JPH01129092A - Production of mesophase pitch - Google Patents
Production of mesophase pitchInfo
- Publication number
- JPH01129092A JPH01129092A JP62287173A JP28717387A JPH01129092A JP H01129092 A JPH01129092 A JP H01129092A JP 62287173 A JP62287173 A JP 62287173A JP 28717387 A JP28717387 A JP 28717387A JP H01129092 A JPH01129092 A JP H01129092A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- components
- insoluble
- pitch
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002904 solvent Substances 0.000 claims abstract description 169
- 238000010438 heat treatment Methods 0.000 claims abstract description 132
- 239000011295 pitch Substances 0.000 claims abstract description 97
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 83
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000008096 xylene Substances 0.000 claims abstract description 64
- 238000009835 boiling Methods 0.000 claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 39
- 239000003208 petroleum Substances 0.000 claims abstract description 10
- 239000003245 coal Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 133
- 239000000463 material Substances 0.000 claims description 62
- 239000002994 raw material Substances 0.000 claims description 58
- 239000000295 fuel oil Substances 0.000 claims description 46
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 41
- 239000004917 carbon fiber Substances 0.000 claims description 41
- 238000004821 distillation Methods 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 24
- 239000010692 aromatic oil Substances 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000001680 brushing effect Effects 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000001747 exhibiting effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 125000002950 monocyclic group Chemical group 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 238000011010 flushing procedure Methods 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 238000009987 spinning Methods 0.000 description 44
- 239000000047 product Substances 0.000 description 32
- 239000003921 oil Substances 0.000 description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000011280 coal tar Substances 0.000 description 18
- 239000000835 fiber Substances 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 13
- 238000012545 processing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000012719 thermal polymerization Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 150000001454 anthracenes Chemical class 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000011294 coal tar pitch Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- KEIFWROAQVVDBN-UHFFFAOYSA-N 1,2-dihydronaphthalene Chemical compound C1=CC=C2C=CCCC2=C1 KEIFWROAQVVDBN-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Working-Up Tar And Pitch (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はピッチ系高性能炭素繊維製造用に好適な、軟化
点が低（、均質なメソフェーズピッチを効率良く展進す
る方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for efficiently developing a homogeneous mesophase pitch having a low softening point and suitable for producing pitch-based high-performance carbon fibers.
さらに詳しくは、石炭系１石油系重質油もしくはそれら
を蒸留、熱処理又は水素化処理して得られる重質成分で
あって、実質的に単環の芳香族系炭化水素溶剤に不溶の
成分を含まないものであるか、もしくは上記重質油又は
重質成分に単環の芳香族系炭化水素溶剤またはこれと同
等の溶解性をもつ溶剤の該重質油又は重質成分に対して
１〜５重量倍量を加えたときに生成する不溶性成分を分
離除去した後に、溶剤を蒸留除去して得られる精製され
た重質油又は重質成分（以後精農重質成分と云う。）を
原料とし、これを管式加熱炉において、物足の条件下に
加熱処理し、キノリン不溶分を生成させることなく、新
たに単環の芳香族系炭化水素溶剤に不溶な成分を生成さ
せる第１工程と、この加熱処理物を蒸留又はブラッシン
グして軽質成分の一部を除き、特定の性状の熱分解重質
成分を得る第２工程と、この熱分解重質成分からＢＴＸ
溶剤またはこれと同等の溶解性を持つ溶剤に不溶の成分
を高分子量歴青物として回収する第３工程と、第３工程
で不溶性成分を除去した清澄液から溶剤を蒸留除去して
可溶性成分を得る第４工程とからなる水素化原料調整工
程において、第４工程で得られる可溶性成分を第１工程
に循環しながら、第１〜第４工程を連続的に実施するこ
とにより、第３工程から高分子量歴青物を得、これを７
に素供与性溶媒の存在下に加熱処理した後、溶媒を蒸留
除去して得られる水素化ピッチをさらに加熱処理するこ
とによりメソフェーズピッチとすることから成る高性能
尿素繊維製造用ピッチの製造方法である。More specifically, it is a coal-based 1 petroleum-based heavy oil or a heavy component obtained by distillation, heat treatment, or hydrogenation treatment of the same, which is a component that is insoluble in a substantially monocyclic aromatic hydrocarbon solvent. or a monocyclic aromatic hydrocarbon solvent or a solvent with an equivalent solubility in the heavy oil or heavy components. After separating and removing insoluble components produced when 5 times the amount by weight is added, purified heavy oil or heavy components (hereinafter referred to as refined agricultural heavy components) obtained by distilling off the solvent are used as raw materials. In the first step, this is heat-treated in a tube heating furnace under suitable conditions to newly generate components insoluble in monocyclic aromatic hydrocarbon solvents without generating quinoline-insoluble components. a second step of distilling or brushing the heat-treated product to remove a part of the light components to obtain a pyrolyzed heavy component with specific properties;
A third step in which components insoluble in the solvent or a solvent with equivalent solubility are recovered as high molecular weight bituminous materials, and a soluble component is obtained by distilling off the solvent from the clarified liquid from which the insoluble components have been removed in the third step. In the hydrogenation raw material preparation step consisting of the fourth step, by continuously carrying out the first to fourth steps while circulating the soluble components obtained in the fourth step to the first step, high Obtain a molecular weight bituminous material, which is 7
A method for producing pitch for producing high-performance urea fibers, which comprises heat-treating the pitch in the presence of an element-donating solvent and then distilling off the solvent to obtain a hydrogenated pitch, which is then further heat-treated to produce mesophase pitch. be.
本発明によれば、軟化点が低く均質なメソ７エーズビ、
チな効率良くまた安定して製造することができる。According to the present invention, homogeneous meso-7Azebi with a low softening point,
It can be manufactured efficiently and stably.
高性能炭素繊維は軽量であり、強度、弾性率が大きいた
め、航空機用、スポーツ用、産業ロボット用等に用いら
れる複合材料の構成要素として注目を集めており、今後
の需要が大きく伸びると期待されている材料である。High-performance carbon fiber is lightweight and has high strength and elastic modulus, so it is attracting attention as a component of composite materials used in aircraft, sports, industrial robots, etc., and demand is expected to grow significantly in the future. This is the material that has been used.
（従来の技術）
従来、高性能のｍｘ＊維としては、ポリアクリロニドニ
ル（ＰＡＮ）を紡糸し、これを酸化雰囲気中で不融化し
、その後不活性雰囲気中で炭化もしくは黒鉛化すること
により製造されるＰＡＮ系炭素炭素繊維流でありたが、
近年、原料として安価なピッチからも、ＰＡＮ系の炭素
繊維と同等もしくはそれ以上の特性をもつ高性能酸素繊
維を製造し得ることが見いだされ、安価な高性能炭素繊
維の展進法として注目を浴びている。(Prior art) Conventionally, high-performance mx* fibers have been produced by spinning polyacrylonidonyl (PAN), making it infusible in an oxidizing atmosphere, and then carbonizing or graphitizing it in an inert atmosphere. Although it was a PAN-based carbon fiber flow produced,
In recent years, it has been discovered that high-performance oxygen fibers with properties equal to or better than PAN-based carbon fibers can be produced from pitch, which is inexpensive as a raw material, and this method is attracting attention as a method for developing inexpensive high-performance carbon fibers. Bathing.
この様など、チ系の高性能炭素繊維を製造する場合には
、その紡糸用ピッチが偏光顕微鏡下に観察した時に、光
学的に異方性をしめずメソフェーズをその主たる構成成
分とした、いわゆるメソフェーズピッチであることが不
可欠であると言われている。When producing high-performance carbon fibers such as this one, the spinning pitch exhibits no optical anisotropy when observed under a polarizing microscope and has a so-called mesophase as its main constituent. It is said that mesophase pitch is essential.
このメソフェーズは重質油又はピッチを加熱処理する際
に生成する一種の液晶であり、また、熱重合により発達
した芳香族平面分子が積層構造を取るために異方性を示
すものである。この様なメソフェーズピッチを用いて、
溶融紡糸法により繊維を製造すると、発達した芳香族平
面分子がノズル孔を通過する際に加わる応力により、繊
維軸方向に配列し、この配向構造はその後の不融化、炭
化の際にも乱れるこ・となく維持されるため、配向性の
良い炭素繊維が得られる。This mesophase is a type of liquid crystal that is generated when heavy oil or pitch is heat-treated, and exhibits anisotropy because the aromatic planar molecules developed through thermal polymerization take a layered structure. Using such a mesophase pitch,
When fibers are manufactured using the melt spinning method, the developed aromatic planar molecules are aligned in the fiber axis direction due to the stress applied when passing through the nozzle hole, and this orientation structure is likely to be disturbed during subsequent infusibility and carbonization. - Carbon fibers with good orientation can be obtained.
逆にメソフェーズを含まない等方性ピッチを用〜また場
合には、その構成成分の平面構造が十分に発達していな
いため、ノズル孔を通過する際の応力によりても繊維軸
方向の配列が十分に起らず、配向性の低い繊維となり、
これを不融化、炭化しても強度の低い炭素繊維しか得ら
れないことになる。したがりて、数多く提案されている
ピッチ系高性能炭素繊維の製造方法は、その大半が紡糸
用ピッチとしてのメソ７エーズビ。On the other hand, if isotropic pitch that does not contain mesophase is used, the planar structure of the constituent components is not sufficiently developed, and the stress when passing through the nozzle hole may cause the fibers to be aligned in the axial direction. It does not fully rise, resulting in fibers with low orientation.
Even if this is made infusible or carbonized, only carbon fibers with low strength can be obtained. Therefore, the majority of methods for producing pitch-based high-performance carbon fibers that have been proposed include meso-7ASB as pitch for spinning.
チないかに製造するかという事に関するものである。It is related to how to manufacture products without any problems.
昭和４０年代には、熱処理により生成したメソフェーズ
は、キノリン、ピリジン等の極性溶剤に不溶であり、メ
ソフェーズとこれらの極性溶剤不溶分とはほぼ同一であ
ると考えられていた。しかし、その後のメソフェーズに
関する研究により、偏光顕微鏡下に異方性を示す部分が
必ずしも極性溶剤不溶分と同一ではなく、メソフェーズ
中には極性溶剤に可溶な成分と不溶な成分が存在するこ
とが認められている。従って最近、メン７エーズは「偏
光顕微鏡で観察した時に光学的に異方性を示す部分」と
して定義されるのが一般的であり、メソフェーズ含有量
も偏光顕微鏡で観察した際の光学的に異方性を示す部分
と等方性を示す部分との面積分率をもって表すことが一
般的である。In the 1960s, it was believed that mesophase produced by heat treatment was insoluble in polar solvents such as quinoline and pyridine, and that mesophase and the components insoluble in these polar solvents were almost the same. However, subsequent research on mesophase revealed that the part that shows anisotropy under a polarizing microscope is not necessarily the same as the part that is insoluble in polar solvents, and that there are components that are soluble and insoluble in polar solvents in mesophase. It recognized. Therefore, recently, men7Aze has been generally defined as "a part that shows optical anisotropy when observed with a polarizing microscope," and mesophase content has also been defined as a part that shows optical anisotropy when observed with a polarizing microscope. It is generally expressed by the area fraction of the part exhibiting anisotropy and the part exhibiting isotropy.
このメソフェーズ含有量は高性能炭素繊維を８遺しよう
とする時の紡糸性ならびに得られる炭素繊維の物性に大
きく影響するものである。This mesophase content greatly affects the spinnability and physical properties of the resulting carbon fiber when producing high-performance carbon fiber.
特開昭５４−５５６８５号くは本質的に１００％のメソ
フェーズを含むピッチについての記載があり、等方性部
分の存在が紡糸操作を妨害するため、極力等方性部分を
少な（することが望ましい旨の説明がなされている。そ
の理由は、メソフェーズ含有量が少ない場合溶融状態に
おいても、異方性を示すメソフェーズより等方性部分の
は５が粘度が低いため、これら二相のピッチが分離する
傾向にあるということである。JP-A No. 54-55685 describes a pitch containing essentially 100% mesophase, and since the presence of an isotropic portion interferes with the spinning operation, the isotropic portion should be kept as small as possible. The reason for this is that when the mesophase content is small, even in the molten state, the viscosity of the isotropic part 5 is lower than that of the anisotropic mesophase, so the pitch of these two phases is This means that they tend to separate.
しかし、メソフェーズ含有量を多くしようとすると、ピ
ッチの軟化点と粘度が著しく高くなり、紡糸が困難とな
る。メソフェーズピッチを用いた高性能炭素線維の製造
におい【最大の問題は、メソフェーズピッチの軟化点が
高いために紡糸温度を著しく高くしなければならないと
いうことである。紡糸温度を３５０℃以上の高温にしな
ければならない様なピッチの場合には、紡糸設備内での
ピッチの分解、変質あるいは熱重合が起り、糸切れ、繊
維強度の低下等の問題が発生する。紡糸温度はメトツー
法で測定される軟化点より２０〜４０℃高いのが一般的
であるので、紡糸温度を３５０℃以下にするためには、
メソフェーズピッチの軟化点を３２０℃以下にする事が
必要である。しかし、特開昭５４−５５６２５号の方法
は、ピッチを比較的低い温度で長時間熱処理する方法で
あり、その明細書中に示されている様に、得られるピッ
チの軟化点は３３０〜３５０℃とかなり高く、したがっ
て３５０℃以上という高い温度で紡糸を実施している。However, increasing the mesophase content significantly increases the softening point and viscosity of the pitch, making spinning difficult. The biggest problem in producing high-performance carbon fibers using mesophase pitch is that the spinning temperature must be significantly increased due to the high softening point of mesophase pitch. If the pitch requires a high spinning temperature of 350° C. or higher, the pitch may undergo decomposition, alteration, or thermal polymerization within the spinning equipment, resulting in problems such as yarn breakage and a decrease in fiber strength. Since the spinning temperature is generally 20 to 40°C higher than the softening point measured by the Metotsu method, in order to lower the spinning temperature to 350°C or less,
It is necessary to keep the softening point of mesophase pitch below 320°C. However, the method of JP-A-54-55625 heat-treats pitch at a relatively low temperature for a long time, and as shown in the specification, the softening point of the pitch obtained is 330 to 350. Therefore, spinning is carried out at a high temperature of 350°C or higher.
また、特開昭５８−１５４７９２号には、キノリン可溶
性メソフェーズについての記載があり、キノリンあるい
はピリジンく不溶なメソフェーズはピッチの軟化点を高
（するため、キノリンに可溶なメソフェーズを特定され
た景以上含有することが必要であると規定している。こ
こではキノリンに不溶なメソフェーズと可溶なメソフェ
ーズについて詳しく説明されていないが、著しく高分子
量化したものがキノリン不溶分となるであろう事は容易
に理解される事であり、キノリン可溶なメソフェーズを
多くしようとする試みは著しく高分子量化した成分の含
有量を少なくし、分子量分布の狭い均質なピッチを製造
しようとする試みでもある。この特開昭５８−１５４７
９２号の方法は特定の範囲の芳香族水素含有率のピッチ
を熱処理するというものであり、紡糸ピッチの４０％以
上がキノリンに可溶なメソフェーズであるが、キノリン
不溶分も多くやはり相当高い温度で紡糸な実施している
。In addition, JP-A-58-154792 describes a quinoline-soluble mesophase.Mesophases that are insoluble in quinoline or pyridine raise the softening point of pitch. It stipulates that it is necessary to contain above quinoline.Although there is no detailed explanation of mesophase that is insoluble in quinoline and mesophase that is soluble in quinoline, it is assumed that substances with significantly high molecular weight will become quinoline-insoluble. It is easy to understand that the attempt to increase the amount of quinoline-soluble mesophase is also an attempt to reduce the content of components with extremely high molecular weight and to produce a homogeneous pitch with a narrow molecular weight distribution. .This Japanese Patent Application Publication No. 58-1547
The method of No. 92 heat-treats pitch with aromatic hydrogen content in a specific range, and although more than 40% of the spinning pitch is mesophase that is soluble in quinoline, there is also a large amount of quinoline-insoluble content, which is heated at a considerably high temperature. Spinning is being carried out.
