha Corporation | Adsorbent for oral administration, preventive or remedy for kidney disease and preventive or remedy for liver disease |
WO2013051680A1 (en) | 2011-10-07 | 2013-04-11 | 帝人ファーマ株式会社 | Orally administered adsorbent |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10316578A (en) * | 1997-05-13 | 1998-12-02 | Kureha Chem Ind Co Ltd | Medicine for improving blood lipoprotein lipase activity-lowering disease |
JPH1129485A (en) * | 1997-07-10 | 1999-02-02 | Kureha Chem Ind Co Ltd | Antiobestic medicine |
JP3522708B2 (en) * | 2001-04-11 | 2004-04-26 | 呉羽化学工業株式会社 | Adsorbent for oral administration |
TWI385120B (en) * | 2004-04-02 | 2013-02-11 | Kureha Corp | Process for preparing spherical activated carbon |
JP2010106007A (en) * | 2008-08-14 | 2010-05-13 | Sony Corp | Drug sustained-release agent, adsorbent, functional food, mask and adhesive sheet |
-
1987
- 1987-01-22 JP JP62012799A patent/JPS62223125A/en active Granted
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005094844A1 (en) * | 2004-04-02 | 2005-10-13 | Kureha Corporation | Adsorbent for oral administration, preventive or remedy for kidney disease and preventive or remedy for liver disease |
WO2013051680A1 (en) | 2011-10-07 | 2013-04-11 | 帝人ファーマ株式会社 | Orally administered adsorbent |
Also Published As
Publication number | Publication date |
---|---|
JPS62223125A (en) | 1987-10-01 |
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