JPH082909A - The composition of petroleum pitch H. Ingredient or B. Pre-treating each component as a raw material separately, extracting these separately with a solvent, and subjecting these extracted components to heat and pressure treatment to create a firing pitch containing fullerene C60, using a special solvent. A method in which fullerene C60 is solvent-extracted, and the extracted solution is poured into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60. - Google Patents
The composition of petroleum pitch H. Ingredient or B. Pre-treating each component as a raw material separately, extracting these separately with a solvent, and subjecting these extracted components to heat and pressure treatment to create a firing pitch containing fullerene C60, using a special solvent. A method in which fullerene C60 is solvent-extracted, and the extracted solution is poured into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60.Info
- Publication number
- JPH082909A JPH082909A JP6169885A JP16988594A JPH082909A JP H082909 A JPH082909 A JP H082909A JP 6169885 A JP6169885 A JP 6169885A JP 16988594 A JP16988594 A JP 16988594A JP H082909 A JPH082909 A JP H082909A
- Authority
- JP
- Japan
- Prior art keywords
- fullerene
- heat
- solvent
- ingredients
- component
- 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
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000004615 ingredient Substances 0.000 title claims abstract description 88
- 239000011295 pitch Substances 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000002994 raw material Substances 0.000 title claims abstract description 23
- 239000002904 solvent Substances 0.000 title claims abstract description 23
- 238000010304 firing Methods 0.000 title claims abstract description 18
- 239000011301 petroleum pitch Substances 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000741 silica gel Substances 0.000 title claims abstract description 13
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000000859 sublimation Methods 0.000 claims abstract description 5
- 230000008022 sublimation Effects 0.000 claims abstract description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000077 silane Inorganic materials 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000007789 gas Substances 0.000 claims description 32
- 238000000638 solvent extraction Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 238000000354 decomposition reaction Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- 229910003472 fullerene Inorganic materials 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 9
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 238000004523 catalytic cracking Methods 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 238000006477 desulfuration reaction Methods 0.000 claims 1
- 230000023556 desulfurization Effects 0.000 claims 1
- 238000009776 industrial production Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000012856 packing Methods 0.000 abstract description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 17
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 239000004071 soot Substances 0.000 description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000001273 butane Substances 0.000 description 5
- 238000010891 electric arc Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
(57)【要約】 （修正有）
【目 的】フラーレンＣ６０の製造方法を提供する。
【構 成】石油系ピッチの組成成分のＨ．成分及びＢ．
成分を夫々加圧高温下にて加熱処理して造る熱に極めて
安定なＨ．成分及びこのＨ．成分より造る熱に極めて安
定な立体構造のＱ．Ｓ．成分等を原料として高温高圧下
にて加熱処理してフラーレンＣ６０を含有する焼成ピッ
チを造り、焼成ピッチを別々に特殊の溶媒にてフラーレ
ンＣ６０を選択的に抽出し、この抽出物をオクタデシル
シラン（ＯＤＳ）のシリカゲルの充填物層に溶媒と共に
流し込み、その溶媒とフラーレンＣ６０を効率良く分離
し、高温高真空下にて昇華してフラーレンＣ６０を精製
する。(57) [Summary] (Modified) [Objective] A method for producing fullerene C 60 is provided. [Composition] The composition of petroleum pitch H. Ingredients and B.
Each of the components is heat-stable under pressure and high temperature, and the H. Ingredients and this H. Q. With a three-dimensional structure that is extremely stable to the heat produced from the ingredients S. The firing pitch containing fullerene C 60 is produced by heat-treating the components as raw materials under high temperature and high pressure, the firing pitch is separately extracted with a special solvent to obtain fullerene C 60 , and the extract is octadecyl. It is poured together with a solvent into a silica gel packing layer of silane (ODS), the solvent and fullerene C 60 are efficiently separated, and the fullerene C 60 is purified by sublimation under high temperature and high vacuum.
Description
【０００１】[0001]
【産業上の利用の分野】本発明は石油系ピッチの特定成
分（Ｈ．成分或いはＢ．成分）に先ず厳しい熱の予備の
処理を実施して造る熱に極めて安定なＨ．成分或いは
Ｂ．成分の單味を亦これ等の成分とこれ等の成分ごとに
造る熱に極めて安定な立体構造のＱ Ｓ．成分との混合
物等を夫々不活性ガス或いは分解生成ガスの気流下高圧
高温にてフラーレンＣ６０を含有する焼成ピッチを造
り、これを特殊な溶剤を用いて選択的に効率良くフラー
レンＣ６０を抽出し、更にその分離した溶液をシリカゲ
ルの充填物を充填した管中に流し込み、その溶液よりに
フラーレンＣ６０のみを分離し、これを更に高温高真空
下にて昇華精製してフラーレンＣ６０を合理的に製造す
る方法を提供することに関するものである。BACKGROUND OF THE INVENTION The present invention relates to a heat-stabilized H.V. produced by first subjecting a specific component (H. component or B. component) of petroleum pitch to severe heat preliminary treatment. Ingredient or B. The ss of the three-dimensional structure of these components and the heat-stable three-dimensional structure produced by each of these components. Build firing pitch containing fullerene C 60 and mixtures of components in a stream under high pressure and high temperature, respectively inert gas or decomposition product gas, extracted selectively and efficiently fullerene C 60 this using a special solvent Then, the separated solution is poured into a tube filled with a silica gel filling, and only fullerene C 60 is separated from the solution, and the fullerene C 60 is further purified by sublimation under high temperature and high vacuum to obtain fullerene C 60 . To provide a method of manufacturing the same.
【０００２】[0002]
【従来の技術】フラーレンＣ６０はサッカーボールやラ
グビーボールの様な型状をしている炭素原子が６０個よ
り構成される１２個の五角型と２０個の六角型より型成
され、五角型同志は隣り合わない切頭５面体構造を持つ
中空多面体の全く新規の炭素の同素体であり、これを１
９８５年英国のクロード氏と米国のスモーリー氏等に依
って始めて発見されたが、これを固体として取り出すこ
とに数多くの研究者達の努力にもかかわらず大変困難な
ものと考えらていた。BACKGROUND OF THE INVENTION Fullerene C 60 is a pentagonal type, which is formed by 12 pentagonal type and 60 hexagonal type which are composed of 60 carbon atoms in the shape of soccer ball or rugby ball. Comrades are all-new carbon allotropes of hollow polyhedra with truncated pentahedron structures that are not next to each other.
It was first discovered in 985 by Mr. Claude of the United Kingdom and Mr. Smalley of the United States, but I thought that it was very difficult to take out this as a solid despite the efforts of many researchers.
【０００３】然るにドイツのクレッチマー氏及び米国の
ハフマン氏等に依って始めて１９９０年に炭素棒に通電
し、アーク放電に依って抵抗加電して超高温下アーク放
電用のグラフイト棒の炭素を炭化し、そのススを冷却す
る過程に於いてそのススの中にフラーレンＣ６０を製造
し、そのススの中にベンゼンに溶解するフラーレンＣ
６０の存在することが発見され、それ以来フラーレンＣ
６０の特性が急に種々研究され、その特性はカリウムを
ドーブしたフラーレンＣ６０の物性は特に驚異的で絶体
温度２０゜Ｋ以下ではそれの電気抵抗の値は殆ど零に近
く、而もフラーレンＣ６０は半導体として光を電気に変
える変換効率も約５３％と極めて高い報告もあり、フラ
ーレンＣ６０が安価に多量に入手出来るようになり、更
にそれが工業的に入手できる様になれば、その特性も種
々研究され、全く新しい素材としてこれを利用した脚光
を浴びる商品の出現が期待さている。However, the carbon rod was first energized in 1990 by Mr. Kletschmer of Germany and Mr. Huffman of the United States, and the carbon of the graphite rod for arc discharge under ultrahigh temperature was carbonized by resistance-charging by arc discharge. In the process of cooling the soot, fullerene C 60 is produced in the soot, and fullerene C is dissolved in benzene in the soot.
It was discovered that there were 60 fullerene C since then
The characteristics of 60 were suddenly studied, and the characteristics of fullerene C 60 doped with potassium were particularly surprising. The electric resistance of the fullerene C 60 was close to zero at an absolute temperature of 20 ° K or less. C 60 is also very high reported about 53 percent conversion efficiency for changing light to electricity as a semiconductor, is as fullerene C 60 can be obtained inexpensively in a large amount, if the way can be further obtained it industrially, Various studies have been conducted on its characteristics, and it is expected that a product that will be in the limelight using this as a completely new material will emerge.