このキノリン不溶分のゐに注目して、これを減少させる
ことは、たとえば熱処理の条件をマイルドにする方法な
どにより容易に達成する事が可能である。しかし、この
場合にはメンフェーズ含有量が著しく減少すると同時に
キシレン等の溶剤に可溶な低分子量成分の含有量が多く
なる。このキシレン等の溶剤に可溶な低分子量成分は紡
糸時の配向を乱す原因となり、また紡糸温度において揮
発して糸切れの原因ともなる。Focusing on this quinoline insoluble content, reducing it can be easily achieved by, for example, making the heat treatment conditions milder. However, in this case, the content of menphase decreases significantly and at the same time the content of low molecular weight components soluble in solvents such as xylene increases. This low molecular weight component that is soluble in solvents such as xylene causes the orientation to be disturbed during spinning, and also causes volatilization at the spinning temperature, causing yarn breakage.
従って、良質な紡糸ピッチを得ようとする場合には、キ
ノリンに不溶な著しく高分子量化した成分を少なくする
ことのみでは十分ではなく、キシレン等に可溶な低分子
ｔｇ分の含有量をも減少させ、中間成分の多い均質なピ
ッチとすることが必要である。Therefore, when trying to obtain a high-quality spinning pitch, it is not enough to reduce the amount of extremely high molecular weight components that are insoluble in quinoline, but also to reduce the content of low molecular weight Tg that is soluble in xylene etc. It is necessary to reduce the pitch and obtain a homogeneous pitch with a large amount of intermediate components.
この様な均質なピッチを得るための方法は、前記以外に
も、たとえば、等方性ピッチを溶媒で抽出し、その不溶
分を２３０〜４００℃に加熱する方法（特開昭５４−１
６０４２７号）、等方性ピッチを水素供与性溶媒の存在
下に水素化した後、加熱処理する方法（％開昭５８−２
１４５３１号、特開昭５８−１９６２９２号）、等方性
ピッチを熱処理し生成したメソフェーズな分離除去して
得たピッチを再度熱処理する方法（特開昭５８−１３６
８３５号）、ピッチを熱処理しメソフェーズ含有量が２
０〜８０％とした後、メソフェーズを沈降し回収する方
法（ｑ！！開昭５７−１１９９８４号）など数多（提案
されている。しかし、これらの方法は、あるものはメソ
フェーズ含有量を高（することはできても軟化点を十分
低くすることができず、またあるものは軟化点は低くて
もメソ７ヱーズ含有量を高くすることができない。また
、あるものは軟化点を低く、メソフェーズ含有量を高く
することはできても、キノリン等に不溶の著しく高分子
量化したメソフェーズ量が多くなり必ずしも均質なピッ
チとは言えないなどの欠点な持つものであり、（１）軟
化点が低く、（２）メソフェーズ含有量が高（、（３）
キノリンネ溶成分が少なく、さらに（４）キシレン可溶
成分が少ないとい５．４つの特性を同時に満足するメソ
フェーズピッチを与えるものではない。In addition to the methods described above, methods for obtaining such a homogeneous pitch include, for example, a method of extracting isotropic pitch with a solvent and heating the insoluble content to 230 to 400°C (Japanese Patent Laid-Open No. 54-1
60427), a method in which isotropic pitch is hydrogenated in the presence of a hydrogen-donating solvent and then heat treated (%
14531, JP-A-58-196292), a method of heat-treating isotropic pitch, separating and removing the generated mesophase, and heat-treating the pitch again (JP-A-58-136).
No. 835), the pitch was heat-treated and the mesophase content was 2.
Many methods have been proposed, including the method of settling and recovering the mesophase after reducing the content to 0 to 80% (q!! 1984-119984). However, some of these methods require a high mesophase content. (Even if it is possible to do so, it is not possible to lower the softening point sufficiently, and some have a low softening point but cannot increase the meso7ase content.Also, some have a low softening point, Although it is possible to increase the mesophase content, there are disadvantages such as the amount of significantly high molecular weight mesophase that is insoluble in quinoline etc., and it cannot necessarily be said that the pitch is homogeneous. (1) The softening point is low. (2) high mesophase content (, (3)
It does not provide a mesophase pitch that simultaneously satisfies the following properties: 5.4 has a small amount of quinoline-soluble components and (4) a small amount of xylene-soluble components.
これらの問題を解決するための方法として、特開昭６１
−１３８７２１号には、コールタールピッチ又はそれを
加熱処理したものを溶剤抽出して不溶分を得、これを水
素化し、さらに熱処理することによりメソ７エーズビ、
チとする方法が開示されている。この方法で得られるピ
ッチはキノリン不溶分が２０％以下、メソフェーズ量が
９０％以上と均質なものであるが、それから得られた尿
素繊維の強度はその実施例にも示されているように、必
ずしも十分高いとは言えない。この方法の問題点は、出
発原料であるコールタール中に存在する溶剤不溶分が、
本来酸素繊維展進用の紡糸ピッチを製造する目的で調整
されたものではないということである。As a method to solve these problems,
No. 138721 discloses that coal tar pitch or its heat-treated product is extracted with a solvent to obtain insoluble matter, which is hydrogenated and further heat-treated to produce meso-7Azbil,
A method is disclosed. The pitch obtained by this method is homogeneous with a quinoline insoluble content of 20% or less and a mesophase content of 90% or more, but the strength of the urea fiber obtained from it is as shown in the examples. It cannot necessarily be said that it is high enough. The problem with this method is that the solvent-insoluble components present in the coal tar, which is the starting material,
This means that it was not originally prepared for the purpose of producing spinning pitch for oxygen fiber expansion.
従って、コールタール又はピッチから、もともと原料中
に存在した溶剤不溶分を取りだして使用する場合には、
その原料がどういう工程を経て製造された物であるかに
よって、得られる紡糸ピッチの性状もしくは炭素繊維の
特性が左右されることになる。Therefore, when extracting and using the solvent-insoluble matter originally present in the raw material from coal tar or pitch,
The properties of the resulting spinning pitch or the properties of the carbon fibers will depend on the process by which the raw material is manufactured.
戻素繊維夷造用紡糸ピッチを製造する場合。When producing spinning pitch for making recombinant fibers.
ピッチ自体が前記の４つの特性を満足していなければな
らない事に加えて、それから得られる炭素繊維の特性も
すぐれたものでなければならない。In addition to the pitch itself having to satisfy the above four properties, the properties of the carbon fiber obtained from it must also be excellent.
ピッチ等の歴青物を水素化した後、熱処理するという方
法は前記特開昭５８−２１４５３１号、特開昭５８−１
９６２９２号、特開昭６１−１３８７２１号の他にもい
（つかの提案がなされており、軟化点の低い紡糸ピッチ
を製造するうえで有効ではあるが、これらの方法におい
てもそのほとんどが水素化用の原料として市販のピッチ
等又はその中に含まれる溶剤不溶分をそのまま水素化原
料とすることを前提としている。すなわち、紡糸用ピッ
チ製造の為に特に調整されたものを水素化するのではな
いので、得られる紡糸ピッチの性状又は炭素繊維の特性
が原料性状に依存することはさけられない。従って、原
料性状の変動を十分に吸収し、安定した紡糸ピッチを製
造し得るプロセスの開発が望まれている。また、コール
タールピッチを熱処理し【溶剤不溶分を増加せしめる方
法を採用する場合には、もともとそのコールタールピッ
チに存在した溶剤不溶分はさらに加熱処理を受け、キノ
リンに不溶な成分等の好ましくない高重合物を生成する
。かかる好ましくない高重合物を含む熱処理物からの溶
剤不溶分を水素化原料とすると、該溶剤不溶分を水素化
した後に多量の固形物をろ過分離しなければならなくな
る。しかし、この水素化溶媒中の不溶分をろ過分離する
という操作は必ずしも効率的ではなく、ろ過速度が遅い
こと、ろ布が目づまりをおこし再利用ができないなど大
屋化する際の問題をはらんでいる。さらにかかる水素化
工程で多量の不溶分が生成する様な原料を用いる場合に
は、プロセスとして効率の良いたとえば管式加熱炉によ
る連続処理法等を採用することができず、効率の悪い一
ツチ式の処理法を取らざるを得ない。The method of hydrogenating bituminous materials such as pitch and then heat-treating them is described in the above-mentioned JP-A-58-214531 and JP-A-58-1.
In addition to No. 96292 and JP-A No. 61-138721, some proposals have been made, and although these methods are effective in producing spinning pitch with a low softening point, most of these methods are not suitable for hydrogenation. It is assumed that commercially available pitch or the solvent-insoluble matter contained therein is used as a raw material for hydrogenation as it is.In other words, it is not hydrogenated that has been specially prepared for the production of pitch for spinning. Therefore, it is inevitable that the properties of the resulting spinning pitch or the properties of the carbon fibers depend on the properties of the raw material.Therefore, it is desirable to develop a process that can sufficiently absorb fluctuations in the properties of the raw material and produce a stable spinning pitch. In addition, when heat-treating coal tar pitch to increase the solvent-insoluble content, the solvent-insoluble content originally present in the coal tar pitch is further heat-treated, and the quinoline-insoluble components are reduced. When the solvent-insoluble matter from the heat-treated product containing such undesirable high-polymers is used as a raw material for hydrogenation, a large amount of solid matter is filtered and separated after the solvent-insoluble matter is hydrogenated. However, this operation of filtering and separating the insoluble matter in the hydrogenation solvent is not necessarily efficient, and there are many problems when converting it into a large-scale factory, such as the filtration speed being slow and the filter cloth clogging, making it impossible to reuse it. Moreover, when using raw materials that generate a large amount of insoluble matter in such a hydrogenation process, it is not possible to adopt a more efficient process such as a continuous treatment method using a tube heating furnace. Therefore, we have no choice but to adopt the inefficient one-shot processing method.
さらに、コールタールピッチから溶剤不溶分を採取する
方法についても特開昭６１−１３８７２１号の本文中に
［５〜２０倍量の溶剤を使用して、煮沸下又はそれに近
い温度で３〜１２時間程度行なうことが好ましい。Ｊと
説明されている様に、必ずしも効率的な方法とは言えな
い。従って溶剤不溶分を原料とする場合には、その不溶
分の採取法についても十分考慮されなければならない。Furthermore, the text of JP-A-61-138721 also describes a method for collecting solvent-insoluble matter from coal tar pitch. It is preferable to do this to a certain extent. As explained by J, it is not necessarily an efficient method. Therefore, when using solvent-insoluble matter as a raw material, sufficient consideration must be given to the method for collecting the insoluble matter.
以上の様に、ピッチ系高性能Ｒｏｌｌ維用の紡糸ピッチ
を製造する方法において、紡糸用メソフェーズピッチ性
状に対する要求と炭素線維特性に対する要求を同時に満
足する方法の開発が望まれており、さらには、効率的か
つ安定的であり、大型化可能なプロセスの開発が望まれ
ている。As described above, it is desired to develop a method for producing spinning pitch for pitch-based high-performance Roll textiles that simultaneously satisfies the requirements for mesophase pitch properties for spinning and the requirements for carbon fiber properties. It is desired to develop a process that is efficient, stable, and can be scaled up.
（解決しよ５とする問題点）
本発明者らは、前記の様な数多くの要求を考慮したうえ
で、高性能炭素繊維を製造するためのメソフェーズピッ
チの製造方法について研究を重ね、出発原料に含まれる
単環の芳香族系炭化水素溶剤に不溶の成分、もしくは出
発原料を蒸留又は熱処理したときに容易に生成する単環
の芳香族系炭化水素溶剤に不溶の成分をあらかじめ除去
し、積属重質成分を得、これを特定の条件下に加熱処理
し、この加熱処理によっ【新たに生成した単環の芳香族
系炭化水素溶剤に不溶の成分を回収し、これを水素供与
性溶媒の存在下に加熱処理することにより水素化し、さ
らに減圧下又は不活性ガスの吹き込み下に熱処理して得
られるメソ７エーズビツチが前記４つの物性を同時に満
足するものであることを見いだし、かかるメソ７エーズ
ピ、チの調法を先に提案した（％願昭６１−１１４２２
１号）。すなわち、石炭系重質油又は石油系重質油から
得られるピッチ等の高分子量歴青物を、水素供与性溶媒
の存在下に加熱処理することにより水素化し、この水素
化された高分子量歴青物を減圧下又は不活性ガスの吹き
込み下に加熱処理するこしくはそれらを蒸留又は熱処理
して得られる重質成分に、単環の芳香族系炭化水素溶剤
の一定量を加え、生成する不溶性成分を遠心分離又はろ
過により分離、除去した後、加えた単環の芳香族系酸化
水素溶剤を蒸留により除去して精製された重質油又は重
質成分を得る工程と、この精製された重質油又は重質成
分を沸点範囲が２００〜４５０℃の間にあり、かつ管式
加熱炉における加熱処理に際し、実質的に単環の芳香族
系炭化水素溶剤に対する不溶分を生成しない芳香族系油
の０〜１倍量の存在下又は非存在下に、管式加熱炉にお
いて加圧下に一定の条件で加熱処理する工程と、この加
熱処理物に単環の芳香族系炭化水素溶剤の一定量を加え
、生成する不溶性成分を遠心分離又はろ過により回収す
る工程を経て得られる高分子量歴青物であることを特徴
とするメソフェーズピッチの製造方法を先に提案した。(Problems to be Solved 5) The present inventors have conducted repeated research on a method for producing mesophase pitch for producing high-performance carbon fibers, taking into consideration the many requirements described above, and have Components that are insoluble in monocyclic aromatic hydrocarbon solvents contained in or that are easily generated when the starting materials are distilled or heat treated are removed in advance, and the This heat treatment recovers the components insoluble in the newly generated monocyclic aromatic hydrocarbon solvent, and converts it into a hydrogen-donating compound. It has been found that meso-7A-Z-BIT, which is obtained by hydrogenation by heat treatment in the presence of a solvent and further heat treatment under reduced pressure or while blowing inert gas, satisfies the above four physical properties at the same time. He first proposed the preparation of 7 Azepi and Chi (% Gansho 61-11422)
No. 1). That is, a high molecular weight bituminous material such as pitch obtained from coal-based heavy oil or petroleum-based heavy oil is hydrogenated by heat treatment in the presence of a hydrogen-donating solvent, and this hydrogenated high molecular weight bituminous material is produced. Insoluble components are produced by adding a certain amount of a monocyclic aromatic hydrocarbon solvent to the heavy components obtained by heat-treating them under reduced pressure or blowing inert gas, or by distilling or heat-treating them. A step of separating and removing the added monocyclic aromatic hydrogen oxide solvent by centrifugation or filtration, and then removing the added monocyclic aromatic hydrogen oxide solvent by distillation to obtain purified heavy oil or heavy components; An aromatic oil whose boiling point range is between 200 and 450°C and which does not substantially produce insoluble matter in a monocyclic aromatic hydrocarbon solvent when heated in a tube heating furnace. A process of heat-treating under pressure in a tube heating furnace under certain conditions in the presence or absence of 0 to 1 times the amount of We have previously proposed a method for producing mesophase pitch, which is a high-molecular-weight bituminous material obtained through a step of adding the above-mentioned mesophase pitch and recovering the resulting insoluble components by centrifugation or filtration.
この方法によれば軟化点が低（極めて均質な紡糸ピッチ
を得ることができた。According to this method, it was possible to obtain a spinning pitch with a low softening point (extremely uniform spinning pitch).
しかし、この方法では、精製された重質油又は重質成分
を特定の条件下で加熱処理することによって、キノリン
不溶分を実質的に生成させることなく新しく単環の芳香
族系炭化水素溶剤に不溶の成分を生成させなければなら
ないため、加熱処理物中の不溶性成分の含有量をむやみ
に高くすることはできず、従って紡糸ピッチの収率も限
られたものとなる。However, in this method, refined heavy oil or heavy components are heat-treated under specific conditions to create a new monocyclic aromatic hydrocarbon solvent without substantially producing quinoline-insoluble components. Since insoluble components must be generated, the content of insoluble components in the heat-treated product cannot be increased unnecessarily, and the yield of spinning pitch is therefore limited.
本発明者らは、この様な問題を解決し、さらに効率の良
いプロセスとするため、さきに提案した方法について引
き続き鋭意研究を重ねた結果、特定の条件で加熱処理し
て生成した不溶性成分を除去した清澄液から溶剤を除去
して得られる可溶性成分を再度同一の条件で加熱処理す
ることにより、新たにかなりの不溶性成分を生成させる
ことができ、またこの不溶性成分な用いてメソフェーズ
ピッチを調整し、ＲＲ線繊維製造した場合にはさらにす
ぐれた物性の炭素繊維が得られることを見いだし本発明
に至った。In order to solve these problems and make the process even more efficient, the inventors of the present invention continued to conduct intensive research on the method proposed earlier, and as a result, the insoluble components produced by heat treatment under specific conditions were By heat-treating the soluble components obtained by removing the solvent from the removed clear liquid under the same conditions again, it is possible to generate a considerable amount of new insoluble components, and this insoluble component can be used to adjust mesophase pitch. However, it was discovered that carbon fibers with even better physical properties can be obtained when RR wire fibers are produced, leading to the present invention.
従りて本発明の目的はピッチ系高性能炭素繊維を製造す
るために用いられるメソフェーズピッチの展進法を与え
るものであり、メトツー法で測定される軟化点が３１０
℃以下、偏光顕微鏡で観察したときの光学的異方性を示
す部分の面積公事によるメソフェーズ含有量が９０％以
上、キノリン不溶分が１０重量％以下、キシレン可溶分
が１０重量％以下という％性を同時に満足する物に均質
なメソフェーズピッチを製造する方法を与えるものであ
る。本発明の方法で得られるメソフェーズピッチを用い
て炭素繊維を夷遺した場合、容易Ｋ１００Ｏ℃における
強度が３００に９／−以上、黒鉛化したときの強度４０
０す／−以上、弾性率６０ ｔｏｎ／−以上の高弾性率
を持つ高性能炭素繊維が得られる。Therefore, the object of the present invention is to provide a method for developing mesophase pitch used for manufacturing pitch-based high-performance carbon fibers, which has a softening point of 310 as measured by the mesophase method.
℃ or less, the area of the part showing optical anisotropy when observed with a polarizing microscope.Mesophase content according to Koji is 90% or more, quinoline insoluble content is 10% by weight or less, and xylene soluble content is 10% by weight or less. The present invention provides a method for producing homogeneous mesophase pitch that satisfies the following properties at the same time. When carbon fibers are made using the mesophase pitch obtained by the method of the present invention, the strength at 100°C is easily 300:9/- or more, and the strength when graphitized is 40%.
A high-performance carbon fiber having a high elastic modulus of 60 tons/- or more can be obtained.
また、本発明の別の目的は精製重質成分から得られるメ
ソフェーズピッチの収率な著しく向上させること、およ
び該収率向上の為の操作を連続的に実施し得る方法を与
えることにある。Another object of the present invention is to significantly improve the yield of mesophase pitch obtained from purified heavy components, and to provide a method in which operations for improving the yield can be carried out continuously.
本発明によればプロセス全体の効率ひいては経済性を著
しく向上させることができる。According to the present invention, the efficiency and economic efficiency of the entire process can be significantly improved.
さらに本発明の別の目的は、紡糸ピッチに含まれてはな
らないコークス状固形物の生成をメソフェーズピッチ製
造の全工程において防止することにより、これらコーク
ス状固形物を除去するという困難な操作を排除すること
にある。Yet another object of the present invention is to prevent the formation of coke-like solids, which should not be included in the spinning pitch, in the entire process of mesophase pitch production, thereby eliminating the difficult operation of removing these coke-like solids. It's about doing.
本発明によればすべての工程を連続化することも可能と
なり、極めて効率の良いプロセスを構成することができ
る。According to the present invention, it is also possible to make all steps continuous, and an extremely efficient process can be constructed.
また、さらに本発明の別の目的は、出発原嬉として用い
る重質油の性状変化を吸収し得るフレキシビリティ−の
あるプロセスを与えることにあり、換言すれば原料性状
の変化に左右されず、安定した性状のメソ７エーズピ、
チを与えることにある。Furthermore, another object of the present invention is to provide a flexible process capable of absorbing changes in the properties of heavy oil used as a starting raw material; in other words, it is not affected by changes in the properties of the raw material; Meso7Asp with stable properties,
The goal is to give the best.
そして、本発明の方法で得られる水素化ピッチならびに
メソフェーズピッチは炭素繊ｔｌａｍ造用としてのみな
らず、その他の炭素製品用の素原料として用いることが
できることは言うまでもない。It goes without saying that the hydrogenated pitch and mesophase pitch obtained by the method of the present invention can be used not only for making carbon fiber tlam, but also as raw materials for other carbon products.
（問題点を解決するための手段）
本発明の要旨は、石炭系重質油、石油系重質油もしくは
それらを蒸留、熱処理又は水素化処理して得られる重質
成分であって、実質的に単環の芳香族系炭化水素溶剤に
不溶の成分を含まないものであるか、もしくは上記重質
油又は重質成分に単環の芳香族系炭化水素溶剤またはこ
れと同等の溶解性を持つ溶剤の該重質油又は重質成分に
対して１〜５重量倍量を加えたときに生成する不溶性成
分を分離除去した後に、溶剤を蒸留除去して得られる精
製された重質油又は重質成分を原料とし、該原料を沸膚
範囲が２００〜３５０℃の間にあり、かつ管式加熱炉に
おける加熱処理に際し、実質的に単環の゛芳香族系炭化
水素溶剤に不溶の成分を生成しない芳香族系を記原料に
対して１重量倍量以下の存在下又は非存在下に管式加熱
炉において加圧下に温度４００〜６００℃の条件で加熱
処理して、実質的にキノリン不溶分を生成させることな
く、キシレン不溶分を加熱処理物中に３〜３０重量％生
成させる連続的な第１工程と、第１工程で得られた加熱
処理物を３５０℃以下の温度で蒸留又はブラッシングし
て、軽質成分の一部を除き、熱分解重質成分を得る連続
的な第２工程と、該熱分解重質成分に単環の芳香族系炭
化水素溶剤又はこれと同等の溶解性を持つ溶剤を該熱分
解重質成分に対して１〜５重量倍量加え、生成する不溶
性成分を分離回収して高分子量歴青物を得る連続的な第
３工程と、第３工程で不溶分を除去した清澄液から溶剤
を蒸留除去して単環の芳香族系炭化水素溶剤に可溶の成
分を得る連続的な第４工程とから成る水素化用原料調整
工程において、第４工程で得られる可溶性成分の全部又
は一部を＠１工程に循環しながら第１〜第４工程を連続
的に実施することにより、第３工程から高分子量歴青物
を得、該高分子量歴青物を水素供与性溶媒の存在下に加
熱処理することにより水素化した後、溶媒を除去して実
質的に等方性の水素化ピッチを得、これをさらに加勢処
理することによりメソフェーズピッチとすることを特徴
とする高性能炭素繊維製造用メソフェーズピッチの製造
方法に存する。(Means for Solving the Problems) The gist of the present invention is to provide coal-based heavy oil, petroleum-based heavy oil, or heavy components obtained by distilling, heat-treating, or hydrotreating them, which are substantially does not contain components that are insoluble in monocyclic aromatic hydrocarbon solvents, or has a monocyclic aromatic hydrocarbon solvent or equivalent solubility in the above heavy oil or heavy components. Refined heavy oil or heavy oil obtained by separating and removing insoluble components produced when 1 to 5 times the weight of the heavy oil or heavy components of the solvent is added, and then removing the solvent by distillation. The boiling range of the raw material is between 200 and 350°C, and during heat treatment in a tube heating furnace, substantially monocyclic aromatic hydrocarbon components insoluble in the solvent are removed. The unproduced aromatic system is heated in a tube heating furnace under pressure at a temperature of 400 to 600°C in the presence or absence of not more than 1 times the weight of the raw material to make it substantially insoluble in quinoline. A continuous first step in which 3 to 30% by weight of xylene-insoluble matter is produced in the heat-treated product without producing any fraction, and the heat-treated product obtained in the first step is distilled or A continuous second step of brushing to remove a part of the light components to obtain a pyrolyzed heavy component, and a monocyclic aromatic hydrocarbon solvent or an equivalent solubility for the pyrolyzed heavy component. 1 to 5 times the weight of the pyrolyzed heavy components, and the resulting insoluble components are separated and recovered to obtain a high molecular weight bituminous material. In the raw material preparation step for hydrogenation, which consists of a continuous fourth step in which the solvent is removed by distillation from the clarified liquid from which the By continuously carrying out the first to fourth steps while circulating all or part of the soluble components @1 step, a high molecular weight bituminous material is obtained from the third step, and the high molecular weight bituminous material is hydrogen-donating. After hydrogenation by heat treatment in the presence of a neutral solvent, the solvent is removed to obtain a substantially isotropic hydrogenated pitch, which is further subjected to force treatment to obtain a mesophase pitch. The present invention relates to a method for producing mesophase pitch for producing high-performance carbon fiber.
本発明において原料として用いる石炭系重質油トは、コ
ールタール、コールタールピッチ、石炭液化油等であり
、石油系重質油とはナフサ分解において副生ずる分解残
油（ナフサタール）、ガスオイル分解において副生する
分解残油（パイロリシスタール）、石油留分の流動接触
分解において副生する分解残油（デカント油）等であり
、また、これらの重質油等に蒸留、熱処理および水素化
処理等の操作を加えて得られるもの、あるいはこれらの
混合物をも使用することができる（以下重質油等と言う
。）。The coal-based heavy oils used as raw materials in the present invention include coal tar, coal tar pitch, coal liquefied oil, etc. Petroleum-based heavy oils include cracked residual oil (naphthatar) produced as a by-product in naphtha cracking, gas oil cracked oil, etc. cracked residual oil (pyrolysis tar) produced as a by-product in fluid catalytic cracking of petroleum fractions, and cracked residual oil (decant oil) produced as a by-produced in fluid catalytic cracking of petroleum fractions. It is also possible to use those obtained by additional operations such as processing, or mixtures thereof (hereinafter referred to as heavy oil etc.).
この重質油等の若干の例について物性例を示せば第１表
のとおりである。Table 1 shows physical properties of some examples of this heavy oil.
また、本発明で言う単環の芳香族系炭化水素溶剤とは、
ベンゼン、トルエン、キシレン等であり、これらを混合
して用いることもできる。Furthermore, the monocyclic aromatic hydrocarbon solvent referred to in the present invention is
These include benzene, toluene, xylene, etc., and a mixture of these can also be used.
これらは勿論純品である必要はなく、実質的にこれらか
らなるものであればよい。また、本発明の方法において
原料重質油等からの不溶分の除去、もしくは管式加熱炉
において新たに生成した不溶性成分の分離回収に用いら
れる溶剤は必スしもこのベンゼン、トルエン、キシレン
等でな（ても良く、ｎ−ヘキサン、ｎ−へブタン、アセ
トン、メチルエチルケトン、メタノール、エタノール、
灯油、軽油、ナフサ等に代表される様な溶解性の低い貧
溶剤と、キノリン、ピリジン、タール軽油、洗浄油、カ
ルボニル油、アントラセン油、もしくは重質油を蒸留し
て得られる芳香族系の軽質油等に代表される様な溶解性
の高い良溶剤とを適当な比率で混合して上記ベンゼン、
トルエン、キシレン等ト同等の溶解性を持つ溶剤とした
ものを用いることもできる。Of course, these do not need to be pure products, and may be made essentially of these. In addition, in the method of the present invention, the solvent used to remove insoluble components from raw material heavy oil, etc., or to separate and recover insoluble components newly generated in a tube heating furnace, is necessarily benzene, toluene, xylene, etc. (Optional, n-hexane, n-hebutane, acetone, methyl ethyl ketone, methanol, ethanol,
Aromatic compounds obtained by distilling poor solvents with low solubility, such as kerosene, light oil, naphtha, etc., and quinoline, pyridine, tar light oil, cleaning oil, carbonyl oil, anthracene oil, or heavy oil. The above benzene,
A solvent having a solubility equivalent to that of toluene or xylene may also be used.
しかし溶剤の回収工程を簡略化するためにはベンゼン、
トルエン、キシレン等の様にできるだけ単純な組成の溶
剤を用いることが好ましい。However, in order to simplify the solvent recovery process, benzene,
It is preferable to use a solvent with the simplest possible composition, such as toluene, xylene, etc.
上記貧溶剤と良溶剤の組合せによる溶剤もその溶解性が
同等であるという点においてベンゼン、トルエン、キシ
レン等の単環の芳香族系炭化水素溶剤の均等物とみなし
うる。以下本発明の明細書においては単環の芳香族系炭
化水素溶剤を、上記組合せ溶剤も含めて、単にＢＴＸ溶
剤と略称する。The combination of the poor solvent and the good solvent described above can be considered equivalent to monocyclic aromatic hydrocarbon solvents such as benzene, toluene, and xylene in that their solubility is the same. Hereinafter, in the specification of the present invention, monocyclic aromatic hydrocarbon solvents, including the above-mentioned combination solvents, will be simply referred to as BTX solvents.
本発明の第１工程である管式加熱炉における加熱処理に
フィードする原料は、該原料に対して１〜５重量倍量の
ＢＴＸ溶剤に混合したときに不溶な成分を実質的に生成
しないものである必要がある。コールタールを例にとっ
て説明すると、コールタールは石炭を高温で乾留する際
に副生ずる重質油であるため、一般にフリーカーボンと
呼ばれる非常に微細なすす状炭素を含んでいる。このフ
リーカーボンは重質油等を加熱処理する際にメソフェー
ズの成長を阻害することが知られており、また本来キノ
リンに不溶な固体であるためメソフェーズピッチ中に存
在すると紡糸時の糸切れの原因となる。また、コールタ
ールはＢＴＸ溶剤に不溶な高分子量成分を含んでおり、
これは加熱処理の際に容易にキノリン不溶分となる。ま
た、このコールタール中のＢＴＸ溶剤不溶分は、コール
タールの製造条件等によってその量、質ともに変るもの
であり、本来酸素繊維用の素原料とするべ（調整された
ものではないので、これを抽出して紡糸ピッチの前駆物
質として用いるとコールタールの性状変動が得られる紡
糸ピッチの性状さらには炭素繊維の特性にまで影響する
ことになる。従って原料の重質油等からフリーカーボン
やＢＴＸ溶剤に不溶な成分を除去してお（ことは、第１
工程の管式加熱炉における加熱に際し、コークス状固形
物の生成による管の閉塞を防ぐ上で重要であるばかりで
なく、最終的に得られるメン７エーズビツチ中のキノリ
ン不溶分を減少させ安定した性状の紡糸ピッチを製造す
るうえで重要である。The raw material to be fed to the heat treatment in the tube heating furnace, which is the first step of the present invention, does not substantially generate insoluble components when mixed with BTX solvent in an amount of 1 to 5 times the weight of the raw material. It must be. Taking coal tar as an example, coal tar is a heavy oil that is produced as a by-product when coal is carbonized at high temperatures, and therefore contains very fine sooty carbon, which is generally called free carbon. This free carbon is known to inhibit the growth of mesophase when heat treating heavy oil, etc., and since it is a solid insoluble in quinoline, its presence in mesophase pitch causes yarn breakage during spinning. becomes. In addition, coal tar contains high molecular weight components that are insoluble in BTX solvents.
This easily becomes quinoline-insoluble during heat treatment. In addition, the amount and quality of the BTX solvent-insoluble content in this coal tar changes depending on the coal tar manufacturing conditions, etc., and it should be used as the raw material for oxygen fibers (as it is not adjusted). If coal tar is extracted and used as a precursor for spinning pitch, the properties of coal tar will change, which will affect the properties of the spinning pitch and even the properties of carbon fibers. Remove components that are insoluble in the solvent (this is the first step)
During heating in the tubular heating furnace during the process, it is important not only to prevent tube clogging due to the formation of coke-like solids, but also to reduce the quinoline insoluble content in the final product, resulting in stable properties. This is important in producing the spinning pitch of .