【０００４】フラーレンＣ６０を多量に製造する方法と
して１９９０年に前述のクレッチマー氏及びハフマン氏
等の開発に依りヘリウムガス中でアーク放電に依る電極
の炭素を気化し、ガス状の炭素を冷却する過程に於てフ
ラーレンＣ６０を生成する方法に関して、現在はその生
成する多量のススの中に製造されるフラーレンＣ６０の
製法そのもの及びその製法の合理化が色々と検討されて
いるが、そのススの中に副産されるフラーレンＣ６Ｏ以
外の炭素数６０以上のフラーレンはフラーレンＣ６０の
製造用の原料として使用出来るとの研究報告は今迄で全
くありません。而もアーク放電に依り電極を高熱化し、
その電極の炭素その物を気化蒸発させる為に、その熱効
率は極めて悪く、その上蒸発気化された炭素に対するフ
ラーレンＣ６０の生成収率も極めて小さく、従ってこの
電極に依るフラーレンＣ６０の製法は工業的製法とは全
く考えられない。その為高純度のフラーレンＣ６０を工
業的に安価に製造する方法を研究開発することが出来れ
ば、その開発に依る安価なフラーレンＣ６０を多量に使
用し、今迄で研究されていないフラーレンＣ６０の特性
を開発研究し、それと今迄で研究された特性を共に活用
して、全く新しい製品が多く商品化され、それ等の商品
が今後の文化及び地球の環境の改善の為に大いに貢献出
来るものと確信することが出来きる。As a method for producing a large amount of fullerene C 60 , the carbon of the electrode was vaporized by the arc discharge in helium gas by the development of Mr. Kletschmer and Mr. Huffman mentioned above in 1990, and the gaseous carbon was cooled. on how to generate a fullerene C 60 at a process, now is the rationalization of large quantities of preparation itself and the method of preparation the fullerene C 60 is produced in the soot of the generation is variously considered, the soot carbon number more than 60 fullerene other than fullerene C6O to be byproduct research report that can be used as a raw material for the production of fullerene C 60 is not at all so far in. Moreover, due to the arc discharge, the electrode is highly heated,
Since the carbon itself of the electrode is vaporized and evaporated, its thermal efficiency is extremely poor, and the production yield of fullerene C 60 relative to the vaporized carbon is also extremely small. Therefore, the method for producing fullerene C 60 by this electrode is industrial. I can't think of it as a static manufacturing method. Therefore, if a method for industrially producing high-purity fullerene C 60 at a low cost can be researched and developed, a large amount of cheap fullerene C 60 resulting from the development will be used, and a fullerene C 60 that has not been studied so far. By developing and researching the characteristics of 60 , and utilizing the characteristics that have been researched so far, many new products are commercialized, and these products will greatly contribute to the future improvement of the culture and the environment of the earth. I can be sure that I can do it.
【０００５】[0005]
【発明が解決しようとする問題点】本発明の目的は熱に
極めて安定なベンゼン核及びナフタリン核を多量に含有
する石油系ピッチの組成成分のＨ．成分或いはＢ．成分
を原料とする合理的なフラーレンＣ６０の製法の為に、
脱硫減圧軽油の熱接触分解（ＦＣＣ）に依り副産される
石油系ピッチを減圧蒸留し、８５％カットして造る初留
４６０℃乃至終留５６０℃（Ｈ．成分２０．０％乃至８
０．０％、Ｂ．成分２０．０％乃至８０．０％、軟化点
４６℃乃至６４℃）を炭素数６乃至８の脂肪族炭化水素
にて溶剤抽出するＨ．成分（Ｈ．成分９９．０％乃至１
００．０％、Ｂ．成分０％乃至１．０％、平均分子量３
１０乃至３６０、軟化点４０℃乃至５０℃）を抽出し、
その抽出で得られるラフイネート（不溶分）を炭素数６
乃至８の芳香族炭化水素の溶剤抽出にて造るＢ．成分
（Ｈ．成分０％乃至１．０％、Ｂ．成分９９．０％乃至
１００．０％、平均分子量３９０乃至４４０、軟化点７
６℃乃至９６℃）を抽出し、夫々別々に原料とし、不活
性ガス或いは分解生成ガスの気流下２０ｋｇ／ｃｍ２乃
至４００ｋｇ／ｃｍ２の加圧下目標温度３００℃乃至６
００℃迄で昇温し、その温度で２時間乃至１０時間の予
備の厳しい加熱処理に依ってＨ．成分を原料として熱に
極めて安定なＨ．成分とこの熱に極めて安定なＨ．成分
が３個熱結合して造る熱に極めて安定な立体構造のＱ．
Ｓ．成分等を含有する焼成ピッチを収率７５％乃至８５
％で造り、これ等の焼成ピッチより炭素数６乃至８の脂
肪族炭化水素の溶剤抽出にて造る熱に極めて安定なＨ．
成分或いはこのＨ．成分とこのＨ．成分が３個熱結合し
て造るキノリン等の溶剤抽出にて抽出される熱に極めて
安定な立体構造のＱ．Ｓ．成分との混合物等を原料とし
て不活性ガス或いは分解生成ガスの気流下５０ｋｇ／ｃ
ｍ２６００ｋｇ／ｃｍ２の加圧下温度６００℃乃至１，
２００℃にて２時間乃至２０時間加熱処理して、フラー
レンＣ６０を４％乃至２０％含有する焼成ピッチを収率
７４％乃至８４％で造り、或いは前述の如く石油系ピッ
チを炭素数６乃至８８の脂肪族炭化水素の溶剤抽出して
造るラフイネートを炭素数６乃至８の芳香族炭化水素に
て溶剤抽出するＢ．成分を不活性ガス或いは分解生成ガ
スの気流下２０ｋｇ／ｃｍ２乃至４００ｋｇ／ｃｍ２の
加圧下温度３００℃乃至６００℃迄で昇温し、その目標
温度で２時間乃至１０時間の予備の厳しい加熱処理に依
ってＢ．成分を原料として熱に極めて安定なＢ．成分と
この熱に極めて安定なＢ．成分が３個熱結合して熱に極
めて安定な立体構造のＱ．Ｓ．成分等を含有する焼成ピ
ッチを収率７２．０％乃至７７．０％で造り、この焼成
ピッチを前述の炭素数６乃至８の芳香族炭化水素の溶剤
抽出にて造る熱に極めて安定なＢ．成分或いはこのＢ．
成分とこのＢ．成分が３個熱結合して造るキノリン等の
溶剤抽出にて造る熱に極めて安定なＱ．Ｓ．成分との混
合物等を原料として不活性ガス或いは分解生成ガスの気
流下５０ｋｇ／ｃｍ２乃至６００ｋｇ／ｃｍ２の加圧下
温度６００℃乃至１，２００℃にて２時間乃至２０時間
の加熱処理して、フラーレンＣ６０を４％乃至２０％含
有する焼成ピッチを収率７０％乃至８４％で造り、この
フラーレンＣ６０を含有する焼成ピッチをメチルアルコ
ールを５％乃至２０％含有するベンゼン或いはメチルア
ルコールを５％乃至２０％含有するテトラヒドロフラン
（ＴＨＦ）を溶剤として使用して効率良く抽出し、この
フラーレンＣ６０等を含有するを溶液をオクタデシルシ
ラン（ＯＤＳ）のシリカゲルの充填物に流し込み、シリ
カゲル系の充填物の作用に依りフラーレンＣ６０を効率
良く分離し、更に之を高温高真空下にて昇華精製して、
フラーレンＣ６０を工業的に安価に製造することが出来
る。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The object of the present invention is to determine the composition of the petroleum pitch composition containing a large amount of benzene and naphthalene nuclei which are extremely stable to heat. Ingredient or B. In order to make a rational fullerene C 60 using the ingredients as raw materials,
Petroleum pitch produced as a by-product by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil is distilled under reduced pressure and cut by 85% to produce initial distillation at 460 ° C to final distillation at 560 ° C (H. component 20.0% to 8%).
0.0%, B.I. Component 20.0% to 80.0%, softening point 46 ° C to 64 ° C) is solvent extracted with an aliphatic hydrocarbon having 6 to 8 carbon atoms. Ingredient (H. ingredient 99.0% to 1
00.0%, B.I. Ingredient 0% to 1.0%, average molecular weight 3
10 to 360, softening point 40 to 50 ° C.),
Raffinate (insoluble matter) obtained by the extraction has 6 carbon atoms.
B. to 8 prepared by solvent extraction of aromatic hydrocarbons. Component (H. component 0% to 1.0%, B. component 99.0% to 100.0%, average molecular weight 390 to 440, softening point 7
Extract the 6 ° C. to 96 ° C.), respectively separately as a raw material, under pressure target temperature 300 ° C. to 6 under a stream 20 kg / cm 2 to 400 kg / cm 2 in an inert gas or decomposition product gas
The temperature was raised to 00 ° C., and H. H. Ingredients and H. Q. The three-dimensional structure, which is extremely stable to the heat produced by heat-bonding three components,
S. Yield of fired pitch containing components etc. is 75% to 85%
%, Which is extremely stable to heat generated by solvent extraction of aliphatic hydrocarbons having 6 to 8 carbon atoms from these fired pitches.
Ingredients or this H. Ingredients and this H. Q. The three-dimensional structure of the quinoline, which is formed by heat-bonding the three components, is very stable to heat and is extracted by solvent extraction. S. 50 kg / c under a stream of an inert gas or decomposition product gas using a mixture with other ingredients as a raw material
m 2 600 kg / cm 2 under pressure 600 ° C. to 1,
Heat treatment is performed at 200 ° C. for 2 hours to 20 hours to produce a fired pitch containing 4% to 20% of fullerene C 60 with a yield of 74% to 84%, or as described above, a petroleum pitch having a carbon number of 6 to 6%. Raufinate produced by solvent extraction of 88 aliphatic hydrocarbons is solvent extracted with aromatic hydrocarbons having 6 to 8 carbon atoms. The components are heated under a pressure of 20 kg / cm 2 to 400 kg / cm 2 under a pressure of 300 ° C. to 600 ° C. under a stream of an inert gas or a decomposition product gas, and a preliminary severe heating is performed for 2 hours to 10 hours at the target temperature. B. depending on the treatment. B. which is extremely stable to heat from the ingredients Ingredients and B. which are extremely stable to this heat Q. The three-dimensional structure is very stable to heat due to three heat-bonded components. S. A fired pitch containing components and the like is produced at a yield of 72.0% to 77.0%, and this fired pitch is produced by solvent extraction of the aromatic hydrocarbon having 6 to 8 carbon atoms. ． Ingredients or this B.I.