上記の原料の重質油等からのＢＴＸ溶剤による不溶分の
除去は、もし原料の重質油等がＢＴＸ溶剤に不溶性の成
分を含んでいないか、もしくはほとんど含んでいない場
合には省略することができる。たとえばナフサクールの
ごとき石油系重質油は一般的にＢＴＸ溶剤にすべて可溶
性の成分からなり、また石炭系の重質油であっても何等
かの理由によってそれがＢＴＸ溶剤に不溶の成分を含ん
でいないか、またはほとんど含Ａ、でいない場合には上
記の精製処理を省略することができる。、なぜならば、
上記の精製処理を行なってもそれによって除去される不
良成分が存在しないため、実質的な効果かえられないた
めである。この様にＢＴＸ溶剤に不溶の成分を含まない
か、もしくはほとんど含まない重質油等は不溶分除去の
処理を潜在的に受けたものとみなし得るので、これも精
製重質成分の定義内にする。上記の場合精製工程を省略
できるとは言うもののより均質な高品質のメソ７エーズ
ビ、チな得ようとする場合には、原料の重質油等をあら
かじめ熱処理し、ＢＴＸ溶剤に不溶な成分を原料に対し
て１０％以下生成させこれを分離除去することは好まし
いことである。この熱処理の方法は、オートクレーブに
よる熱処理の様なバッチ式でも、管式加熱炉による熱処
理の様な連続式でも良いが、ＢＴＸ溶剤により不溶分と
して除去される量が多くなりすぎると、最軒的に得られ
るメソフェーズピッチの収率低下をまねくため効率が悪
くなる。The above-mentioned removal of insoluble components from the raw material heavy oil, etc. using a BTX solvent should be omitted if the raw material heavy oil, etc. does not contain or contains almost no component insoluble in the BTX solvent. Can be done. For example, petroleum-based heavy oils such as naphtha cool generally consist of all components that are soluble in BTX solvents, and even coal-based heavy oils may contain components that are insoluble in BTX solvents for some reason. If it does not contain A or almost no A, the above purification treatment can be omitted. ,because,
This is because even if the above-mentioned purification treatment is performed, there are no defective components to be removed by the purification treatment, so that no substantial effect can be obtained. In this way, heavy oils that contain no or almost no components that are insoluble in BTX solvents can be considered to have potentially undergone treatment to remove insoluble components, so they are also included within the definition of refined heavy components. do. Although the refining process can be omitted in the above case, if you want to obtain a more homogeneous and high quality meso-7A, the raw material heavy oil etc. should be heat treated in advance to remove the components insoluble in the BTX solvent. It is preferable to generate 10% or less of the raw material and separate and remove it. This heat treatment method may be a batch method such as heat treatment using an autoclave or a continuous method such as heat treatment using a tube heating furnace, but if the amount removed as insoluble matter by the BTX solvent becomes too large, This leads to a decrease in the yield of mesophase pitch obtained, resulting in poor efficiency.
たとえば、比重１．０７５１、キシレン不溶分Ｏｗｔ％
のナフサタールを、内径６１１１１．長さ４０ｍのヒー
ターチューブを溶融塩浴中に浸漬した構造の管式加熱炉
において、圧力２０に９／ｄＧ、原料送入量１７．５
ｋｌｌ／ ｈｒとじ【加熱処理する場合、温度を４４０
〜５００℃と変化させて得られる加熱処理物中のキシレ
ン不溶分を測定すると、処理温度４４０，４６０，４８
０，４９０゜および５００℃についてそれぞれキシレン
不溶分は０．２．１．２．４．０．８．１および２７．
６ｗｔ％であった。したがって、上記の様な管式加熱炉
を用いる連続式加熱処理の場合は、温度４６０〜４９０
℃で加熱処理してキシレン不溶分を生成させ、これを除
去することが好ましい。また、同じナフサタールをオー
トクレーブを用いて、バッチ式で加熱処理する場合、オ
ートクレーブの圧力を１５に９／ｃｉＩＧ 、処理時間
を２時間として、処理温度を４００〜４４０℃と変化さ
せて、得られる加熱処理物中のキシレン不溶分を測定す
ると、温度４００．４１０．４２０．４３０および４４
０℃について、それぞれキシレン不溶分は０．３．１．
５．３．１．６．８および１３．５ｗｔ％であった。し
たがって上記の様なバッチ式加熱処理の場合は温度４１
０〜４３０℃で加熱処理して、キシレン不溶分を生成さ
せ、これを除去することが好ましい。この様に、同じす
７サタールでありても、その加熱処理を管式加熱炉にお
いて連続的に実施する場合と、オートクレーブの様なバ
ッチ式で実施する場合の温度等の条件は異なるので、用
いる方法によってその処理条件を求めることが望ましい
。For example, specific gravity 1.0751, xylene insoluble content Owt%
of naphsatal with an inner diameter of 61111. In a tube heating furnace with a structure in which a 40 m long heater tube is immersed in a molten salt bath, the pressure is 20 to 9/dG, and the feed rate of raw materials is 17.5.
kll/hr binding [When heat-treated, the temperature should be set to 440℃.
When measuring the xylene insoluble matter in the heat-treated product obtained by changing the temperature to ~500℃, the treatment temperature was 440, 460, 48℃.
The xylene insolubles at 0,490° and 500°C are 0.2.1.2.4.0.8.1 and 27.0, respectively.
It was 6wt%. Therefore, in the case of continuous heat treatment using a tube heating furnace as described above, the temperature is 460 to 490.
It is preferable to perform heat treatment at °C to generate xylene-insoluble matter and remove this. In addition, when the same naphsatal is heat-treated in a batch process using an autoclave, the pressure of the autoclave is set to 15 to 9/ciIG, the processing time is set to 2 hours, and the processing temperature is varied from 400 to 440°C. When measuring the xylene insoluble matter in the treated material, the temperature was 400.410.420.430 and 44.
At 0°C, the xylene insoluble content is 0.3.1.
5.3.1.6.8 and 13.5 wt%. Therefore, in the case of batch heat treatment as described above, the temperature is 41
It is preferable to perform a heat treatment at 0 to 430° C. to generate xylene-insoluble matter and remove this. In this way, even if the same Su7 satal is used, the conditions such as temperature are different when the heat treatment is carried out continuously in a tube heating furnace and when it is carried out in a batch process such as an autoclave. It is desirable to determine the processing conditions depending on the method.
また、前記の例のうち、加熱処理を管式加熱炉で実施し
た場合部３！温度５００℃で得られた加熱処理物中には
キノリン不溶分はほとんど存在しなかったが、加熱処理
をオートクレーブによるバッチ式で温度４４０℃、処理
時間２時間の条件で行なりたものの場合、加熱処理物中
のキシレン不溶分が１３．５ｗｔ％と、管式加熱炉の場
合より少ないにもかかわらず、すでにキノリン不溶分が
１．３ｗｔ％生成していた。この結果からも明らかな様
に１重質油を加熱処理する場合には、その加熱処理の方
法についても十分考慮しなければならず、キノリン不溶
分の様に過度に熱重合した高分子量歴青物の生成をさけ
ようとする場合には、管式加熱炉による連続的な処理を
することが好ましい。In addition, among the above examples, part 3 is the case where the heat treatment is performed in a tube heating furnace! There was almost no quinoline insoluble matter in the heat-treated product obtained at a temperature of 500°C, but when the heat treatment was performed in a batch manner using an autoclave at a temperature of 440°C and a treatment time of 2 hours, the heating Although the xylene insoluble matter in the treated material was 13.5 wt%, which was less than in the case of the tube heating furnace, 1.3 wt% of quinoline insoluble matter had already been produced. As is clear from this result, when heat-treating heavy oil, sufficient consideration must be given to the heat treatment method. In order to avoid the formation of , it is preferable to carry out continuous treatment using a tube heating furnace.
不溶分の分ｉｗＫ用いられるＢＴＸ溶剤の量は、処理し
ようとする重質油等の景に対して１〜５重量倍量が適当
である。溶剤量が少ないと、混合液の粘度が高くなり不
溶分の分離効率が悪くなる。逆に溶剤量な多くすると処
理量の増大をまねき不経済である。通常ＢＴＸ溶剤の使
用量は重質油等に対して１〜３重量倍量が好ましい。The appropriate amount of BTX solvent to be used for insoluble matter is 1 to 5 times the weight of the heavy oil to be treated. If the amount of solvent is small, the viscosity of the mixed liquid will increase and the efficiency of separating insoluble matter will deteriorate. On the other hand, increasing the amount of solvent increases the throughput and is uneconomical. Usually, the amount of BTX solvent used is preferably 1 to 3 times the weight of heavy oil.
また、重質油等にＢＴＸ溶剤を１〜５重量倍量加えた時
に生成する不溶分量と、物性のパラメーターとしての溶
剤不溶分量を測定する際の様に数十重量倍量以上の多量
の溶剤を加えた時に生成する不溶分量とは必ずしも同じ
ではなく、溶剤量が少ない時には生成する不溶分量も少
なくなる。従りて、溶剤量な１〜５重量倍量として不溶
分を生成させこれを除去して得られる精製重質成分を、
数十重量倍量以上の溶剤を用いて分析すると少量の不溶
分が検出されることがある。しかしこの不溶分の存在は
、本発明方法の実施には支障がない。In addition, when measuring the amount of insoluble matter produced when adding 1 to 5 times the weight of BTX solvent to heavy oil, etc., and the amount of solvent insoluble matter as a parameter of physical properties, a large amount of solvent of several tens of times the weight or more is measured. The amount of insoluble matter produced when the solvent is added is not necessarily the same as the amount of insoluble matter produced when the amount of solvent is small. Therefore, the purified heavy component obtained by generating insoluble matter and removing it in 1 to 5 times the amount by weight of the solvent,
A small amount of insoluble matter may be detected when an analysis is performed using several tens of times the weight of the solvent or more. However, the presence of this insoluble matter does not pose a problem in carrying out the method of the present invention.
不溶分の分離方法は遠心分離あるいはろ過等任意の分離
方法で良いが、フリーカーボン、触媒、不純物等の微細
な固形物を含むものの場合には、それら固形物を完全に
除去することが必要であるためろ過の方法を取ることが
好ましい。Any separation method such as centrifugation or filtration may be used to separate the insoluble matter, but if it contains fine solids such as free carbon, catalysts, and impurities, it is necessary to completely remove these solids. Therefore, it is preferable to use a filtration method.
この様にして不溶分を除去した清澄液からＢＴＸ溶剤を
蒸留除去して精製重質成分が得られる。The BTX solvent is removed by distillation from the clarified liquid from which insoluble matter has been removed in this way, and purified heavy components are obtained.
本発明の方法に用いられる精製重質成分に要求される別
の望ましい物性は、沸点が２００〜３５０″Ｃにある軽
質成分を少なくとも１００重量以上、好ましくは２０重
量％以上含み、かつ１００℃における粘度が１０００セ
ンチストークス以下であるということである。ＢＴＸ溶
剤に不溶の成分を含まないものであっても、沸点３５０
℃以下の軽質成分を全く含まないものの場合、その溶融
温度が著しく高くなるため、第１工程へその原料を送入
するためのポンプ等の設備を高温にしなければならない
という不都合が生じるうえ、軽質成分が存在しない状態
で加熱処理した場合には熱重合速度が速くなり、好まし
くないコークス状固形物を生成しやす（なる。軽質成分
の存在が熱重合速度に影響するということは、特開昭５
９−８２４１７号、米国咎許第４，５２２，７０１号に
も説明されている様に、すでに知られていることである
。一般に入手可能なコールタール、ナフサタール、パイ
ロリシスタールおよびデカント油はこの特性を満足する
ものであるが、これら重質油に蒸留、熱処理または水素
化処理等の操作を加えたものを用いる場合には、上記特
性の範囲から大きく逸脱しない重質成分を得ることが望
まれる。しかし、ＢＴＸ溶剤に不溶の成分は全く含まな
いが上記特性の範囲からはずれたものの場合には沸点範
囲が２００〜３５０℃の間にある芳香族系油で希釈して
用いることもできる。また、重質油等が沸点２００℃以
下の軽質成分を多量に含むものである場合には、後記第
１工程の管式加熱炉での加熱処理における蒸気圧が高く
なり、処理圧力を高くしなければならないので不利であ
る。Another desirable physical property required of the purified heavy component used in the method of the present invention is that it contains at least 100% by weight or more, preferably 20% by weight or more, of light components having a boiling point of 200 to 350"C, and This means that the viscosity is 1000 centistokes or less.Even if the BTX solvent does not contain insoluble components, the boiling point is 350 centistokes or less.
If the material does not contain any light components below ℃, its melting temperature will be extremely high, which will cause the inconvenience of having to raise the temperature of equipment such as pumps to feed the raw material to the first step. If heat treatment is carried out in the absence of light components, the rate of thermal polymerization will increase, and undesirable coke-like solids will be likely to be formed.The fact that the presence of light components affects the rate of thermal polymerization has been reported 5
This is already known, as explained in U.S. Pat. No. 9-82417 and U.S. Patent No. 4,522,701. Generally available coal tar, naphsatal, pyrolysis tar, and decant oil satisfy these characteristics, but when using these heavy oils that have been subjected to operations such as distillation, heat treatment, or hydrogenation treatment, , it is desirable to obtain a heavy component that does not deviate significantly from the above-mentioned range of properties. However, in the case of a BTX solvent that does not contain any components insoluble in the solvent but whose characteristics are outside the above range, it can be diluted with an aromatic oil having a boiling point range of 200 to 350°C. In addition, if heavy oil etc. contains a large amount of light components with a boiling point of 200°C or less, the steam pressure during the heat treatment in the tube heating furnace in the first step described below will be high, and the treatment pressure must be increased. This is disadvantageous because it does not.
次に本発明の方法について詳細に説明すると、第１工程
は、上記精製重質成分を管式加熱炉において加熱処理し
新たにキシレン不溶分を加熱処理物中に３〜３０重量％
生成せしめる工程である。この第１工程の加熱処理は加
圧下に温度４００〜６００℃で実施される。このとき、
管式加熱炉の出口において温度４００〜６００℃、圧力
１〜１００に９／ｄＧの範囲とすることが好ましく、ま
た温度４５０〜５５０℃、圧力２〜５０ｋＩＩ／ｃｒｌ
Ｇの範囲とすることが籍に好ましい。Next, to explain the method of the present invention in detail, the first step is to heat-treat the purified heavy components in a tube heating furnace to add 3 to 30% by weight of xylene-insoluble matter to the heat-treated product.
This is the process of generating it. The heat treatment in this first step is carried out at a temperature of 400 to 600° C. under pressure. At this time,
At the outlet of the tube heating furnace, the temperature is preferably 400 to 600°C and the pressure is 1 to 100 to 9/dG, and the temperature is 450 to 550°C and the pressure is 2 to 50 kII/crl.
It is preferable to set it in the range of G.
また、この加熱処理の際には沸点範囲が２００〜３５０
℃の間にあり、かつ管式加熱炉における加熱処理に際し
実質的にＢＴＸ溶剤に不溶な成分を生成しない芳香族系
油を共存させることが好ましい。ここで言う芳香族系油
とは、原料として用いる重質油等を蒸留して得られる沸
点範囲が２００〜３５０℃の間にあるものであり、たと
えばコールタールの２４０〜２８０℃の留分である洗浄
油（吸収油とも言う。）、２８０〜３５０℃の留分であ
るアント２セン油あるいは石油系重質油の上記沸点範囲
の芳香族系油等である。プロセスの経済性を考えると、
異種原料から得られる芳香族系油を用いるよりも、メソ
フェーズピッチを製造しようとするその原料重質油から
得られる芳香族系油な用いることが好ましいことは言う
までもない。この芳香族系油を共存させることにより、
管式加熱炉内での過度の熱重合を防ぎ精製重質成分に十
分な熱分解を起させるだけの滞留時間を与えることがで
きると同時に、コークス生成による管の閉塞を防ぐこと
ができる。従っ【、使用する芳香族系油自体が管式加熱
炉で著しく熱重合する様なものは、かえって管の閉塞を
促進することになるため不都合であり、沸点の高い成分
を多量に含むものは使用出来ない。また、沸点が２００
℃より低い成分を多量に含むものは、管式加熱炉でこれ
を液状に保ったための圧力が著しく高くなり不利である
。また、上記目的のために使用する芳香族系油の量は精
製重質成分に対し１重量倍量以下で良い。また、精製重
質成分が上記沸点範囲の芳香族系油な十分に含んでいる
ものの場合には、新しく芳香族系油な添加もしくは追加
しなくても良い。In addition, during this heat treatment, the boiling point range is 200 to 350.
It is preferable to coexist with an aromatic oil which is between 0.degree. The aromatic oil referred to here is one obtained by distilling heavy oil used as a raw material and has a boiling point range of 200 to 350°C, for example, the 240 to 280°C fraction of coal tar. These include certain cleaning oils (also referred to as absorption oils), anto-2-sene oil which is a fraction of 280 to 350°C, or aromatic oils in the above-mentioned boiling point range of petroleum heavy oils. Considering the economics of the process,
It goes without saying that it is more preferable to use an aromatic oil obtained from heavy oil as a raw material for producing mesophase pitch than to use an aromatic oil obtained from a different type of raw material. By coexisting with this aromatic oil,
It is possible to prevent excessive thermal polymerization in the tube heating furnace and provide sufficient residence time for purified heavy components to cause sufficient thermal decomposition, and at the same time, it is possible to prevent tube clogging due to coke formation. Therefore, it is inconvenient if the aromatic oil itself undergoes significant thermal polymerization in a tube heating furnace, as it will actually promote clogging of the tube; Cannot be used. Also, the boiling point is 200
A material containing a large amount of components whose temperature is below 0.degree. C. is disadvantageous because the pressure required to maintain it in a liquid state in a tube heating furnace becomes extremely high. Further, the amount of aromatic oil used for the above purpose may be at most 1 times the weight of the refined heavy components. Further, if the refined heavy component contains a sufficient amount of aromatic oil having the above boiling point range, it is not necessary to add new aromatic oil or to add the aromatic oil.
加熱処理の温度と滞留時間は、加熱処理物中のキシレン
不溶分が３〜３０重量％となる様に。The temperature and residence time of the heat treatment are such that the xylene insoluble content in the heat treated product is 3 to 30% by weight.
かつキノリン不溶分が実質的に生成しない様に選択すべ
きであり、一般的に言りて温度が低すぎるか又は滞留時
間が短かすぎるとＢＴＸ溶剤に不溶な成分の生成量が少
なく効率が悪いばかりでなく、得られるＢＴＸ溶剤不溶
性成分の分子量が低すぎるため、水素化後の熱処理にお
いてメソフェーズ化のための処理条件を厳しくする必要
が生じ、そのためにかえりてメソフェーズピッチ中のキ
ノリン不溶分量がやや増加するようである。逆に温度が
高すぎるか又は滞留時間が長ずざると、過度の熱重合が
起りキノリン不溶分が生成するばかりでなく、コークス
の生成による管の閉塞をまね（。温度４００〜６００℃
における滞留時間は通常１０〜２０００ ｓｅｃが適当
であり、好ましくは３０〜１０００ ｓｅｃである。さ
らに重要なことは、この第１工程で生成するＢＴＸ溶剤
不溶分が実質的にキノリン不溶分を含まないことに加え
、その後の水素化処理で用いる水素供与性溶媒に不溶の
成分を多量に含有しない様な条件を選択すべきであると
いうことである。その量は水素供与性溶媒の程類によっ
て変るので定量的に限定することはできないが、生成し
たＢＴＸ溶剤不溶分を取りだし、これを水素供与性溶媒
の必要量に混合溶解した後、８０〜１００℃で一昼夜静
置したときに不溶物の沈殿分離が見られない様であれば
十分である。不溶性沈殿物が多量に生成する様な場合に
は、水素化処理を連続的に実施しようとすると、ポンプ
および配管の閉塞等により運転不能となる。前記静置に
よって沈降しない様な微細な不溶物の場合は水素化処理
によってそれが可溶性に改質されるうえ、溶媒自体が水
素を放出し溶解力を増すので問題とはならない。この様
なコントロールは第１工程の加熱処理原料としてＢＴＸ
溶剤に不溶な成分を実質的に含まない精製重質成分を用
いることによって初めて可能となる。The selection should also be made so that substantially no quinoline insoluble components are generated.Generally speaking, if the temperature is too low or the residence time is too short, the amount of components insoluble in the BTX solvent will be small and the efficiency will be reduced. Not only is this bad, but because the molecular weight of the resulting BTX solvent-insoluble components is too low, it becomes necessary to tighten the processing conditions for mesophase formation in the heat treatment after hydrogenation, and as a result, the amount of quinoline-insoluble components in the mesophase pitch increases. It seems that there will be a slight increase. On the other hand, if the temperature is too high or the residence time is too long, excessive thermal polymerization will occur, not only producing quinoline insoluble matter but also simulating tube blockage due to coke formation (temperature 400-600°C).
The residence time in is normally 10 to 2000 sec, preferably 30 to 1000 sec. More importantly, in addition to the fact that the BTX solvent-insoluble matter produced in this first step does not substantially contain quinoline-insoluble matter, it also contains a large amount of components insoluble in the hydrogen-donating solvent used in the subsequent hydrogenation treatment. This means that conditions should be selected that will prevent this from occurring. The amount varies depending on the degree of hydrogen donating solvent, so it cannot be quantitatively limited, but after taking out the generated BTX solvent insoluble matter and mixing and dissolving it in the required amount of hydrogen donating solvent, It is sufficient if no precipitation of insoluble matter is observed when the solution is allowed to stand overnight at ℃. If a large amount of insoluble precipitates are produced, if the hydrogenation treatment is attempted to be carried out continuously, the pumps and piping may become clogged, making operation impossible. In the case of fine insoluble matter that does not precipitate upon standing, it is not a problem because it is modified to be soluble by the hydrogenation treatment and the solvent itself releases hydrogen and increases its dissolving power. This kind of control is achieved by using BTX as the raw material for heat treatment in the first step.
This is only possible by using purified heavy components that are substantially free of components insoluble in solvents.
また、加熱処理の圧力が低すぎる場合、精製重質成分ま
たは芳香族系油中の軽質留分が気化し、気液の分離が起
り、液相部が著しく重合し易くなりキノリン不溶分の生
成と管の閉塞が起こり易（なる。従って圧力は高い方が
好ましいと言えるが、圧力を１００−／ｃｄＧ以上とす
ることは、装置の建設費が高くなり経済的ではない。必
要とされる圧力は加熱処理される精製重質成分または芳
香族系油な実質的に液相に保つに足りる圧力であればよ
い。In addition, if the pressure of heat treatment is too low, refined heavy components or light fractions in aromatic oils will vaporize, gas-liquid separation will occur, and the liquid phase will be extremely prone to polymerization, resulting in the formation of quinoline-insoluble components. Therefore, it can be said that a higher pressure is preferable, but setting the pressure to 100-/cdG or higher increases the construction cost of the equipment and is not economical.The required pressure The pressure may be sufficient to maintain the refined heavy components or aromatic oil to be heat-treated in a substantially liquid phase.
この第１工程における加熱処理は、最終的に得られるメ
ソフェーズピッチの物性、ひいては炭素繊維の物性にま
で影響を及ぼす。また、この加熱処理は一般的に用いら
れているオートクレーブの様なバッチ式の加圧加熱処理
設備では到来実施出来ないものである。なぜなら、バッ
チ式設備において１０〜２０００ｓｅｃという短い滞留
時間をコントロールすることは不可能であるため、時間
単位の長い滞留時間を持たせる様に処理温度を低くせざ
るを得ない。この様な条件でＢＴＸ溶剤に不溶な成分が
生成するまで加熱処理すると、キノリンに不溶なコーク
ス状固形物が多量に生成することを本発明者らは経験し
ている。十分に熱分解灰石を起させ、かつ過度の熱重合
を防ぐためにはこの第１工程な本発明の方法による管式
加熱炉を用い、特定された条件下で実施する必要がある
。The heat treatment in this first step affects the physical properties of the mesophase pitch finally obtained, and even the physical properties of the carbon fiber. In addition, this heat treatment cannot be carried out in commonly used batch-type pressurized heat treatment equipment such as an autoclave. This is because it is impossible to control a short residence time of 10 to 2000 seconds in a batch-type facility, so the treatment temperature must be lowered so as to have a long residence time in units of hours. The present inventors have experienced that when heat treatment is performed under such conditions until components insoluble in the BTX solvent are produced, a large amount of coke-like solids insoluble in quinoline are produced. In order to sufficiently generate pyrolyzed ashes and prevent excessive thermal polymerization, it is necessary to carry out the first step using a tube heating furnace according to the method of the present invention under specified conditions.
上記の様なことを考慮して、この工程における加熱処理
条件が選定されるが、その条件が適当であるかどうかの
判断をする一つの基準として、得られる加熱処理物中の
キノリン不溶分を測定する方法がある。得られる加熱処
理物中のキノリン不溶分がｔｗｔ％以上となる様な条件
は、すでに管式加熱炉において過度の熱重合が起ってい
ることを示しており、管の閉塞を予想させるものである
。また、この様な厳しい条件で処理して得た加熱処理物
を用いる場合には、生成した高重合物をその後の工程の
どこかで分離除去することが不可欠となる。逆に、加熱
処理物中のキノリン不溶分が１ｗｔ％以下である場合は
、その後の工程でこれを除去しなくても良い。The heat treatment conditions in this step are selected in consideration of the above, but one criterion for determining whether the conditions are appropriate is to determine the quinoline insoluble content in the resulting heat treated product. There is a way to measure it. Conditions in which the quinoline insoluble content in the resulting heat-treated product is twt% or more indicate that excessive thermal polymerization has already occurred in the tube heating furnace, and can lead to the prediction of tube clogging. be. Further, when using a heat-treated product obtained by processing under such severe conditions, it is essential to separate and remove the generated high polymer product at some point in the subsequent process. Conversely, if the quinoline insoluble content in the heat-treated product is 1 wt% or less, it is not necessary to remove it in the subsequent process.
加熱処理物中のキノリン不溶分量に関して、上記の様な
厳密なコントロールと評価が可能となりたのは、この工
程の加熱処理を管式加熱炉で実施することに加え、原料
としてキシレン不溶分な含まないかもしくはこれを除去
したものを用いることによるものである。The above-mentioned strict control and evaluation of the amount of quinoline insolubles in the heat-treated product was made possible because the heat treatment in this step was carried out in a tube heating furnace, and also because the raw material contained xylene insolubles. This is done by using a material that does not have this or has it removed.
また、管式加熱炉の直後にソーキングドラムを設置して
加熱処理の滞留時間を調整する方法が知られており、本
発明の方法においてもこのソーキングドラムを必要に応
じて設置することが出来る。しかし、ノーキングドラム
での滞留時間を非常に長くしなければならない様な温度
等の条件を選択すると、バッチ式処理の場合と同様にキ
ノリン不溶分生成の問題が発生するので好ましくない。Furthermore, a method is known in which a soaking drum is installed immediately after the tube heating furnace to adjust the residence time of the heat treatment, and this soaking drum can also be installed as necessary in the method of the present invention. However, if conditions such as temperature are selected that require a very long residence time in the noking drum, this is not preferable because the problem of quinoline insoluble matter formation will occur as in the case of batch processing.
したがって、必要に厄じてソーキングドラムを設置する
場合であっても、管式加熱炉における前記要件を十分考
慮しておく必要がをる。Therefore, even if a soaking drum is installed out of necessity, it is necessary to fully consider the above-mentioned requirements for a tube heating furnace.
次の第２工程は、第１工程で得られる加熱処理物を常圧
下又は減圧下に３５０℃（常圧換算）以下の温度で蒸留
又はブラッシングして熱分解重質成分を得る工程である
。この工程では、得られる重質成分が、沸点範囲が２０
０〜３５０℃の間にある軽質成分を少なくとも１０重量
％以上、好ましくは２０重量％以上含み、１００℃にお
ける粘度が１０００センチストークス以下となる様に蒸
留又はブラッシングの条件が選定される。The next second step is a step of distilling or brushing the heat-treated product obtained in the first step at a temperature of 350° C. (normal pressure equivalent) or less under normal pressure or reduced pressure to obtain a pyrolyzed heavy component. In this process, the heavy components obtained have a boiling point range of 20
Conditions for distillation or brushing are selected so that the light components between 0 and 350°C are contained at least 10% by weight, preferably 20% by weight or more, and the viscosity at 100°C is 1000 centistokes or less.
また、該重質成分から不溶分を除いて得ら庇る可溶性成
分は第１工程への循環用重質成分となるので、該可溶性
成分が第１工程に送入される加熱処理用原料としての等
性を満たす様にこの第２工程で調整しておくことが好ま
しい。また、この工程の蒸留又はブラッシングの条件は
得られる熱分解重質成分の沸点範囲が、第３工程で用い
るＢＴＸ溶剤の沸点よりも高くなる様に選定することが
好ましい。なぜなら、熱分解重質成分中に用いるＢＴＸ
溶剤とほぼ同じ沸点範囲の熱分解軽質油が含まれている
場合には。In addition, the soluble components obtained by removing the insoluble components from the heavy components become the heavy components for circulation to the first step, so the soluble components are used as raw materials for heat treatment to be sent to the first step. It is preferable to adjust in this second step so as to satisfy the equality. Further, the conditions for distillation or brushing in this step are preferably selected so that the boiling point range of the resulting pyrolyzed heavy component is higher than the boiling point of the BTX solvent used in the third step. This is because BTX used in pyrolysis heavy components
If it contains pyrolysis light oil with approximately the same boiling point range as the solvent.
第４工程の溶剤回収に際しこの熱分解軽質油とＢＴＸ溶
剤を分離するために分留効率の高い精留塔が必要となる
からである。This is because a rectification column with high fractionation efficiency is required to separate the pyrolyzed light oil and the BTX solvent during solvent recovery in the fourth step.
また、この第２工程で得られる熱分解重質成分は、ＢＴ
Ｘ溶剤不溶分を３〜３０重量％、通常５〜２０重量％含
み、キノリン不溶分を実質的に含まないものである。In addition, the pyrolyzed heavy components obtained in this second step are BT
It contains 3 to 30% by weight, usually 5 to 20% by weight, of solvent-insoluble matter, and is substantially free of quinoline-insoluble matter.
また、この第２工程では、蒸留又はブラッシングされた
沸点３５０℃以下の軽質成分をさらに沸点範囲、が２０
０〜３５０℃の間にある成分とそれ以下の沸点範囲の成
分に分ける操作を同時におこなっても良い。ここで得ら
れる沸点範囲が２００〜３５０℃の間にある成分は、第
１工程で芳香族系油を希釈油として用いる場合に、その
まま該第１工程の希釈油として用いることができる。In addition, in this second step, the distilled or brushed light components with a boiling point of 350°C or less are further added to the boiling point range of 20°C.
The operation of separating the components into a component having a boiling point between 0 and 350°C and a component having a boiling point below that range may be performed at the same time. The component having a boiling point range of 200 to 350° C. obtained here can be used as it is as the diluent oil in the first step when an aromatic oil is used as the diluent oil in the first step.
次の第３工程は、熱分解重質成分にＢＴＸ溶剤を加え、
生成する不溶性成分を分離回収する工程である。ここで
は、ＢＴＸ溶剤を加えようとする熱分解重質成分が、該
溶剤の沸点以下の温度で十分流動性のある液状であるこ
とが望ましい。なぜなら、この熱分解重質成分が溶剤の
沸点以上の温度で固体もしくは著しく粘度の高いもので
ある場合には、それをＢＴＸ溶剤に混合溶解するための
考別な設備、例えば加圧加熱溶解設備のようなものが必
要となり、また常温近辺の温度で混合溶解を実施しよう
とすると。The next third step is to add BTX solvent to the pyrolyzed heavy components,
This is a process of separating and recovering the insoluble components produced. Here, it is desirable that the thermally decomposed heavy component to which the BTX solvent is added is in a liquid state with sufficient fluidity at a temperature below the boiling point of the solvent. This is because, if this thermally decomposed heavy component is solid or extremely viscous at a temperature higher than the boiling point of the solvent, special equipment is required to mix and dissolve it in the BTX solvent, such as pressurized heating melting equipment. If you are trying to perform mixing and melting at a temperature close to room temperature, you will need something like this.
混合溶解のための時間が著しく長くなり効率が悪いから
である。This is because the time required for mixing and dissolving becomes extremely long, resulting in poor efficiency.
熱分解重質成分が溶剤の沸点以下の温度で十分流動性の
ある液状である場合には、溶剤への溶解が短時間で終了
するため、熱分解重質成分を１００℃穆度にしておき、
この配管にＢＴＸ溶剤を送入することで十分混合溶解が
可能であり、また必要に応じ簡単な溶解槽の様な設備を
設置するだけで十分である。上記した第２工程の諸条件
を満たす様にして取得された熱分解重質成分は、一般に
溶剤の沸点以下の温度で十分流動性のある液状となる。If the pyrolyzed heavy components are in liquid form with sufficient fluidity at a temperature below the boiling point of the solvent, dissolution in the solvent will be completed in a short time, so the pyrolyzed heavy components should be kept at 100°C. ,
Sufficient mixing and dissolution is possible by feeding the BTX solvent into this pipe, and it is sufficient to install simple equipment such as a dissolution tank as necessary. The pyrolyzed heavy components obtained in a manner that satisfies the conditions of the second step described above generally become liquid with sufficient fluidity at a temperature below the boiling point of the solvent.
従って、第３工程における溶剤処理の条件は、通常、常
温から用いる溶剤の沸点までの温度で、かつ当該熱分解
重質成分が十分な流動性を持つに足りる温度で、常圧〜
２ｋｌ？／ｃｉＩＧ程度の圧力下に、可溶性成分が溶解
するに十分な時間攪拌するのが適当であり、また、当該
熱分解重質成分のみを加熱しておき、これに常温近辺の
溶剤を加えることも可能である。Therefore, the conditions for the solvent treatment in the third step are usually from room temperature to the boiling point of the solvent used, at a temperature sufficient for the pyrolyzed heavy components to have sufficient fluidity, and from normal pressure to
2kl? It is appropriate to stir the mixture under a pressure of about /ciIG for a sufficient time to dissolve the soluble components.Also, it is also possible to heat only the pyrolyzed heavy components and add a solvent at around room temperature to this. It is possible.