Ingredients and this B. Q. Very stable to heat produced by solvent extraction of quinoline etc. S. It was heated for 2 hours to 20 hours mixtures at the pressure temperature 600 ° C. inert gas or decomposition products under a stream 50 kg / cm 2 to 600 kg / cm 2 gas to 1,200 ° C. as a raw material of the component A burned pitch containing 4% to 20% fullerene C 60 with a yield of 70% to 84%, and a burned pitch containing fullerene C 60 containing benzene or methyl alcohol containing 5% to 20% methyl alcohol. Tetrahydrofuran (THF) containing 5% to 20% is efficiently extracted as a solvent, and a solution containing this fullerene C 60 etc. is poured into a silica gel packing of octadecylsilane (ODS) to fill a silica gel system. Efficiently separates fullerene C 60 depending on the action of the substance, and further purifies it by sublimation under high temperature and high vacuum.
Fullerene C 60 can be manufactured industrially at low cost.
【０００６】従来のフラーレンＣ６０の製法は、ヘリウ
ムガスの如き不活性ガス中にアーク放電に依り、放電用
の電極の炭素を気化し、その超高温に依って加熱気化し
た六角型に配列された炭素の気体を冷却する過程に於い
てフラーレンＣ６０が製造されている。併も従来の方法
はその熱効率は極めて悪く、而も従来のフラーレンＣ
６０の製造に於いて炭素数６０以上の単なるススも極め
て多く、炭素の６０個のフラーレンＣ６０の含有量は生
成物のススの中に極めて微小で、そのススの生成物より
フラーレンＣ６０の溶剤分離は極めて困難で非能率的で
ある。In the conventional method for producing fullerene C 60 , carbon of an electrode for discharge is vaporized by an arc discharge in an inert gas such as helium gas, and the carbon is heated and vaporized by its ultrahigh temperature to form a hexagonal array. Fullerene C 60 is manufactured in the process of cooling the carbon gas. At the same time, the thermal efficiency of the conventional method is extremely poor, and the conventional fullerene C is also used.
60 just soot or 60 carbon atoms in the production of even very large, the content of 60 fullerene C 60 carbon is extremely small in the product soot, fullerene C 60 from the product of the soot Solvent separation is extremely difficult and inefficient.
【０００７】従来のフラーレンＣ６０の製法に対して本
法はフラーレンＣ６０製法に於いて障害となる原料の石
油系ピッチの組成成分のＨ．成分或いはＢ．成分の芳香
族化合物の側鎖のアルキル基がフラーレンＣ６０の生成
過程に於いてフラーレンＣ６０以外の炭素のみのススを
生成し、フラーレンＣ６０生成分離を困難にする為、予
備の加熱処理に依り原料の石油系ピッチのＨ．成分或い
はＢ．成分の側鎖のアルキル基の炭素を極力除去した６
個の炭素の六角型の配列のベンゼン核と１０個の炭素の
配列したナフタリン核の化合物を主成分とする熱に極め
て安定なＨ．成分を單味で亦この熱に極めて安定なＨ．
成分とこのＨ．成分が３個熱結合して造る熱に極めて安
定な立体構造のＱ．Ｓ．成分等との混合物を、或いは熱
に極めて安定なＢ．成分を單味で、亦この熱に極めて安
定なＢ．成分とこのＢ．成分が３個熱結合して造る熱に
極めて安定な立体構造のＱ．Ｓ．成分等との混合物を不
活性ガス或いは分解生成ガスの気流下高圧高温加熱処理
し、不純物の極めて少ないフラーレンＣ６０を多く含有
する焼成ピッチをメチルアルコールを５％乃至２０％含
有するベンゼン或いはメチルアルコールを５％乃至２０
％含有するテトラヒドロフラン（ＴＨＦ）を溶媒抽出用
の溶剤として使用して効率良く分離し、この抽出液をオ
クタデシルシラン（ＯＤＳ）の充填層に流し込み、フラ
ーレンＣ６０を抽出溶液より効率良く分離し、更に之を
高温度高真空下にて昇華して生成することに依り始めて
高純度の物性の優れたフラーレンＣ６０を合理的に安価
に多量に製造することが可能になった。[0007] Act against preparation of conventional fullerene C 60 is H. composition components petroleum pitch feedstock that interfere at the fullerene C 60 Preparation Ingredient or B. Alkyl group in the side chain of the aromatic compound of the component is at the process of generating the fullerene C 60 to generate soot only carbon other than fullerene C 60, to the difficulty of fullerene C 60 product separation, the pre-heat treatment Therefore, H. Ingredient or B. The carbon of the alkyl group of the side chain of the component was removed as much as possible 6
H.H., which is composed of a compound of a benzene nucleus having a hexagonal arrangement of 10 carbons and a naphthalene nucleus having an arrangement of 10 carbons as a main component and is extremely stable to heat. H. Ingredients are very stable to this heat.
Ingredients and this H. Q. The three-dimensional structure, which is extremely stable to the heat produced by heat-bonding three components, S. B. which is extremely stable to a mixture with components or the like, or to heat. Ingredients are very aromatic, and the heat of the heat is extremely stable. Ingredients and this B. Q. The three-dimensional structure, which is extremely stable to the heat produced by heat-bonding three components, S. Benzene or methyl alcohol containing 5% to 20% of methyl alcohol is used as a firing pitch containing a large amount of fullerene C 60 containing very few impurities, by subjecting a mixture of the components and the like to a high-pressure high-temperature heat treatment under a stream of an inert gas or a decomposition product gas. 5% to 20
% Of tetrahydrofuran (THF) is used as a solvent for solvent extraction for efficient separation, and this extract is poured into a packed bed of octadecylsilane (ODS) to separate fullerene C 60 more efficiently than the extraction solution. It became possible to reasonably produce a large amount of fullerene C 60 having a high purity and excellent physical properties at a reasonable cost only by sublimating and producing the fullerene under high temperature and high vacuum.
【０００８】本法は石油系ピッチのＨ．成分及びＢ．成
分の精密化学分析法及びこれの成分より造られる熱に極
めて安定なＨ．成分及びＢ．成分、その他熱に極めて安
定なＱ．Ｓ．成分等を原料として高温高圧下にて加熱処
理過程の生成物のスペクトル分解に依ってフラーレンＣ
６０生成過程の生成物の化学分析法の開発研究に依って
次の事実が判明した。即ちＨ．成分及びＢ．成分を予備
の厳しい加熱処理に依って造られる熱に極めて安定な
Ｈ．成分の化学組成及びそれの化学構造、このＨ．成分
より造る熱に極めて安定なＨ．成分が３個結合して立体
構造を型成する熱に極めて安定なＱ．Ｓ．成分の化学組
成及びそれの構造、亦Ｂ．成分の予備の厳しい加熱処理
に依って造られる熱に極めて安定なＢ．成分の化学組成
及びそれの化学構造、このＢ．成分より造る熱に極めて
安定なＢ．成分が３個結合して立体構造を型成する熱に
極めて安定なＱ．Ｓ．成分の化学組成及びそれの構造も
判明し、これ等を原料として不活性ガス或いは分解生成
ガスの気流下５０ｋｇ／ｃｍ２乃至６００ｋｇ／ｃｍ２
の加圧下温度６００℃乃至１，２００℃にて２時間乃至
２０時間加熱処理して造る熱に極めて安定なＨ．成分及
びこのＨ．成分より造る熱に極めて安定なＱ．Ｓ．成分
等、亦熱に極めて安定なＢ，成分及びこのＢ．成分より
造る熱に極めて安定なＱ．Ｓ．成分等を原料としてフラ
ーレンＣ６０を製造するそれの製造過程の中間生成物の
構造を各種の吸収スペクトルに依って炭素数２０或いは
２８の化合物而もそれが六角型及び五角型より構成され
ることも判明し、これ等の熱に極めて安定なＨ．成分亦
熱に極めて安定なＢ．成分を原料とするフラーレンＣ
６０の生成過程を管理してフラーレンＣ６０を４％乃至
２０％含有する焼成ピッチを収率７０％乃至８４％で造
り、この焼成ピッチをメチルアルコールを５％乃至２０
％含有するベンゼン或いはメチルアルコールを５％乃至
２０％含有するテトラヒドロフラン（ＴＨＦ）を溶剤と
して使用して選択的に効率良く抽出しこの抽出溶液をオ
クタデシルシラン（ＯＤＳ）のシリカゲル充填層に流し
込み、フラーレンＣ６０をその溶液より効率良く分離
し、更に之を高温高真空下にて昇華精製して始めて高純
度の物性の優れたフラーレンＣ６０を合理的に工業的に
精製することを特徴とする方法である。This method is applied to petroleum pitch H.264. Ingredients and B. A method of fine chemical analysis of components and H. Ingredients and B. Ingredients and other heat extremely stable Q. S. Fullerene C based on the spectral decomposition of the product of the heat treatment process at high temperature and high pressure using the components as raw materials
The following facts have been revealed by the research and development of the chemical analysis method of the product in the 60 production process. That is, H. Ingredients and B. H. H., which is extremely stable to the heat produced by the preliminary severe heat treatment of the ingredients. The chemical composition of the components and their chemical structure, this H. H.V. which is extremely stable to heat produced from its ingredients Extremely stable Q.I. S. Chemical composition of components and structure thereof, B. The heat-stable B.I. produced by the preliminary rigorous heat treatment of the ingredients. The chemical composition of the components and their chemical structure, this B.I. B. which is extremely stable to heat produced from its ingredients Extremely stable Q.I. S. The chemical composition of the components and the structure of the components have been clarified, and these are used as raw materials under an inert gas or decomposition product gas stream of 50 kg / cm 2 to 600 kg / cm 2.