第３工程で用いるＢＴＸ溶剤の量は熱分解重質成分に対
し１〜５重量倍量が適当である。この範囲が好ましい理
由は、原料の精良における場合と同様であり、下限は不
溶性成分の分離効率から、また上限は処理操作の経済性
から規定されるものである。通常は熱分解重質成分に対
して１〜３重量倍量の溶剤を使用するのが好ましい。The appropriate amount of BTX solvent used in the third step is 1 to 5 times the weight of the thermally decomposed heavy components. The reason why this range is preferable is the same as in the case of refining raw materials; the lower limit is determined by the separation efficiency of insoluble components, and the upper limit is determined by the economic efficiency of processing operations. Usually, it is preferable to use the solvent in an amount of 1 to 3 times the weight of the pyrolyzed heavy components.
また、この第３工程でＢＴＸ溶剤よりも溶解性の著しく
低い貧溶剤を用いた場合には得られる不溶性成分の中に
メソフェーズ化しにくい低分子量成分が多量に含まれる
ことになり均質なメソフェーズピッチを得ることが困難
になる。Additionally, if a poor solvent with significantly lower solubility than the BTX solvent is used in this third step, the resulting insoluble components will contain a large amount of low molecular weight components that are difficult to form into mesophase, resulting in a homogeneous mesophase pitch. becomes difficult to obtain.
逆にＢＴＸ溶剤よりも著しく溶解性の高い良溶剤を用い
ると得られる不溶性成分の収率が低下するばかりでなく
、可溶成分中に高分子量の成分が含まれることになり、
これを循環して第１工程で加熱処理する際にキノリン不
溶分等の好ましくない成分が生成することになる。On the other hand, if a good solvent with significantly higher solubility than the BTX solvent is used, not only will the yield of insoluble components decrease, but also high molecular weight components will be included in the soluble components.
When this is circulated and heat treated in the first step, undesirable components such as quinoline insoluble matter will be generated.
不溶性成分の分離回収の方法は沈降分離、液体サイクロ
ン、遠心分離あるいは口過等任意の分離方法で良いが、
連続運転が可能な分離方法を選択することが好ましい。The method for separating and recovering insoluble components may be any separation method such as sedimentation, hydrocyclone, centrifugation, or oral filtration.
It is preferable to select a separation method that allows continuous operation.
また、分離、回収した不溶性成分をくりかえしＢＴＸ溶
剤で洗浄しても良い。本発明の方法の場合、％に洗浄ニ
ーを取入れなくても、十分目的とするメンフェーズピッ
チは得られるが、メソフェーズ化の遅い成分を極力除去
するために２回以内の洗浄をすることは好ましいことで
ある。不溶性成分分離または回収の条件は、用いる溶剤
の沸点以下の温度が好ましく、通常、常温近辺の温度で
十−の溶剤を用いることがより好ましい。Furthermore, the separated and recovered insoluble components may be washed repeatedly with the BTX solvent. In the case of the method of the present invention, the desired mesophasing pitch can be obtained sufficiently without incorporating washing knee into the %, but it is preferable to wash the pitch no more than twice in order to remove as much as possible the components that are slow to mesophasize. That's true. The conditions for separating or recovering insoluble components are preferably a temperature below the boiling point of the solvent used, and it is usually more preferable to use a solvent at a temperature around room temperature.
この第３工程で得られる不溶性成分すなわち高分子量歴
青物は、通常、キシレン不溶分が１重量％以下、キシレ
ン不溶分が４０重量％以上、好ましくは５０重量％以上
であり、かつ光学的に等方性である。またこの高分子量
歴青物中にはＢＴＸ溶剤に可溶な成分も一部残存しうる
が、それは第２工程で設定した蒸留又はブラッシングの
条件に対応する沸点近辺の比較的沸点の低い成分を含む
重質油であり、従りてその大半はたとえば減圧蒸留、熱
処理等によって容易に除去されるものである。上記本発
明の第２工程の規定を逸脱して３５０℃以上の高温で重
質油等の加熱処理物を蒸留して高軟化点ピッチとしたも
のからＢＴＸ溶剤不溶分を得た場合には、洗浄が不十分
であったために残存する可溶性成分はすでに高温で蒸留
して除去されなかった高沸点物であるため、それを後の
処理で除去するのは容易ではなく、従って洗浄を十分に
行なう必要があり不経済とならざるを得ない。この様な
高軟化点ピッチから得られたＢＴＸ溶剤不溶分と本発明
の第３工程で得られる高分子量歴青物とでは、その中に
残存するＢＴＸ溶剤可溶分の組成、性質にも違いがあり
、この点も本発明の方法において特徴的なことである。The insoluble component, that is, the high molecular weight bituminous material obtained in this third step, usually has a xylene insoluble content of 1% by weight or less, a xylene insoluble content of 40% by weight or more, preferably 50% by weight or more, and is optically equivalent. It is directional. In addition, some components soluble in the BTX solvent may remain in this high molecular weight bituminous material, but this includes components with relatively low boiling points near the boiling point corresponding to the distillation or brushing conditions set in the second step. It is a heavy oil, and therefore most of it is easily removed, for example, by vacuum distillation, heat treatment, etc. If the BTX solvent-insoluble content is obtained from a high softening point pitch obtained by distilling a heat-treated product such as heavy oil at a high temperature of 350°C or higher, deviating from the provisions of the second step of the present invention, The soluble components remaining due to insufficient washing are high-boiling substances that have not been removed by distillation at high temperatures, so it is not easy to remove them in subsequent processing, so it is necessary to wash thoroughly. It is necessary and uneconomical. There are also differences in the composition and properties of the BTX solvent-soluble content remaining in the BTX solvent-insoluble content obtained from such a high softening point pitch and the high molecular weight bituminous material obtained in the third step of the present invention. This point is also characteristic of the method of the present invention.
また、この第３工程で得られる高分子量歴青物は、その
中のキシレン不溶分がほぼ１００重量％近くになるまで
洗浄した場合には、メトツー法で測゛定される軟化点が
３５０℃以上となり、メトツー法による軟化点の測定が
不能となるが、キシレン不溶分が６０〜８０重量％であ
る場合には、１５０〜３００℃程度の軟化点を示す。こ
れらの高分子量層ｆ物は、３５０℃未満の温度で加熱、
融解し、冷却してもその組織はやはり光学的に等方性で
あり、はぼ全面異方性を示す様なメソフェーズピッチと
はならない。In addition, when the high molecular weight bituminous material obtained in this third step is washed until the xylene insoluble matter in it becomes approximately 100% by weight, the softening point measured by the Met-To method is 350°C or higher. Therefore, it becomes impossible to measure the softening point by the Meto-Two method, but when the xylene insoluble content is 60 to 80% by weight, the softening point is about 150 to 300°C. These high molecular weight layer materials are heated at a temperature below 350°C,
Even if it is melted and cooled, its structure is still optically isotropic, and it does not become a mesophase pitch that exhibits almost total anisotropy.
次の第４工程は、第３工程で不溶性成分を除去して得ら
れる清澄液から溶剤を蒸留除去して、必要に応じ該清澄
液中に残存する余剰の軽質成分をも留去して、可溶性成
分を回収する工程である。この第４工程は単なる蒸留操
作であり特別の技術を必要とするものではない。しかし
、得られる可溶性成分は、第２工程の蒸留又はブラッシ
ングの条件により低沸点側が、また第３工程のＢＴＸ溶
剤による不溶性成分の除去により高沸点側が決められた
特定の組成を持つものであり、また、一般に、実質的に
ＢＴＸ溶剤に不溶な成分を含まず、沸点範囲が２００〜
３５０℃の間にある軽質成分を１０重量％以上、好まし
くは２０重量％以上含み、かつ１００℃における粘度が
１０００センチストークス以下という特性を満足すると
いう意味において、本質的に第１工檻に送入される精製
重質成分と同じものであると言うことができる。In the next fourth step, the solvent is distilled off from the clarified liquid obtained by removing the insoluble components in the third step, and if necessary, excess light components remaining in the clarified liquid are also distilled off. This is a step of recovering soluble components. This fourth step is a simple distillation operation and does not require any special technique. However, the resulting soluble components have a specific composition with a low boiling point determined by the conditions of distillation or brushing in the second step, and a high boiling point determined by the removal of insoluble components by the BTX solvent in the third step, In addition, it generally does not contain substantially any components insoluble in the BTX solvent and has a boiling point range of 200 to 200.
In the sense that it contains 10% by weight or more, preferably 20% by weight or more of light components between 350°C and satisfies the characteristics that the viscosity at 100°C is 1000 centistokes or less, it is essentially sent to the first cage. It can be said that they are the same as the purified heavy components that are introduced.
本発明の方法においては、この第４工程で得られる可溶
性成分は第１工程に連続的に循環されて加熱処理を受け
、新しくＢＴＸ溶剤に不溶の成分を生成する。第４工程
で得られる可溶性成分が第１工程の原料として好適に使
用できること、またそれから得られる炭素繊維の特性が
すぐれたものであるということは次の例からも明らかで
ある。In the method of the present invention, the soluble component obtained in the fourth step is continuously circulated to the first step and subjected to heat treatment to generate a new component insoluble in the BTX solvent. It is clear from the following example that the soluble component obtained in the fourth step can be suitably used as a raw material in the first step, and that the carbon fiber obtained therefrom has excellent properties.
市販のコールタール（Ａ）から沸点２８０℃以下の軽質
油を除去して得た重質成分に２重量倍量のキシレンを混
合し、生成した不溶分をろ過により除去した後、キシレ
ンを蒸留除去して精製重質成分を得た。この精製重質成
分を内径６謔、長さ４０ｍの加熱管を溶融塩浴中に浸漬
した構造を持つ管式加熱炉において温度５２０℃、圧力
２０ｋｌ？／ｃ！ｌＧ、原料チャージ量１７．５に９／
ｈｒの条件で加熱処理し、続いて常圧下２８０℃にて蒸
留して熱分解重質成分を得た。これに２重量倍童のキシ
レンを入れ混合溶解した後、生成した不溶分を連続的に
遠心分離した。得られた不溶分をさらに２重量倍量のキ
シレン中に分散混合した後、遠心分離して不溶分の洗浄
を行なった。この不溶分を減圧乾燥して得られた高分子
量歴青物は精製重質成分に対して１１．１重量％であっ
た。また、不溶分を除去して得た清澄液からキシレンを
蒸留除去して得た可溶性成分を原料として、上記と同一
条件で加熱処理、蒸留、不溶分の採取および減圧乾燥を
行なったところ、可溶性成分に対して８．４重量％の高
分子量歴青物が得られた。この２つの高分子量歴青物を
それぞれ３重量倍量の水素化アントラセン油に溶解し、
内径１０ｍ、長さ１００ｍの加熱管を溶融塩浴中に浸漬
した構造を持つ管式加熱炉において温度４４０℃、圧力
５０ｋｌ？／ｃｄＧ。Two times the weight of xylene is mixed with the heavy component obtained by removing light oil with a boiling point of 280°C or less from commercially available coal tar (A), and after removing the generated insoluble matter by filtration, the xylene is distilled off. A purified heavy component was obtained. This purified heavy component was heated in a tube heating furnace with a structure in which a heating tube with an inner diameter of 6 m and a length of 40 m was immersed in a molten salt bath at a temperature of 520°C and a pressure of 20 kl. /c! lG, raw material charge amount 17.5 to 9/
The mixture was heat-treated under conditions of 1.5 hours, and then distilled at 280° C. under normal pressure to obtain thermally decomposed heavy components. After adding 2 times the weight of xylene to the mixture and mixing and dissolving it, the resulting insoluble matter was continuously centrifuged. The obtained insoluble matter was further dispersed and mixed in twice the weight of xylene, and then centrifuged to wash the insoluble matter. The high molecular weight bituminous material obtained by drying the insoluble matter under reduced pressure was 11.1% by weight based on the purified heavy components. In addition, when soluble components obtained by distilling off xylene from the clear liquid obtained by removing insoluble components were used as raw materials, heat treatment, distillation, collection of insoluble components, and drying under reduced pressure were performed under the same conditions as above. A high molecular weight bituminous material of 8.4% by weight based on the components was obtained. These two high molecular weight bituminous substances were each dissolved in 3 times the weight of hydrogenated anthracene oil,
In a tube heating furnace with a structure in which a heating tube with an inner diameter of 10 m and a length of 100 m is immersed in a molten salt bath, the temperature is 440 ° C and the pressure is 50 kl? /cdG.
原料チャージ量６．５ ｋｇ／ ｈｒの条件下で加熱処
理し、続いて常圧下４００℃で７ラツシー蒸留すること
により溶媒と軽質成分を除去して水素化ピッチを得た。The mixture was heat-treated at a raw material charge of 6.5 kg/hr, and then subjected to 7 Lacey distillation at 400° C. under normal pressure to remove the solvent and light components to obtain hydrogenated pitch.
それぞれの水素化ピッチを重合フラスコに入れ窒素吹き
込み量８０１／ｍ１ｎ（ピッチ１ｋｇ当り）として、温
度４５０℃で熱処理して、メトラー法軟化点約３００℃
の紡糸ピッチを調整した。それぞれの紡糸ピッチから炭
素繊維を製造し、１０００℃で炭化したものの特性を測
定したところ、もとの精Ｊ！ｌＩ！重質取分から得たも
のの強度は２８９ｋｇ／−であり、可溶性成分から得た
ものの強度は３０３ｋｌ？／−でありた。Each hydrogenated pitch was placed in a polymerization flask and heat treated at a temperature of 450°C with a nitrogen blown amount of 801/ml (per 1kg of pitch) to reach a Mettler method softening point of approximately 300°C.
The spinning pitch was adjusted. When carbon fibers were produced from each spinning pitch and carbonized at 1000°C, their properties were measured, and it was found that the original quality J! lI! The strength of the material obtained from heavy extraction is 289 kg/-, and the strength of the material obtained from soluble components is 303 kl? It was /-.
また、別のコールタール（Ｂ）を用い″′Ｃ同様の比戟
テストを行なった場合にも、精製重質成分から得た炭素
繊維の強度は３００ゆ／−１可溶性成分から得たものの
強度は３１７ｋｌ？／−であり、可溶性成分を加熱処理
することにより新たに生成するＢＴＸ溶剤不溶性成分を
用いて炭素繊維を製造すると、よりすぐれたへ性の炭！
！繊維が得られることが見いだされた。In addition, when a comparison test similar to ''C was conducted using another coal tar (B), the strength of the carbon fiber obtained from the purified heavy component was 300 Yu/-1, which was the strength of that obtained from the soluble component. is 317kl?/-, and when carbon fiber is manufactured using the BTX solvent-insoluble component newly generated by heat-treating the soluble component, the charcoal becomes even more hemispherical!
! It has been found that fibers can be obtained.
すなわち本発明の構成が紡糸ピッチ収率な高くし、さら
に良質な紡糸ピッチおよび炭素繊維を製造するうえで極
めて効果的であるとＷｌ識されたのは上記の様な知見を
得ることができたことによるものである。In other words, it was possible to obtain the above knowledge that the structure of the present invention was found to be extremely effective in increasing the spinning pitch yield and producing high-quality spinning pitch and carbon fiber. This is due to a number of reasons.
また、第１工程に循環される量は、原料である精製重質
成分に対して１重量倍量以上であることが好ましく、特
に２〜６重量倍量であることが好ましい。この循環量は
原料である精製重質成分に対する高分子量歴青物すなわ
ち水素化用原料の収率に大きく影響する。従って循環量
が非常に少ないと、収率の大幅な向上が期待できない。Further, the amount recycled to the first step is preferably 1 times or more by weight, particularly preferably 2 to 6 times the weight of the purified heavy components as raw materials. The amount of circulation greatly affects the yield of high molecular weight bituminous material, that is, the raw material for hydrogenation, relative to the refined heavy components that are the raw materials. Therefore, if the circulation amount is very small, a significant improvement in yield cannot be expected.
また、第４工程で得られる可溶性成分の量は、第１工程
の加熱処理の際にＢＴＸ溶剤不溶分をどの程度生成させ
るかということと。Furthermore, the amount of soluble components obtained in the fourth step depends on how much BTX solvent insoluble components are generated during the heat treatment in the first step.
第２工程で軽質成分をどの程度除去するかということに
よって決るものであり、循環可能な最大量はおのずと決
るものである。しかし、必ずしも全量を循環する必要は
なく、原料と条件によりて決る循環可能最大量以下の範
囲で任意に選択できる。収率の向上、プロセスの効率を
考えると循環量は２〜６重量倍量とするのが特に好まし
い。This is determined by how much light components are removed in the second step, and the maximum amount that can be recycled is determined naturally. However, it is not necessarily necessary to circulate the entire amount, and the amount can be arbitrarily selected within the range of the maximum recyclable amount determined by the raw materials and conditions. Considering the improvement in yield and the efficiency of the process, it is particularly preferable that the circulating amount be 2 to 6 times the amount by weight.
本発明の方法によって、水素化用高分子量歴青物ひいて
は紡糸用メソ７エーズビツチの収率が高くなることを例
をもつ【説明する。It will be explained by way of example that the method of the present invention increases the yield of high molecular weight bituminous material for hydrogenation and thus of meso-7A bituminous material for spinning.
先に述べた市販のコールタール（Ａ）から得た精製重質
成分を内径６關、長さ２７．５ｍの加熱管を溶融塩浴中
に浸漬した構造を持つ管式加熱炉において温度５１０℃
、圧力２０）Ｃ９／ｉＧ、原料チャージ量１２．０ ｋ
ｇ／ ｈｒの条件で加熱処理した後、常圧下２８０℃で
蒸留して熱分解重質回収し、さらに２重量倍量のキシレ
ンで洗浄後、キシレンを乾燥除去して得た高分子量歴青
・偕は精製重質成分に対して７．８重量％であった。−
方、同じ精製重質成分を用い、上記と同じ条件で加熱処
理および不溶性成分の回収を行なうと同時に、不溶性成
分を除去した清澄液からキシレンを蒸留除去して可溶性
成分を回収し、この可溶性成分を精製重質成分に対して
３重量倍量となる様に管式加熱炉に循環しながら、連続
的に運転を実施した。このとき、精製重質成分の送入量
は３．０ ｋｇ／ ｈｒ 、循環される可溶性成分の量
を９．０ ｋｇ／ ｈｒとし、管式加熱炉における滞留
時間が同じになる様にした。この運転で得られた不溶性
成分を２重量倍量のキシレンで洗浄後乾燥して得た高分
子量歴青物は、もとの精製重質成分に対して３１．０重
量％であった。これは可溶性成分を循環しなかった場合
の約４倍に相当する。循環量を３重量倍にしたときに得
られの高分子量歴青物が得られていることになり、可溶
性成分を単ａＩ／ｃ加熱処理したときの結果からは予想
できなかったことである（前記したように、精製抽出成
分らの不溶性成分の収率が１１．１重量％の場合清澄液
の単独循環では不溶性成分の収率は８）４重量％にすぎ
ない。）。また、この運転では、可溶性成分が精製重質
成分に対して約２３重量％余剰でありたので、循環量を
さらに多くすることが可能であり、高分子量歴青物の収
率はさらに多くすることができると予想される。この様
に本発明の方法により水素化用の高分子量層ｆｅＪの収
率な飛躍的に向上させることができる。The purified heavy components obtained from the commercially available coal tar (A) mentioned above were heated to a temperature of 510°C in a tube heating furnace having a structure in which a heating tube with an inner diameter of 6 mm and a length of 27.5 m was immersed in a molten salt bath.
, pressure 20) C9/iG, raw material charge amount 12.0 k
After heat treatment under conditions of g/hr, distillation at 280°C under normal pressure to recover thermal decomposition, and further washing with 2 times the weight of xylene, the xylene was removed by drying to obtain high molecular weight bitumen. The weight was 7.8% by weight based on the purified heavy components. −
On the other hand, using the same purified heavy components, heat treatment and recovery of insoluble components are performed under the same conditions as above, and at the same time, xylene is distilled off from the clear liquid from which insoluble components have been removed to recover soluble components. The operation was carried out continuously while circulating through the tube heating furnace in an amount 3 times the weight of the purified heavy components. At this time, the amount of refined heavy components fed was 3.0 kg/hr, and the amount of soluble components circulated was 9.0 kg/hr, so that the residence times in the tube heating furnaces were the same. The high molecular weight bituminous material obtained by washing the insoluble components obtained in this operation with twice the weight of xylene and drying was 31.0% by weight based on the original purified heavy components. This corresponds to approximately four times as much as if the soluble components were not recycled. This means that a high molecular weight bituminous material is obtained when the circulation amount is increased by 3 times by weight, which could not be expected from the results when the soluble components were heat-treated with single aI/c (as mentioned above). As described above, when the yield of insoluble components such as purified extract components is 11.1% by weight, the yield of insoluble components is only 8) 4% by weight when the clarified liquid is circulated alone. ). In addition, in this operation, the soluble components were in excess of the purified heavy components by approximately 23% by weight, so it was possible to further increase the circulation amount, and the yield of high molecular weight bituminous materials could be further increased. It is expected that this will be possible. As described above, the method of the present invention can dramatically improve the yield of high molecular weight layer feJ for hydrogenation.
前述の様にして本発明の第１〜第４工程を経て、
さらに第４工程から第１工程に可溶性
成分を循環しながら連続的に加熱処理と不溶分の回収を
行ない、このとき第３工程から得られる不溶性成分、す
なわち高分子量層ｔ＊は続いて水素化処理を受ける。After the first to fourth steps of the present invention as described above,
Furthermore, while circulating the soluble components from the fourth step to the first step, heat treatment and recovery of insoluble components are continuously performed, and at this time, the insoluble components obtained from the third step, that is, the high molecular weight layer t*, are subsequently hydrogenated undergo processing.
この高分子量歴青′物はそのまま触媒を用いて、水素ガ
ス加圧下に水素化することは困難であるため、水素供与
性溶媒の存在下に加熱処理して水素化する必要がある。Since it is difficult to hydrogenate this high molecular weight bituminous material directly using a catalyst under pressure of hydrogen gas, it is necessary to hydrogenate it by heat treatment in the presence of a hydrogen-donating solvent.
また第３工程で得られる高分子量歴青物は、使用したＢ
ＴＸ溶剤を含んだままのものであるので、これを除去す
ることが望ましい。その除去方法は、常圧下または減圧
下における単なる加熱蒸発あるいは蒸留等任意の手段で
良く、またその除去の時期も特に限定の要なく、たとえ
ば水素供与性溶媒と混合する前でも良く、あるいは溶剤
を含んだままのペースト状の不溶成分をそのまま水素供
与性溶媒に混合した後にＢＴＸ溶剤を選択的に除去する
こともできる。In addition, the high molecular weight bituminous material obtained in the third step is
Since it still contains the TX solvent, it is desirable to remove it. The removal method may be any method such as simple thermal evaporation or distillation under normal pressure or reduced pressure, and there is no particular limitation on the timing of the removal, for example, it may be before mixing with the hydrogen-donating solvent, or it may be removed before mixing with the hydrogen-donating solvent. It is also possible to selectively remove the BTX solvent after mixing the still-containing paste-like insoluble components with the hydrogen-donating solvent.
また、Ｉｊｃ素供与性溶媒を用いたピッチ等高分子量歴
青物の水素化は、叫開昭５８−１９６２９２号、特開昭
５８−２１４５３１号、特開昭５８−１８４２１号など
によりすでに公知の方法を用いることができるが、触媒
を用いる処理はその触媒を分離する工程が必要となるの
で、無触媒下での処理が経済的で望ましい。ここで用い
る水素供与性溶媒とはテトラヒドロキノリン、テトラリ
ン、ジヒドロナフタリン、ジヒドロアントラセン、水添
した洗浄油、水添したアントラセン油、ナフサタール又
はパイロリシスタールの軽質分を部分水添したものが含
まれるが、先に述べた様に、水素供与性溶媒の選択にあ
たっては、第３工程で得られる高分子量歴青物に対する
溶解性を十分に考慮する必要があり、高分子量歴青物に
対する溶解力を考えると、テトラヒドロキノリン、水添
した洗浄油、水添したアントラセン油が好適である。Furthermore, the hydrogenation of high molecular weight bituminous materials such as pitch using an Ijc element-donating solvent is already known by methods such as Kokai No. 58-196292, JP-A No. 58-214531, and JP-A No. 58-18421. However, since treatment using a catalyst requires a step to separate the catalyst, treatment without a catalyst is economical and desirable. The hydrogen-donating solvent used here includes tetrahydroquinoline, tetralin, dihydronaphthalene, dihydroanthracene, hydrogenated cleaning oil, hydrogenated anthracene oil, partially hydrogenated light components of naphthatal or pyrolisistal. As mentioned earlier, when selecting a hydrogen donating solvent, it is necessary to fully consider the solubility of the high molecular weight bituminous material obtained in the third step, and considering the dissolving power for the high molecular weight bituminous material, Tetrahydroquinoline, hydrogenated cleaning oils, hydrogenated anthracene oils are preferred.
また、水素化の方法は、オートクレーブの様なバッチ式
で自生圧下に行なうこともできるが、バッチ式の場合、
大型化するにしたがってその温度コントロールが難しく
なると同時に、容器内外の温度差が大きくなることなど
の理由から、水素化処理時にコークス状の固形物が生成
しやすくなる。この固形物を水素化後にろ過等の方法に
より除去するのは容易ではないので、水素化処理時に固
形物を生成しない方法が好ましい。In addition, the hydrogenation method can be carried out under autogenous pressure in a batch system such as an autoclave, but in the case of a batch system,
As the size increases, it becomes more difficult to control the temperature, and at the same time, coke-like solids are more likely to be produced during hydrogenation treatment due to the large temperature difference between the inside and outside of the container. Since it is not easy to remove this solid matter by a method such as filtration after hydrogenation, a method that does not generate solid matter during hydrogenation treatment is preferred.
その好ましい方法の一つは、高分子量歴青物を水素供与
性溶媒の１〜５重量倍量の存在下に。One of the preferred methods is to use a high molecular weight bituminous material in the presence of 1 to 5 times the weight of a hydrogen-donating solvent.
管式加熱炉において温度４００〜４６０℃、圧力２０〜
１００に９／ｄＧの条件下に連続的に水素化する方法で
ある。この方法によれば、水素化が連続的に実施できる
ので効率が良いばかりでなく、コークス状固形物を生成
させることなく、高分子量歴青物を１ｊＣＲ化すること
ができる。In a tube heating furnace, the temperature is 400 to 460℃, the pressure is 20 to
This is a method of continuous hydrogenation under conditions of 100 to 9/dG. According to this method, hydrogenation can be carried out continuously, which is not only efficient, but also allows high molecular weight bituminous materials to be converted into 1jCR without producing coke-like solids.
用いる溶媒の量は高分子量歴青物の水素化が十分効果的
であり、かつ経済的な理由から上記の様［１〜５ｘ量倍
量とするのが好ましい。また。The amount of solvent to be used is preferably 1 to 5 times the amount as described above for hydrogenation of high molecular weight bituminous materials to be sufficiently effective and for economical reasons. Also.
この方法の場合、温度４００〜４６０℃における滞留時
間は通常１０〜１２０分の範囲が好ましい。In the case of this method, the residence time at a temperature of 400 to 460°C is usually preferably in the range of 10 to 120 minutes.
次に水素化された混合液は、蒸留等任意の方法により溶
媒を除去して水素化ピッチを得る。Next, the solvent is removed from the hydrogenated mixture by an arbitrary method such as distillation to obtain hydrogenated pitch.
この方法は通常のバッチ式または連続式の蒸留設備で実
施し得るが、本発明の方法により第３工程から得られる
高分子量歴青物はＢＴＸ溶剤に可溶な比較的沸点の低い
成分を含んでいるので、水素化処理の後、処理された混
合液を、フラッシュ蒸留塔において圧力０〜３に９／ｃ
ｒ／ｌＡ。Although this process can be carried out in conventional batch or continuous distillation equipment, the high molecular weight bituminous product obtained from the third step according to the process of the present invention contains relatively low boiling point components that are soluble in the BTX solvent. After hydrogenation, the treated mixture is heated to a pressure of 0 to 3 9/c in a flash distillation column.
r/lA.
温度３００〜５３０℃の条件下に連続的にフラッシュ蒸
留することにより、溶媒と高分子量歴青物中の低沸点成
分および水素化処理により生成した軽質成分等を同時に
分離除去して、フラッジＳ蒸留塔底から水素化されたピ
ッチを得る方法が好適である。この方法によれば、軟化
点が１００〜２００℃、キノリン不溶分が１重量％以下
、キシレン不溶分が４０重量％以上の光学的に等方性で
ある水素化ピッチを連続的に得ることができる。上記以
外の方法を用いて水素化及び溶媒除去を実施する場合に
おいても、水素化ピッチの性状が上の範囲になる様にす
ることが望ましい。キノリン不溶分についてはすでに述
べた通りであるが、キシレン不溶分についてはこれが著
しく少ない場合には次の熱処理でメソフェーズ含有量を
９０％以上とするための処理条件が厳しくなりすぎるた
め、この熱処理においてキノリン不溶分が多量に生成す
ることＫなり好ましくない。また、溶媒や軽質成分が多
量に残留したものを次の熱処理にかけるのは処理量の増
大をまねき好ましくない。これらの条件を満足する水素
化ピッチの軟化点は通常１００〜２００℃の範囲となる
。Continuous flash distillation at a temperature of 300 to 530°C simultaneously separates and removes the solvent, low-boiling components in the high molecular weight bituminous material, and light components generated by hydrogenation treatment, resulting in a Flood S distillation column. Methods that obtain hydrogenated pitch from the bottom are preferred. According to this method, it is possible to continuously obtain optically isotropic hydrogenated pitch with a softening point of 100 to 200°C, a quinoline insoluble content of 1% by weight or less, and a xylene insoluble content of 40% by weight or more. can. Even when hydrogenation and solvent removal are carried out using a method other than the above, it is desirable that the properties of the hydrogenated pitch fall within the above range. The quinoline-insoluble content has already been mentioned, but if the xylene-insoluble content is extremely low, the treatment conditions for increasing the mesophase content to 90% or more in the next heat treatment will be too severe, so in this heat treatment, It is undesirable that a large amount of quinoline insoluble matter is produced. Further, it is not preferable to subject a material in which a large amount of solvent and light components remain to the subsequent heat treatment because it increases the amount of processing. The softening point of hydrogenated pitch that satisfies these conditions is usually in the range of 100 to 200°C.
溶媒を蒸留除去して得られた水素化ピッチは次に熱処理
される。その方法は、減圧下もしくは不活性ガスの吹き
込み下に３５０〜５００℃の温度で１０〜３００分間熱
処理するというすでに公知の方法を採用することができ
るが３８０〜４８０℃、時間１０〜１８０分とすること
が好ましい。また、この溶媒を除去して得られた水素化
ピッチを、たとえば減圧下又は常圧下に不活性ガス等の
流通下薄膜蒸発装置、流下膜式熱処理装置等を用いて連
続的に３−５０〜５００℃の温度で熱処理をしても良い
。The hydrogenated pitch obtained by distilling off the solvent is then heat treated. As the method, the already known method of heat treatment at a temperature of 350 to 500°C for 10 to 300 minutes under reduced pressure or while blowing inert gas can be adopted. It is preferable to do so. Further, the hydrogenated pitch obtained by removing the solvent is continuously heated for 3-50 to 300 ml using a thin film evaporator under reduced pressure or normal pressure, a falling film heat treatment equipment, etc. under a flow of inert gas, etc. Heat treatment may be performed at a temperature of 500°C.
この熱処理過程でピッチのメンフェーズ化が起り、実質
的に等方性の水素化ピッチが、はぼ全面異方性を示すメ
ソフェーズピッチへと転換される。本発明の方法で得ら
れる高分子量歴青物を用いる場合には、それが物足の方
法と条件で製造された厳選された成分であるため、容易
に全面異方性のメソフェーズピッチへと転換することが
可能であり、従来技術では製造できなかった（１）軟化
点が低（、（２）メソフェーズ含有量が高く、（３）キ
ノリン不溶分が少なく、さらに（４）キシレン可溶分が
少ないという４つの特性を同時に満足する肴に均質なメ
ソフェーズピッチを製造することができる。During this heat treatment process, the pitch undergoes menphasing, and the substantially isotropic hydrogenated pitch is converted into a mesophase pitch that exhibits nearly all-over anisotropy. When using the high molecular weight bituminous material obtained by the method of the present invention, it is easily converted into mesophase pitch with total anisotropy because it is a carefully selected component manufactured by a satisfactory method and conditions. (1) low softening point, (2) high mesophase content, (3) low quinoline-insoluble content, and (4) low xylene-soluble content, which could not be produced using conventional technology. It is possible to produce homogeneous mesophase pitch for dishes that simultaneously satisfy the following four characteristics.