H.V. which is extremely stable to heat produced by heat treatment at a temperature of 600 ° C. to 1,200 ° C. under pressure for 2 hours to 20 hours. Ingredients and this H. Extremely stable to heat generated from the ingredients Q. S. Ingredients such as B, which are extremely stable against heat, and the ingredients and B. Extremely stable to heat generated from the ingredients Q. S. Fullerene C 60 is produced by using components as raw materials, and the structure of an intermediate product in the production process thereof is a compound having 20 or 28 carbon atoms depending on various absorption spectra, and that it is composed of hexagonal type and pentagonal type. It was also found that H. B. which is extremely stable against heat Fullerene C made from ingredients
Build firing pitch manages 60 generation process of containing fullerene C 60 4% to 20% in the 70% to 84% yield, 5% to methyl alcohol This baked pitch 20
% Of benzene or methyl alcohol containing 5% to 20% of tetrahydrofuran (THF) as a solvent is selectively and efficiently extracted, and the extracted solution is poured into a silica gel packed layer of octadecylsilane (ODS) to obtain fullerene C. 60 is efficiently separated from the solution, and the fullerene C 60 having a high purity and excellent physical properties is rationally and industrially purified by sublimation purification under high temperature and high vacuum. is there.
【００９】石油系ピッチを炭素数６乃至８の脂肪族炭化
水素或いは芳香族炭化水素の溶剤抽出にて造るＨ．成分
或いはＢ．成分を原料として予備の厳しい加圧加熱する
反応で造る熱に極めて安定なＨ．成分或いはそれのＱ．
Ｓ．成分、亦は熱に極めて安定なＢ．成分或いはそれの
Ｑ．Ｓ．成分等を原料としてフラーレンＣ６０を含有す
る焼成ピッチを造る加圧加熱する反応に使用する不活性
ガスは、窒素、メタン、エタン、プロパン等或いはこれ
等の混合ガス、亦更に焼成ピッチを製造する際に副生す
る分解生成ガス（その１例として水素６．０％、メタン
７４．６％、エタン１３．４％、プロパン３．６％、ブ
タン１．３％、ペタン０．９％、オレフイン類０．１％
等）を挙げることが出来る。H. H. Producing petroleum pitch by solvent extraction of aliphatic or aromatic hydrocarbons having 6 to 8 carbon atoms. Ingredient or B. H.H.O., which is extremely stable to the heat produced by the reaction of preliminarily rigorous pressure heating using the ingredients as raw materials Ingredient or its Q.
S. Ingredients and ingredients are extremely stable to heat. Ingredient or its Q. S. The inert gas used in the reaction of pressurizing and heating for producing a fired pitch containing fullerene C 60 from the ingredients as raw materials is nitrogen, methane, ethane, propane or the like, or a mixed gas thereof, and further produces a fired pitch. Decomposition gas produced as a by-product (hydrogen 6.0%, methane 74.6%, ethane 13.4%, propane 3.6%, butane 1.3%, petane 0.9%, olefin). Class 0.1%
Etc.) can be mentioned.
【００１０】[0010]
【実施例１】脱硫減圧軽油の熱接触分解（ＦＣＣ）に依
り副生される石油系ピッチを減圧蒸留し、８５％カット
して造る留分（初留４６０℃乃至終留５６０℃、Ｈ．成
分７１．７％、平均分子量３４２、軟化点４６℃乃至４
９℃、Ｂ．成分２８．１％、平均分子量４３２、軟化点
９２℃乃至９６℃、ベンゼン不溶分０．１％以下）をヘ
プタンにて溶剤抽出して造るＨ．成分（Ｈ．成分９９．
９％、平均分子量３４２、軟化点４６℃乃至４９℃、
Ｂ．成分０．１％以下）を原料として、焼成ピッチを製
造する際に副生する分解生成ガス（水素６．０％、メタ
ン７４．６％、エタン１３．４％、プロパン３．６％、
ブタン１．３％、ペンタン０．９％、オフレイン類０．
１％等）の気流下１００ｋｇ／ｃｍ２の加圧下温度４０
０℃にて５時間加熱処理し、ベンゼン核１個及びナフタ
リン核１個に出来るだけ炭素数の少ない側鎖のアルキル
基を有する熱に極めて安定なＨ．成分（平均分子量２６
５、軟化点３６℃乃至３８℃）及びこの熱に極めて安定
なＨ．成分が３個熱結合して立体構造を型成する熱に極
めて安定なＱ．Ｓ．成分（平均分子量７３２、軟化点３
０８℃乃至３１４℃）等を含有する焼成ピッチを収率８
１％で造り、この焼成ピッチをヘプタンにて溶剤抽出し
て造る熱に極めて安定なＨ．成分（平均分子量２６５、
軟化点３６℃乃至３８℃）を原料として前述の分解生成
ガスの気流下３００ｋｇ／ｃｍ２の加圧下温度１，００
０℃にて６時間加熱し、フラーレンＣ６０を８％含有す
る熱成ピッチを収率７６％で造り、この焼成ピッチをメ
チルアルコールを１０％含有するベンゼンを溶媒として
フラーレンＣ６０等を効率良く選択的に溶剤抽出しその
溶液をオクタデシルシラン（ＯＤＳ）のシリカゲルの充
填層に流し込み、フラーレンＣ６０をその溶液より効率
良く分離し、更に高温高真空下にて精製して工業的にフ
ラーレンＣ６０を製造することが出来る。Example 1 A fraction produced by distilling petroleum pitch produced as a by-product of thermal catalytic cracking (FCC) of desulfurized vacuum gas oil under reduced pressure and cutting it by 85% (initial distillation 460 ° C to final distillation 560 ° C, H.V. Component 71.7%, average molecular weight 342, softening point 46 ° C to 4
9 ° C, B.I. H.C. made by solvent extraction of 28.1% of components, average molecular weight of 432, softening point of 92 to 96 ° C., benzene insoluble content of 0.1% or less) with heptane. Ingredient (H. Ingredient 99.
9%, average molecular weight 342, softening point 46 ° C to 49 ° C,
B. (Composition 0.1% or less) as a raw material, a decomposition product gas (6.0% hydrogen, 74.6% methane, 13.4% ethane, 3.6% propane), which is a by-product when manufacturing a fired pitch.
Butane 1.3%, Pentane 0.9%, Ofrains 0.
1%, etc.) under a pressure of 100 kg / cm 2 under a temperature of 40
Heat treatment was carried out at 0 ° C. for 5 hours to obtain a highly stable H.O.I. having a side chain alkyl group having as few carbon atoms as possible in one benzene nucleus and one naphthalene nucleus. Ingredient (average molecular weight 26
5, softening point 36 ° C. to 38 ° C.) and H.V. Q. The three components are heat-bonded and form a three-dimensional structure. S. Ingredient (average molecular weight 732, softening point 3
(8 ° C. to 314 ° C.), etc.
It is made of 1%, and this fired pitch is solvent-extracted with heptane to produce H.V. Ingredient (average molecular weight 265,
With a softening point of 36 ° C. to 38 ° C. as a raw material, a temperature of 100 kg under pressure of 300 kg / cm 2 under the flow of the above-mentioned decomposition product gas.
0 ℃ at heated 6 hours, the NetsuNaru pitch containing fullerene C 60 8% build in 76% yield, efficiently fullerene C 60, etc. The fired pitch as a solvent of benzene containing 10% methyl alcohol Selective solvent extraction is performed and the solution is poured into a packed bed of octadecylsilane (ODS) silica gel to efficiently separate fullerene C 60 from the solution and further purified under high temperature and high vacuum to industrially obtain fullerene C 60. Can be manufactured.
【００１１】[0011]
【実施例２】脱硫減圧軽油の熱接触分解（ＦＣＣ）に依
って副生される石油系ピッチを減圧蒸留し、８５％カッ
トして造る留分（初留４６０℃乃至５６０℃、Ｈ．成分
７１．７％、平均分子量３４２ 軟化点４６℃乃至４９
℃、Ｂ．成分２８．１％、平均分子量４３２、軟化点９
２℃乃至９６℃、ベンゼン不溶分０．１％以下）をヘプ
タンにて溶剤抽出して造るＨ．成分（Ｈ．成分９９．９
％、平均分子量３４２、軟化点４６℃乃至４９℃、Ｂ．
成分０．１％以下）を原料として、焼成ピッチを製造す
る際に副生する分解生成ガス（水素６．０％、メタン７
４．６％、エタン１３．４％、プロパン３．６％、ブタ
ン１．３％、ペンタン０．９％、オフレイン類０．１％
等）の気流下１００ｋｇ／ｃｍ２の加圧下５００℃にて
２時間加熱処理して熱に極めて安定なＨ．成分（平均分
子量２６５、軟化点３６℃乃至３８℃）及びこのＨ．成
分が３個熱結合して造る立体構造を型成する熱に極めて
安定なＱ．Ｓ．成分（平均分子量７３２、軟化点３０８
℃乃至３１４℃）との混合物を含有する焼成ピッチを収
率８１％で造り、これをヘプタンにて抽出するＨ．成分
とヘプタンにて抽出するラフイネート（不溶分）をキノ
リンにて溶剤抽出するＱ．Ｓ．成分との混合物を前述の
分解生成ガスの気流下３００ｋｇ／ｃｍ２の加圧下温度
１，０００℃にて６時間加熱してフラーレンＣ６０を８
％含有する熱成ピッチを収率７６％で造り、之をメチル
アルコールを１０％含有するベンゼンを溶剤として溶剤
抽出し、そのフラーレンＣ６０を分離除去した残渣の焼
成ピッチを１００部に対して、Ｈ．成分を原料として予
備の厳しい加熱処理に依って造る熱に極めて安定なＨ．
成分（平均分子量２６５、軟化点３６℃乃至３８℃）及
びこのＨ．成分が３個熱結合して造るり立体構造を型成
する熱に極めて安定なＱ．Ｓ．成分（平均分子量７３
２、軟化点３０８℃乃至３１４℃）との混合物１００部
を添加し充分混合し、この混合物を分解生成ガス（水素
６．０％、メタン７４．６％、エタン１３．４％、プロ
パン３．６％、ブタン１．３％、ペンタン０．９％、オ
フレイン類０．１％等）の気流下３００ｋｇ／ｃｍ２の
加圧下１，０００℃にて５時間加熱処理し、フラーレン
Ｃ６０を８％含有する焼成ピッチを収率８２％で造り、
この焼成ピッチをメチルアルコールを１０％含有するベ
ンゼンを溶剤としてフラーレンＣ６０を選択的に溶剤抽
出し、その溶液をオクタデシルシラン（ＯＤＳ）のシリ
カゲル充填層に流し込み、フラーレンＣ６０のみ効率良
く分離し、更に之を高温高真空下にて精製して工業的に
フラーレンＣ６０を製造することが出来る。Example 2 A fraction produced by distilling petroleum pitch produced as a by-product of thermal catalytic cracking (FCC) of desulfurized vacuum gas oil under reduced pressure and cutting it by 85% (initial distillation 460 to 560 ° C., H. 71.7%, average molecular weight 342, softening point 46 ° C to 49
C., B.I. Component 28.1%, average molecular weight 432, softening point 9
H.C. produced by solvent extraction of benzene-insoluble matter of 0.1% or less (2 ° C to 96 ° C) with heptane. Ingredient (H. ingredient 99.9
%, Average molecular weight 342, softening point 46 ° C. to 49 ° C., B.I.
A decomposition product gas (hydrogen 6.0%, methane 7) produced as a by-product when a fired pitch is produced by using a component of 0.1% or less as a raw material.
4.6%, ethane 13.4%, propane 3.6%, butane 1.3%, pentane 0.9%, ophthalanes 0.1%
Etc.) under a pressure of 100 kg / cm 2 under a pressure of 500 ° C. for 2 hours to perform heat treatment for 2 hours. Ingredient (average molecular weight 265, softening point 36 ° C to 38 ° C) and this H. Q. Very stable to heat, which forms a three-dimensional structure created by heat-bonding three components. S. Ingredient (average molecular weight 732, softening point 308
C. to 314.degree. C.) to produce a fired pitch containing 81% yield, which is extracted with heptane. Component and raffinate (insoluble matter) extracted with heptane are solvent extracted with quinoline Q. S. The mixture with the components was heated for 6 hours at a temperature of 1,000 ° C. under a pressure of 300 kg / cm 2 under a stream of the above-mentioned decomposition product gas to give fullerene C 60 at 8
% Of the thermal-formed pitch was produced with a yield of 76%, and the solvent-extracted benzene containing 10% of methyl alcohol was used as a solvent, and the fullerene C 60 was separated and removed. H. H.V., which is extremely stable to the heat produced by the preliminary severe heat treatment using the ingredients as raw materials
Ingredient (average molecular weight 265, softening point 36 ° C to 38 ° C) and this H. The three components are heat-bonded to form a three-dimensional structure. S. Ingredient (average molecular weight 73
2, 100 parts of a mixture with a softening point of 308 ° C. to 314 ° C.) was added and thoroughly mixed, and this mixture was decomposed and produced gas (hydrogen 6.0%, methane 74.6%, ethane 13.4%, propane 3. 6%, butane 1.3%, pentane 0.9%, ophthalanes 0.1%, etc.) under a pressure of 300 kg / cm 2 under pressure of 1,000 ° C. for 5 hours to give fullerene C 60 at 8 % To produce a firing pitch containing 82%,
Fullerene C 60 is selectively solvent-extracted from this baked pitch using benzene containing 10% methyl alcohol as a solvent, and the solution is poured into a silica gel packed layer of octadecylsilane (ODS) to efficiently separate only fullerene C 60 . Further, the fullerene C 60 can be industrially produced by refining under high temperature and high vacuum.
【００１４】[0014]
【実施例３】石油系ピッチンＣ６０のＢ．成分（Ｈ．成
分０．１％以下、Ｂ．成分９９．９％、平均分子量４３
２、軟化点９２％乃至９６℃）を原料とし、焼成ピッチ
を製造する際に副生する分解生成ガス（水素６．０％、
メタン７４．６％、エタン１３．４％、プロパン３．６
％、ブタン１．３％、ペンタン０．９％、オフレイン類
０．１％等）の気流下１００ｋｇ／ｃｍ２の加圧下温度
５００℃にて３時間加熱処理してベンゼン核２個とナフ
タリン核１個に出来るだけ炭素数の少ない側鎖のアルキ
ル基を有する熱に極めて安定なＢ．成分（平均分子量３
６８、軟化点８２℃乃至８６℃）及びこのＢ．成分が３
個熱結合して立体構造を型成する熱に極めて安定なＱ．
Ｓ．成分（平均分子量８４２、軟化点３５０℃乃至３５
５℃）等を有する焼成ピッチを収率７４％で造り、この
焼成ピッチをベンゼンにて抽出する熱に極めて安定な
Ｂ．成分及びベンゼンの溶剤抽出にて造るラフイネート
（不溶分）をキノリンの溶剤抽出に依って造る熱に極め
て安定なＱ．Ｓ．成分との混合物を原料として前述の分
解生成ガス（水素６．０％、メタン７４．６％、エタン
１３．４％、プロパン３．６％、プタン１．３％、ペン
タン０．９％、オフレイン類０．１％等）の気流下３０
０ｋｇ／ｃｍ２の加圧下温度１，０００℃にて８時間加
熱処理してフラーレンＣ６０を６％含有する焼成ピッチ
を収率７４％で造り、この焼成ピッチをメチルアルコー
ルを１０％含有するベンゼンを溶媒としてフラーレンＣ
６０を選択的に抽出分離した残渣１００部に、Ｂ．成分
を原料として予備の厳しい加熱処理に依って造る熱に極
めて安定なＢ．成分（平均分子量３６８、軟化点８２℃
乃至８６℃）とこのＢ．成分が３個熱結合して立体構造
を型成する熱に極めて安定なＱ．Ｓ．成分（平均分子量
８４２、軟化点３５０℃乃至３５５℃）との混合物１０
０部を充分混合し、これを前述の分解生成ガスの気流下
３００ｋｇ／ｃｍ２の加圧下１，０００℃にて５時間加
熱処理し、フラーレンＣ６０を８％含有する焼成ピッチ
を収率８０％で造り、この焼成ピッチをメチルアルコー
ルを１０％含有するベンゼンを溶媒としてフラーレンＣ
６０を選択的に溶剤抽出し、その溶液をオクタデシルシ
ラン（ＯＤＳ）のシリカゲルの充填層に流し込み、フラ
ーレンＣ６０のみを効率良く分離し、更に之を高温高真
空下にて精製して工業的にフラーレンＣ６０を精製する
ことが出来る。[Example 3] Petroleum pitchin C 60 B.I. Component (H. component 0.1% or less, B. component 99.9%, average molecular weight 43
2. Using a softening point of 92% to 96 ° C. as a raw material, a decomposition product gas (hydrogen 6.0%, by-produced when a fired pitch is produced,
Methane 74.6%, ethane 13.4%, propane 3.6
%, Butane 1.3%, pentane 0.9%, ophthalenes 0.1%, etc.) and heat treatment at a temperature of 500 ° C. under a pressure of 100 kg / cm 2 for 3 hours to obtain 2 benzene nuclei and naphthalene nuclei. A highly heat-stable B.I. having one side chain alkyl group having as few carbon atoms as possible. Ingredient (average molecular weight 3
68, softening point 82 ° C to 86 ° C) and this B.I. 3 ingredients
Extremely stable Q.
S. Ingredients (average molecular weight 842, softening point 350 ° C to 35
A fired pitch having a yield of 74% was produced with a yield of 74%, and B. The component and rafinate (insoluble matter) produced by solvent extraction of benzene are produced by solvent extraction of quinoline. S. The decomposition product gas (6.0% hydrogen, 74.6% methane, 13.4% ethane, 3.6% propane, 1.3% pentane, 0.9% pentane, and orain Under 0.1% of air flow)
By heat-treating at a temperature of 1,000 ° C. under a pressure of 0 kg / cm 2 for 8 hours, a fired pitch containing 6% of fullerene C 60 was produced with a yield of 74%, and the fired pitch was benzene containing 10% of methyl alcohol. Fullerene C as a solvent
100 parts of the residue obtained by selectively extracting and separating 60 . B. which is extremely stable to heat produced by a preliminary severe heat treatment using the ingredients as raw materials. Ingredients (average molecular weight 368, softening point 82 ° C
~ 86 ° C) and this B. Q. The three components are heat-bonded and form a three-dimensional structure. S. Mixture 10 with components (average molecular weight 842, softening point 350 ° C to 355 ° C)
0 parts was thoroughly mixed, and this was heat-treated at 1,000 ° C. for 5 hours under a pressure of 300 kg / cm 2 under a stream of the above-mentioned decomposition product gas to obtain a firing pitch containing 8% of fullerene C 60 at a yield of 80. %, And this fired pitch is fullerene C using benzene containing 10% of methyl alcohol as a solvent.
60 is selectively solvent-extracted, the solution is poured into a packed bed of octadecylsilane (ODS) silica gel, the fullerene C 60 is efficiently separated, and further purified under high temperature and high vacuum to industrially Fullerene C 60 can be purified.
【００１５】[0015]
【発明の効果】脱硫減圧軽油の熱接触分解（ＦＣＣ）に
依って副産される石油系ピッチ（Ｈ．成分とＢ．成分と
の混合物）を溶剤抽出に依ってＨ．成分とＢ．成分とに
夫々分離抽出し、夫々を先ず過激な予備の加熱処理を実
施し、石油の油種及び石油系ピッチの製法に全く関係無
く、ベンゼン核とナフタリン核を主成分とする出来るだ
け炭素数の少ないアルキル基の側鎖を有する熱に極めて
安定なＨ．成分を單味で、或いはこのＨ．成分とこの
Ｈ．成分が３個熱結合して造る立体構造を型成する熱に
極めて安定なＱ．Ｓ．成分との混合物を造り、亦熱に極
めて安定なＢ．成分を單味で、或いはこのＢ．成分とこ
のＢ．成分が３個熱結合して造る立体構造を型成する熱
に極めて安定なＱ．Ｓ．成分との混合物を夫々原料とし
て不活性ガス或いは分解生成ガスの気流下高圧高温度に
て加熱処理してフラーレンＣ６０を４％乃至２０％含有
する焼成ピッチを造り、これ等の焼成ピッチを夫々別々
に溶剤としてメチルアルコールを５％乃至２０％含有す
るベンゼン或いはメチルアルコールを５％乃至２０％含
有するテトラヒドロフラン（ＴＨＦ）の溶液を使用して
フラーレンＣ６０選択的に溶剤抽出し、その溶液をオク
タデシルシラン（ＯＤＳ）のシリカゲルの充填層に流し
込み、フラーレンＣ６０のみを分離し、更に之を高温高
真空下にて昇華して精製し、合理的に且つ工業的に製造
することが始めて可能となった。EFFECT OF THE INVENTION Petroleum pitch (a mixture of H. component and B. component) produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil is mixed with H. Ingredients and B. Separately and extract each of the components, and first carry out a radical preliminary heat treatment, regardless of the oil type of the petroleum and the production method of the petroleum-based pitch, and have as many carbon atoms as possible with the benzene nucleus and the naphthalene nucleus as the main components. A highly heat-stable H.V. having a side chain of a low-alkyl group. Ingredients with a taste or this H. Ingredients and this H. Q. Very stable to heat, which forms a three-dimensional structure created by heat-bonding three components. S. The mixture with the ingredients is made, and B. which is extremely stable against heat. Ingredients are tasted, or this B. Ingredients and this B. Q. Very stable to heat, which forms a three-dimensional structure created by heat-bonding three components. S. The mixture with the components is heated as a raw material at a high pressure and a high temperature under a stream of an inert gas or a decomposition product gas to form a firing pitch containing 4% to 20% of fullerene C 60, and the firing pitch of each of these is obtained. Separately, fullerene C 60 was selectively solvent-extracted using a solution of benzene containing 5% to 20% of methyl alcohol or tetrahydrofuran (THF) containing 5% to 20% of methyl alcohol as a solvent, and the solution was octadecyl. It becomes possible for the first time to rationally and industrially manufacture by pouring into a packed bed of silica gel of silane (ODS), separating only fullerene C 60 , and further sublimating under high temperature and high vacuum for purification. It was
フロントページの続き (54)【発明の名称】 石油系ピッチの組成成分のＨ．成分或いはＢ．成分を夫々別々に原料として予備処理し、これ等 を別々に溶剤抽出しこれ等の抽出成分を加熱加圧処理し、フラーレン▲Ｃ60▼を含有する焼成ピ ッチを造り、これを特殊な溶剤にてフラーレン▲Ｃ60▼を溶剤抽出し、この抽出溶液をシリカゲ ル系の充填層に流し込みフラーレン▲Ｃ60▼を効率良く選択的に分離精製する方法。Continuation of front page (54) [Title of Invention] H. Ingredient or B. The components are separately preliminarily treated as raw materials, these are separately solvent-extracted, and these extracted components are heat-pressed to make a firing pitch containing fullerene ▲ C60 ▼. A method of solvent-extracting fullerene C60 and pouring this extraction solution into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60.
Claims (2)
ン１５０ｃｃで温度９８．４℃で抽出される成分。 ２ Ｂ．成分：試料のＨ．成分の溶剤抽出で得られる
Ｈ．成分不溶分（ラフイネート）からベンゼン１５０ｃ
ｃで温度８０．１ ℃で抽出される成分。 ３ Ｑ．Ｓ．成分：前述のＢ．成分の溶剤抽出で得られ
るＢ．成分不溶分（ラフイネート）からキノリン１５０
ｃｃで温度２３７℃で抽出される成分。 ４ Ｑ．ｉ．成分：前述のＱ．Ｓ．成分の溶剤抽出で得
られるＱ．Ｓ．成分不溶分（ラフイネート）と定める。 脱硫減圧軽油の熱接触分解（ＦＣＣ）に依り副産される
石油系ピッチを減圧蒸留して８５％カットして造る初留
４６０℃乃至終留５６０℃（Ｈ．成分２０．０％乃至８
０．０％、Ｂ．成分２０．０％乃至８０．０％、平均分
子量３６０乃至４１０、軟化点４６℃乃至６４℃）を炭
素数６乃至８の脂肪族炭化水素の溶剤抽出にて得られる
Ｈ．成分（Ｈ．成分９９．０％乃至１００．０％、Ｂ．
成分０％乃至１．０％、平均分子量３１０乃至３６０、
軟化点４０℃乃至５０℃）を抽出し、そのＨ．成分を不
活性ガス或いは分解生成ガスの気流下２０ｋｇ／ｃｍ２
乃至４００ｋｇ／ｃｍ２の加圧下温度３００℃乃至６０
０℃迄で昇温し、その目標温度で２時間乃至１０時間加
熱する予備処理を実施し、熱に極めて安定なベンゼン核
１個とナフタリン核１個を主成分とし出来るだけ炭素数
の少ないアルキル基の側鎖を有する熱に極めて安定な
Ｈ．成分（平均分子量２６２乃至２７２、軟化点３６℃
乃至４０℃）とこのＨ．成分が３個熱結合して立体構造
を型成する溶剤抽出で得られるラフイネートをキノリン
等にて抽出する熱に極めて安定なＱ．Ｓ．成分（平均分
子量７２０乃至７４４、軟化点３０６℃乃至３１６℃）
等、或いはベンゼン核３個を主成分として出来るだけ炭
素の少ないアルキル基の側鎖を有する熱に極めて安定な
Ｈ．成分（平均分子量３０４乃至３１２、軟化点４０℃
乃至４２℃）とこのＨ．成分が３個熱結合して立体構造
を型成する溶剤抽出で得られるラフイネートをキノリン
等にて抽出する熱に極めて安定なＱ．Ｓ．成分（平均分
子量９２４乃至９３６、軟化点３８０℃乃至３９４℃）
等を含有する焼成ピッチを収率７５％乃至８５％で造
り、炭素数６乃至８の脂肪族炭化水素の溶剤抽出で得ら
れる熱に極めて安定なＨ．成分（平均分子量２６２乃至
２７２、軟化点３６℃乃至４０℃）を單味で、或いはこ
の熱に極めて安定なＨ．成分と焼成ピッチを炭素数６乃
至８の脂肪族炭化水素の溶剤抽出で得られるラフイネー
トをキノリン等にて抽出するＱ．Ｓ．成分（平均分子量
７２０乃至７４４、軟化点３０６℃乃至３１６℃）との
混合物を原料として不活性ガス或いは分解生成ガスの気
流下５０ｋｇ／ｃｍ２乃至６００ｋｇ／ｃｍ２の加圧下
６００℃乃至１，２００℃にて２時間乃至２０時間加熱
してフラーレンＣ６０を４％乃至２０％含有する焼成ピ
ッチを収率７６．０％乃至８４％で造り、亦前述の加熱
処理して造る焼成ピッチを炭素数６乃至８の脂肪族炭化
水素の溶剤抽出で得られる熱に極めて安定なＨ．成分
（平均分子量３０４乃至３１２、軟化点４０℃乃至４２
℃）を單味で、或いはこの熱に極めて安定なＨ．成分と
このＨ．成分が３個熱結合して造る立体構造を型成する
溶剤抽出で得られるラフイネートをキノリン等にて抽出
する熱に極めて安定なＱ．Ｓ．成分（平均分子量９２４
乃至９３６、軟化点３８０℃乃至３９４℃）等との混合
物を原料として不活性ガス或いは分解生成ガスの気流下
５０ｋｇ／ｃｍ２乃至６００ｋｇ／ｃｍ２の加圧下温度
６００℃乃至１，２００℃にて２時間乃至２０時間加熱
してフラーレンＣ６０を４％乃至２０％含有する焼成ピ
ッチを収率７４．０％乃至８４．０％で造り、この焼成
ピッチをメチルアルコールを５％乃至２０％含有するテ
トラヒドロフラン（ＴＨＦ）との混合物を溶剤として選
択的に溶剤抽出し、分離した抽出物をオクタデシルシラ
ン（ＯＤＳ）のシリカゲルを充填した分離管中に溶剤と
共に通過させてフラーレンＣ６０を分離し、この分離物
を更に高温高真空下にて昇華して精製するフラーレンＣ
６０の工業的製造法。1. A 1H. Components: Components extracted from 3 gr of sample with 150 cc of n-heptane at a temperature of 98.4 ° C. 2 B. Component: H. H. coli obtained by solvent extraction of the components. Insoluble component (rafuinate) to benzene 150c
Ingredients extracted in c at a temperature of 80.1 ° C. 3 Q. S. Ingredients: B. B. obtained by solvent extraction of the components Quinoline 150 from insoluble ingredients (rafuinate)
Ingredients extracted at a temperature of 237 ° C in cc. 4 Q. i. Ingredient: Q. S. Q. Obtained by solvent extraction of components S. Determined as insoluble component (rafuinate). Desulfurization Decompressed petroleum-based pitch produced by thermal catalytic cracking (FCC) of petroleum pitch is distilled under reduced pressure and cut by 85% to make initial distillation at 460 ° C to final distillation at 560 ° C (H. component 20.0% to 8%).
0.0%, B.I. Component 20.0% to 80.0%, average molecular weight 360 to 410, softening point 46 ° C to 64 ° C) obtained by solvent extraction of an aliphatic hydrocarbon having 6 to 8 carbon atoms. Component (H. component 99.0% to 100.0%, B.
Ingredient 0% to 1.0%, average molecular weight 310 to 360,
(Softening point 40 ° C. to 50 ° C.) is extracted, and the H. 20 kg / cm 2 under a stream of inert gas or decomposition product gas
To 400 kg / cm 2 under pressure 300 ° C. to 60
A pre-treatment of heating up to 0 ° C and heating at the target temperature for 2 to 10 hours is carried out, and an alkyl having 1 benzene nucleus and 1 naphthalene nucleus, which are extremely stable to heat, as main components and having as few carbon atoms as possible. A highly heat stable H. Ingredients (average molecular weight 262 to 272, softening point 36 ° C)
To 40 ° C.) and this H. The heat-stable Q.V. which is obtained by extracting the raffinate obtained by solvent extraction in which three components are thermally bonded to form a three-dimensional structure with quinoline or the like. S. Ingredients (average molecular weight 720 to 744, softening point 306 ° C to 316 ° C)
Etc., or a highly stable H.V. having a side chain of an alkyl group containing three benzene nuclei as the main component and having as few carbons as possible. Ingredients (average molecular weight 304 to 312, softening point 40 ° C
To 42 ° C) and this H. The heat-stable Q.V. which is obtained by extracting the raffinate obtained by solvent extraction in which three components are thermally bonded to form a three-dimensional structure with quinoline or the like. S. Ingredients (average molecular weight 924 to 936, softening point 380 ° C to 394 ° C)
And the like, which are extremely stable to heat, obtained by solvent extraction of aliphatic hydrocarbons having 6 to 8 carbon atoms. The component (average molecular weight 262 to 272, softening point 36 ° C to 40 ° C) is H. The raffinate obtained by solvent extraction of the component and the firing pitch with an aliphatic hydrocarbon having 6 to 8 carbon atoms is extracted with quinoline or the like. S. Mixture with components (average molecular weight 720 to 744, softening point 306 ° C to 316 ° C) is used as a raw material under a stream of an inert gas or decomposition product gas under pressure of 50 kg / cm 2 to 600 kg / cm 2 600 ° C to 1,200 The firing pitch containing fullerene C 60 at 4% to 20% by heating at ℃ for 2 to 20 hours is produced at a yield of 76.0% to 84%, and the firing pitch produced by the above heat treatment has a carbon number of The heat-stable H.V. obtained by solvent extraction of 6-8 aliphatic hydrocarbons. Components (average molecular weight 304 to 312, softening point 40 ° C to 42
H) which is extremely stable to the heat. Ingredients and this H. A heat-stable Q. S. Ingredient (average molecular weight 924
To 936, a softening point of 380 ° C. to 394 ° C.) as a raw material under a flow of an inert gas or a decomposition product gas at a temperature of 600 ° C. to 1,200 ° C. under a pressure of 50 kg / cm 2 to 600 kg / cm 2 . By heating for 2 to 20 hours, a fired pitch containing 4% to 20% of fullerene C 60 is produced with a yield of 74.0% to 84.0%, and this fired pitch contains 5% to 20% of methyl alcohol. A mixture with tetrahydrofuran (THF) is selectively subjected to solvent extraction as a solvent, and the separated extract is passed together with the solvent through a separation tube filled with octadecylsilane (ODS) silica gel to separate fullerene C 60 , and this separation is performed. Fullerene C for sublimation and purification of materials under high temperature and high vacuum
60 industrial manufacturing methods.
り副産される石油系ピッチを減圧蒸留して造る初留４６
０℃乃至終留５６０℃（Ｈ．成分２０．０％乃至８０．
０％、Ｂ．成分２０．０％乃至８０．０％、平均分子量
３６０乃至４１０、軟化点４６℃乃至６４℃）を炭素数
６乃至８の脂肪族炭化水素の溶剤抽出にて得られるラフ
イネート（不溶分）を炭素数６乃至８の芳香族炭化水素
の溶媒抽出にて得られるＢ．成分（Ｈ．成分０％乃至
１．０％、Ｂ．成分９９．０％乃至１００．０％、平均
分子量３９０乃至４４０、軟化点７６℃乃至９６℃）を
抽出し、そのＢ．成分を不活性ガス或いは分解生成ガス
の気流下２０ｋｇ／ｃｍ２乃至４００ｋｇ／ｃｍ２の加
圧下温度３００℃乃至６００℃迄昇温し、その目標温度
で２時間乃至１０時間加熱する予備処理を実施し、熱に
極めて安定なベンゼン核２個とナフタリン核１個を主成
分とし出来るだけ炭素数の少ないアルキル基の側鎖を有
する熱に極めて安定なＢ．成分（平均分子量３６２乃至
３７６、軟化点８０℃乃至８６℃）とこの熱に極めて安
定なＢ．成分が３個結合して立体構造を型成する熱に極
めて安定なＱ．Ｓ．成分（平均分子量８２４乃至８４
８、軟化点３４７℃乃至３５７℃）等を含有する焼成ピ
ッチを収率７２％乃至７７％で造り、この焼成ピッチを
炭素数６乃至８の芳香族炭化水素の溶剤抽出で得られる
熱に極めて安定なＢ．成分（平均分子量３６２乃至３７
６、軟化点８０℃乃至８６℃）を單味で、或いはこの熱
に極めて安定なＢ．成分と焼成ピッチを炭素数６乃至８
の芳香族炭化水素の溶剤抽出で得られるラフイネートを
キノリン等にて抽出するＱ．Ｓ．成分（平均分子量８２
４乃至８４８、軟化点３４７℃乃至３５７℃）との混合
物を原料として不活性ガス或いは分解生成ガスの気流下
５０ｋｇ／ｃｍ２乃至６００ｋｇ／ｃｍ２の加圧下温度
６００℃乃至１，２００℃にて２時間乃至２０時間加熱
してフラーレンＣ６０を４％乃至２０％含有する焼成ピ
ッチを収率７６％乃至８４％で造り、或いは亦前述の予
備の加熱処理して造る焼成ピッチを炭素数６乃至８の芳
香族炭化水素の溶剤抽出で得られる熱に極めて安定なベ
ンゼン核１個とナフタリン核２個を主成分とし出来るだ
け炭素数の少ないアルキル基の側鎖を有する熱に極めて
安定なＢ．成分（平均分子量４１２乃至４１６、軟化点
７４℃乃至７６℃）を單味で、或いはこの熱に極めて安
定なＢ．成分と焼成ピッチを炭素数６乃至８の芳香族炭
化水素の溶剤抽出で得られるラフイネートをキノリン等
にて抽出するこの熱に極めて安定なＢ．成分が３個結合
して立体構造を型成する熱に極めて安定なＱ．Ｓ．成分
（平均分子量８７６乃至９００、軟化点３６８℃乃至３
７８℃）との混合物を不活性ガス或いは分解生成ガスの
気流下５０ｋｇ／ｃｍ２乃至６００ｋｇ／ｃｍ２の加圧
下温度６００℃乃至１，２００℃にて２時間乃至２０時
間加熱してフラーレンＣ６０を４％乃至２０％含有する
焼成ピッチを収率７０％乃至８４％で造り、これ等の焼
成ピッチをメチルアルコールを５％乃至２０％含有する
ベンゼン或いはメチルアルコールを５％乃至２０％含有
するテトラヒドロフラン（ＴＨＦ）を溶剤として溶剤抽
出し、分離した抽出物をオクタデシルシラン（ＯＤＳ）
のシリカゲルを充填した分離管中に溶剤と共に通過させ
てフラーレンＣ６０を分離し、この分離物を更に高温高
真空下にて昇華して生成するフラーレンＣ６０の工業的
製造法。2. A first distillate 46 produced by vacuum distillation of petroleum-based pitch produced by thermal catalytic cracking (FCC) of desulfurized vacuum gas oil.
0 ° C. to final distillation 560 ° C. (H. component 20.0% to 80.
0%, B.I. Ingredient 20.0% to 80.0%, average molecular weight 360 to 410, softening point 46 ° C to 64 ° C) is used to convert raffinate (insoluble matter) obtained by solvent extraction of an aliphatic hydrocarbon having 6 to 8 carbon atoms into carbon. B. obtained by solvent extraction of aromatic hydrocarbons of several 6 to 8 Component (H. component 0% to 1.0%, B. component 99.0% to 100.0%, average molecular weight 390 to 440, softening point 76 ° C. to 96 ° C.) is extracted, and the B. The inert gas or under pressure Temperature 300 ° C. to 600 ° C. MadeNoboru heated airflow under 20 kg / cm 2 to 400 kg / cm 2 of the decomposition product gas component, a preliminary treatment of heating for 2 hours to 10 hours at that target temperature However, B. which has a side chain of an alkyl group having as few carbon atoms as possible and having two benzene nuclei and one naphthalene nuclei which are extremely stable to heat is extremely stable. Component (average molecular weight 362 to 376, softening point 80 ° C to 86 ° C) and B. Extremely stable Q.I. S. Ingredients (average molecular weight 824 to 84
(8, softening point 347 ° C. to 357 ° C.), etc., to produce a fired pitch with a yield of 72% to 77%, and this fired pitch is extremely resistant to the heat obtained by solvent extraction of an aromatic hydrocarbon having 6 to 8 carbon atoms. Stable B. Ingredients (average molecular weight 362 to 37
6, softening point 80 ° C to 86 ° C) has a taste or is extremely stable to this heat. Ingredients and firing pitch have 6 to 8 carbon atoms
The raffinate obtained by solvent extraction of the aromatic hydrocarbons of 1. is extracted with quinoline or the like. S. Ingredient (average molecular weight 82
4 to 848 and a softening point of 347 ° C. to 357 ° C.) as a raw material under a flow of an inert gas or a decomposition product gas at a temperature of 600 ° C. to 1,200 ° C. under a pressure of 50 kg / cm 2 to 600 kg / cm 2 . A firing pitch containing fullerene C 60 of 4% to 20% is produced at a yield of 76% to 84% by heating for 2 hours to 20 hours, or a firing pitch produced by the above-mentioned preliminary heat treatment has a carbon number of 6 to The heat-stable B.8, which has as its main components 1 benzene nucleus and 2 naphthalene nuclei which are extremely stable to heat obtained by solvent extraction of aromatic hydrocarbons and has side chains of alkyl groups having as few carbon atoms as possible. Ingredients (average molecular weight 412 to 416, softening point 74 ° C. to 76 ° C.) with a taste of B. The heat-stable B. component which is obtained by solvent extraction of aromatic hydrocarbons having 6 to 8 carbon atoms and firing pitch is extracted with quinoline or the like. Extremely stable Q.I. S. Ingredients (average molecular weight 876 to 900, softening point 368 ° C to 3
Fullerene C 60 by heating the mixture of the above (78 ° C) and an inert gas or a decomposition product gas under pressure of 50 kg / cm 2 to 600 kg / cm 2 at a temperature of 600 ° C to 1,200 ° C for 2 hours to 20 hours. A burnt pitch containing 4% to 20% of silane with a yield of 70% to 84%, and these burnt pitches include benzene containing 5% to 20% of methyl alcohol or tetrahydrofuran containing 5% to 20% of methyl alcohol. Solvent extraction was performed using (THF) as a solvent, and the separated extract was octadecylsilane (ODS).
Of silica gel was passed together with the solvent during the separation tube filled with the fullerene C 60 was separated, industrial production process of the fullerene C 60 to generate by sublimating this separation was further under high temperature and high vacuum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6169885A JPH082909A (en) | 1994-06-20 | 1994-06-20 | The composition of petroleum pitch H. Ingredient or B. Pre-treating each component as a raw material separately, extracting these separately with a solvent, and subjecting these extracted components to heat and pressure treatment to create a firing pitch containing fullerene C60, using a special solvent. A method in which fullerene C60 is solvent-extracted, and the extracted solution is poured into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6169885A JPH082909A (en) | 1994-06-20 | 1994-06-20 | The composition of petroleum pitch H. Ingredient or B. Pre-treating each component as a raw material separately, extracting these separately with a solvent, and subjecting these extracted components to heat and pressure treatment to create a firing pitch containing fullerene C60, using a special solvent. A method in which fullerene C60 is solvent-extracted, and the extracted solution is poured into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH082909A true JPH082909A (en) | 1996-01-09 |
Family
ID=15894767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6169885A Pending JPH082909A (en) | 1994-06-20 | 1994-06-20 | The composition of petroleum pitch H. Ingredient or B. Pre-treating each component as a raw material separately, extracting these separately with a solvent, and subjecting these extracted components to heat and pressure treatment to create a firing pitch containing fullerene C60, using a special solvent. A method in which fullerene C60 is solvent-extracted, and the extracted solution is poured into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60. |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082909A (en) |
-
1994
- 1994-06-20 JP JP6169885A patent/JPH082909A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2813920A (en) | Production of ethylene | |
| JPS6158510B2 (en) | ||
| DE19914226A1 (en) | Process for the production of acetylene and synthesis gas | |
| JPH03178935A (en) | Preparation of alkylaromatic hydrocarbon from natural gas | |
| JPH0542477B2 (en) | ||
| JPS6239191B2 (en) | ||
| CN101323433A (en) | Process and device for separating hydrogen from gas flows by a pressure swing adsorption process | |
| JPH08506082A (en) | Low molecular weight C from cracked gas ▲ below 2 ▼ ▲ below + ▼ hydrocarbon recovery method | |
| JP2001523298A (en) | Enhanced olefin yield in catalytic processes using diolefins. | |
| JPS6239192B2 (en) | ||
| KR20160060150A (en) | Fractional extraction of butadiene | |
| JPH082909A (en) | The composition of petroleum pitch H. Ingredient or B. Pre-treating each component as a raw material separately, extracting these separately with a solvent, and subjecting these extracted components to heat and pressure treatment to create a firing pitch containing fullerene C60, using a special solvent. A method in which fullerene C60 is solvent-extracted, and the extracted solution is poured into a silica gel-based packed bed to efficiently and selectively separate and purify fullerene C60. | |
| CN109628141A (en) | A method of by F- T synthesis hydrofined oil separating monomer n-alkane | |
| US20030049195A1 (en) | Polynuclear aromatic hydrocarbons for fullerene synthesis in flames | |
| JPS6247852B2 (en) | ||
| JPH07300308A (en) | Method for producing fulleren c60 by each preliminarily treating component h or component h of composition of petroleum-based pitch as raw material and further thermally treating treated material under high temperature and pressure and selectively extracting baked pitch containing fulleren c60 with specific solvent | |
| JPH07215710A (en) | Method for producing fullerene c60 by heating component b of composition component of petroleum pitch under high pressure and temperature | |
| KR20190092470A (en) | Method for preparing hexadecahydropyrene | |
| JP2013199641A (en) | Method for producing carbon black | |
| JPH1029812A (en) | Production of fullerene c20 by using extremely heat stable component produced by pressurized heat treatment of petroleum pitch as source material and then treating source material in fused state under high pressure and high temperature condition | |
| US4115208A (en) | Recovery of styrene from cracked hydrocarbon fractions | |
| JPH07144908A (en) | Production of fullerene c60 from h component of petroleum pitch by heat treatment at high pressure and high temperature | |
| Patney et al. | Fullerenes and nanotubes from coal | |
| JP3766985B2 (en) | Method for producing high-purity dicyclopentadiene | |
| JPS60240792A (en) | Starting material for production of straight-chain paraffin |