さらに図面をもって本発明の第１〜第４工程を説明する
。Further, the first to fourth steps of the present invention will be explained with reference to the drawings.
第１図において、１はＢＴＸ溶剤不溶分を除去した精製
重質成分タンクであり、この精製重質成分はライン２を
通り管式加熱炉５に送られる。このとき必要に石じて芳
香族系油タリク３からライン４を通り希釈用の芳香族系
油がライン２に混合される。管式加熱炉５で加熱処理さ
れた処理液はライン６を通って蒸留塔７に送られ、ここ
で軽質成分が塔頂からライン１７を通して系外に除去さ
れ、塔底液として熱分解重質成分が得られる。管式加熱
炉５での加熱処理に希釈剤として芳香族系油な使用する
場合には、蒸留塔７においてこの留分を分離し、これを
ライン８を通して芳香族系油タンク３にもどす。In FIG. 1, 1 is a purified heavy component tank from which BTX solvent insoluble matter has been removed, and this purified heavy component is sent to a tube heating furnace 5 through a line 2. At this time, aromatic oil for dilution is mixed into line 2 from aromatic oil tarik 3 through line 4 if necessary. The treated liquid heat-treated in the tubular heating furnace 5 is sent through a line 6 to a distillation column 7, where light components are removed from the top of the column through a line 17 to the outside of the system. ingredients are obtained. When aromatic oil is used as a diluent in the heat treatment in the tube heating furnace 5, this fraction is separated in the distillation column 7 and returned to the aromatic oil tank 3 through a line 8.
蒸留塔７の塔底液である熱分解重質成分はライン９を通
って不溶分分離機１０へ送られ、そのときＢＴＸ溶剤タ
ンク１１からＢＴＸ溶剤がライーン１２を通って送られ
熱分解重質成分と混合される。このときライン９とライ
ン１２の合流点の後、不溶分分離機１０の前に混合タン
クを設置しても良い。熱分解重質成分とＢＴＸ溶剤の混
合物は、不溶分分離機ｌＯに送られここで溶剤不溶分す
なわち高分子量歴青吻がライン１８を通して回収される
。不溶分を除去した清澄液はライン１３を通って溶剤回
収塔１４に送られ、ここで溶剤が回収されライン１５を
通りてＢＴＸ溶剤タンクｌ１ｇもどされる。一方、溶剤
回収塔１４の塔底液として得られる可溶性成分はライン
１６を通って２イン２へ循環されさらに加熱処理を受け
る。回収した溶剤可溶性成分の一部のみを循環する場合
は、ライン１６の任意の場所から系外に副生油として取
り出すことができる。The pyrolyzed heavy components, which are the bottom liquid of the distillation column 7, are sent through line 9 to the insoluble matter separator 10, and at this time, BTX solvent is sent from the BTX solvent tank 11 through line 12 to remove the pyrolyzed heavy components. mixed with ingredients. At this time, a mixing tank may be installed after the confluence of lines 9 and 12 and before the insoluble matter separator 10. The mixture of pyrolysis heavy components and BTX solvent is sent to an insolubles separator IO where the solvent insolubles, or high molecular weight bitumen, is recovered via line 18. The clarified liquid from which insoluble matter has been removed is sent through line 13 to solvent recovery tower 14, where the solvent is recovered and returned through line 15 to BTX solvent tank l1g. On the other hand, the soluble components obtained as the bottom liquid of the solvent recovery column 14 are circulated to the 2-in-2 through the line 16 and further subjected to heat treatment. When only a portion of the recovered solvent-soluble components are recycled, they can be taken out of the system as by-product oil from any location in the line 16.
第１図は本発明の第１〜第４工程が理解され易い様にす
るために簡略化して書かれているが、本発明の方法はこ
の図に制約されるものではない。たとえば、第１図中の
第２工程の蒸留塔７をフラッシュ塔又はフラッシュドラ
ムにし、この７ラツシエ塔又はフラッシュドラムでは除
去すべき軽質成分の一部のみを除去し、第４工程の溶剤
回収塔１４を分留塔にして、この分留塔において溶剤の
回収と残余の軽質成分の除去を同時に行なう様にするな
ど、本発明の必須の構成を逸脱することな（設備やその
組合わせの変更をすることは可能である。Although FIG. 1 is drawn in a simplified manner to make the first to fourth steps of the present invention easier to understand, the method of the present invention is not limited to this diagram. For example, the distillation column 7 in the second step in FIG. No. 14 is a fractionating column, and this fractionating column recovers the solvent and removes the remaining light components at the same time. It is possible to do this.
なお、この明細書中で用いたキシレン不溶分およびキノ
リン不溶分の定量は下記の手段によった。Note that the xylene-insoluble content and quinoline-insoluble content used in this specification were determined by the following means.
試料１．９を遠沈管に精秤し、これに３０ｃｃの溶剤（
キシレン又はキノリン）を入れ、８０℃の湯浴中に遠沈
管を浸し、約１時間攪拌しながら溶解する。遠沈管を湯
浴から取り出し、室温まで冷却した後、５０００ｒｐｍ
の遠心分虐機により１０分間遠心分離する。遠沈管の上
澄み液を注射器にて静かに抜き出す。遠沈管に３０ｃｃ
の溶剤を入れ、８０℃の湯浴巾約３０分間攪拌しながら
沈でん物を洗浄分散させる。遠沈管を湯浴から取り出し
室温にて上記遠心分離を行なう。上澄み液を注射器によ
り抜き出した後、再度溶剤３０ｃｃを加え、上記洗浄分
散と遠心会心操作を行なう。上澄み液を抜き出し、遠沈
管に残った不溶分をキシレンにより洗い出し、Ｇ−４ガ
ラスフイルターに移し吸引ろ過する。Precisely weigh sample 1.9 into a centrifuge tube, and add 30 cc of solvent (
xylene or quinoline), immerse the centrifuge tube in a water bath at 80°C, and dissolve while stirring for about 1 hour. After taking out the centrifuge tube from the water bath and cooling it to room temperature, the centrifuge tube was heated at 5000 rpm.
Centrifuge for 10 minutes using a centrifugal shaker. Gently remove the supernatant from the centrifuge tube with a syringe. 30cc in centrifuge tube
Add a solvent and wash and disperse the precipitate while stirring in a hot water bath at 80°C for about 30 minutes. Remove the centrifuge tube from the water bath and perform the above centrifugation at room temperature. After the supernatant liquid is taken out with a syringe, 30 cc of solvent is added again, and the above-mentioned washing and dispersion and centrifugation operations are performed. The supernatant liquid is extracted, and the insoluble matter remaining in the centrifuge tube is washed out with xylene, and the tube is transferred to a G-4 glass filter and filtered by suction.
ガラスフィルター中の内容物をキシレン約１０ＣＣで２
回洗浄し、さらにアセトン１０ｃｃで洗浄した後、１１
０℃の乾燥基中で乾燥して秤量する。The contents in the glass filter were diluted with about 10cc of xylene.
After washing twice and further with 10 cc of acetone,
Dry in a dry base at 0° C. and weigh.
（発明の効果）
本発明の方法は、ＢＴＸ溶剤に不溶な成分を実質的に含
まない精製重質成分を、等定の方法と条件で加熱処理し
たときに新たに生成するＢＴＸ溶剤に不溶な成分を回収
し、これをメソフェーズビクチ製造用の原料とするため
、従来の方法では得ることのできなかった軟化点が低く
極めて均質なメン７エーズビツチを製造することが可能
である。さらに本発明の方法で得られたメソフェーズピ
ッチからは特に優れた特性をもつ炭素繊維を得ることが
できる。すなわち本発明の方法で得られるメンフェーズ
ピッチは（１）軟化点が低く（メトツー法軟化点３１０
℃以下）、（２）メソフェーズ含有量が高く（９０％以
上） 、 （３）キノリン不溶分が少なく（１０重量％
以下） 、 （４１キシレン可溶分が少なく（１０重量
％以下）、さらに（５）それから１０００℃で炭化した
ものの強度３００ｋｇ／−以上、黒鉛化したときの強度
４００ｋｇ／ｄ、弾性率６０ ｔｏｎ／ｍｊ以上の高性
能炭素線維が容易に得られるという、５つの特性を同時
に満足するということにおいて従来のメソフェーズピッ
チとは明らかに異なるものである。(Effects of the Invention) The method of the present invention provides newly produced BTX solvent-insoluble components when purified heavy components that do not substantially contain components insoluble in the BTX solvent are heat-treated using the same method and conditions. Since the components are recovered and used as raw materials for producing mesophase vinegar, it is possible to produce extremely homogeneous mesophase vinegar with a low softening point that could not be obtained by conventional methods. Furthermore, carbon fibers with particularly excellent properties can be obtained from the mesophase pitch obtained by the method of the present invention. That is, the menphase pitch obtained by the method of the present invention (1) has a low softening point (Metho2 method softening point 310
℃ or less), (2) high mesophase content (90% or more), (3) low quinoline insoluble content (10% by weight).
(41) The xylene soluble content is low (10% by weight or less), and (5) the strength when carbonized at 1000℃ is 300 kg/- or more, the strength when graphitized is 400 kg/d, and the elastic modulus is 60 ton/ It is clearly different from conventional mesophase pitch in that it simultaneously satisfies the five characteristics of easily obtaining high-performance carbon fibers with mj or higher.
さらに、時定の条件下に処理することによって、回収さ
れる可溶性成分を原料の精製重質成分と本質的に同等の
ものとすることができるため、これを循環して使用する
ことにより水素化用高分子量歴青物の収率を飛躍的［１
ｔ２ｉめることが可能であり、またその工程を連続的に
実施できるので極めて効率的である。また、ＢＴＸ溶剤
不溶分を実質的に含まない精製重質成分を原料とし、特
定の方法と条件で処理するため、メン７エーズビツチを
製造するすべての工程においてコークス状固形物の生成
を防ぐことができ、従ってこの固形物を除去する工程を
必ずしも必要としない点においても極めて効率的である
。Furthermore, by processing under timed conditions, the recovered soluble components can be made essentially equivalent to the purified heavy components of the raw material, so they can be recycled and used for hydrogenation. Dramatically increased the yield of high molecular weight bituminous materials [1
t2i, and the process can be carried out continuously, making it extremely efficient. In addition, since the raw materials are purified heavy components that do not substantially contain BTX solvent-insoluble matter and are processed using specific methods and conditions, it is possible to prevent the formation of coke-like solids in all processes of manufacturing Men 7 A's Bitch. Therefore, it is extremely efficient in that it does not necessarily require the step of removing this solid matter.
さらに本発明の方法では、水素化用高分子量歴青物がす
べて人為的に造り出されるものであるため、その性状の
コントロール、ひいてはメソフェーズピッチの性状のコ
ントロールが容易である。このことは、本発明の方法が
出発原料の性状変化に十分対応できるということを意味
し、効率的である上に、フレキシビリティ−のあるプロ
セスであるといえる。さらに本発明の方法で得られたメ
ソフェーズピッチからは極めてすぐれた特性の炭素繊維
を製造することが可能である。Furthermore, in the method of the present invention, since the high molecular weight bituminous material for hydrogenation is entirely produced artificially, it is easy to control its properties and, by extension, the properties of mesophase pitch. This means that the method of the present invention can sufficiently respond to changes in the properties of the starting materials, and can be said to be an efficient and flexible process. Furthermore, it is possible to produce carbon fibers with extremely excellent properties from the mesophase pitch obtained by the method of the present invention.
（実施例）
以下、実施例および比較例をあげて本発明をさらに具体
的に説明する。以下の実施例および比較例において「％
」および「倍量」はそれぞれ籍記しない限り「重量％」
および「重量倍量」を意味する。(Examples) Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples. In the following Examples and Comparative Examples, “%
” and “double amount” are “weight%” unless otherwise noted.
and "double weight".
実施例１
第２表に示す性状の市販のコールタールを２８０℃で蒸
留して軽質成分を除去し、重質成分を得た。これに２倍
量のキシレンを加え混合溶解後、生成した不溶性成分を
常温下に連続ろ過機（・川崎重工リーフフィルター）Ｋ
てろ過し、不溶性成分を除去した。得られたろ液を蒸留
してキシレンを除去し、もとのコールタールに対し７０
．０％の収率で精製重質成分を得た。Example 1 Commercially available coal tar having the properties shown in Table 2 was distilled at 280°C to remove light components and obtain heavy components. Double the amount of xylene is added to this, mixed and dissolved, and the resulting insoluble components are filtered at room temperature using a continuous filter (Kawasaki Heavy Industries Leaf Filter) K.
and filtered to remove insoluble components. The obtained filtrate was distilled to remove xylene, and the original coal tar was
．． Purified heavy components were obtained with a yield of 0%.
この精製重質成分を原料として、第１図に示した方法で
第１工程の加熱処理から第４工程の可溶成分の回収まで
を連続的に実施した。各工程の運転条件は以下の様に設
定した。Using this purified heavy component as a raw material, steps from heat treatment in the first step to recovery of soluble components in the fourth step were carried out continuously in the method shown in FIG. The operating conditions for each process were set as follows.
（第１工程）
フィード量 精製重質取分 ３ｋｐ／ｈｒ可
溶成分循環＠ ９に９／ｈｒ
合計 １２ｋｌＩ／ｈｒ
循環比（リサイクル比） ３
管式加熱炉 構造 内径６ｆｌ、長さ２７．５ｍの
加熱管を溶融塩浴中に浸漬
したもの
加熱管出口温度 ５１０℃
加熱管出口圧力 ２０ｋｌ？／ｃｄＧ（第２工程）
蒸留塔 温 度 ２８０℃
圧 力 常 圧
（第３工程）
溶 剤 キシレン
溶 剤 比 第２工程の蒸留塔底液（ｉ＠分解重質
成分）に対し２倍量
熱分解重質成分 常圧下、約１００℃で流れる熱分と溶
剤の混合法 解重質成分の配管中に２倍量のキシレンを
送入、混合後クーラーに
て常温まで冷却。(1st step) Feed amount Refined heavy fraction 3 kp/hr Soluble component circulation @ 9 to 9/hr Total 12 klI/hr Circulation ratio (recycling ratio) 3 Pipe heating furnace Structure Inner diameter 6 fl, length 27.5 m A heating tube immersed in a molten salt bath.Heating tube outlet temperature: 510℃ Heating tube outlet pressure: 20kl? /cdG (2nd step) Distillation column Temperature 280℃ Pressure Normal pressure (3rd step) Solvent Decomposed heavy components A method of mixing heat flowing at approximately 100℃ under normal pressure and a solvent. Double the amount of xylene is sent into the decomposed heavy component piping, and after mixing, it is cooled to room temperature in a cooler.
不溶分の分離 分離機 石川島播磨重工業製ミニデカ
ンタ−
条 件 常温、常圧
（第４工程）
溶剤回収塔 塔頂温度 １４５℃塔底温度
２１０℃
圧 力 常 圧
この運転で得られた不溶性成分は精製重質成分に対して
９４．５％士あった。このものはキシレンとキシレン可
溶性成分を含んでいるので、さらに２倍量のキシレン中
に分散し、常温下に混合して前と同じ遠心分離機で再度
不溶性成分を分離回収することにより洗浄を行なった。Separation of insoluble matter Separator Mini decanter manufactured by Ishikawajima Harima Heavy Industries Conditions Normal temperature, normal pressure (4th step) Solvent recovery column Top temperature 145℃ Bottom temperature
210° C. Pressure Normal pressure The insoluble components obtained in this operation were 94.5% of the purified heavy components. Since this product contains xylene and xylene-soluble components, it is further dispersed in twice the amount of xylene, mixed at room temperature, and washed by separating and recovering the insoluble components using the same centrifuge as before. Ta.
洗浄を行なって得た不溶性成分を減圧下に加熱してキシ
レンを除去した不溶性成分すなわち高分子量歴青物を得
た。このものの収率は精製重質成分に対し３１．０％で
あり、キシレン不溶分７４．７％、キノリン不溶分０．
２％で全面等方性であった。また、この運転中、各工程
での生成物をサンプリングし、分析した結果は第３表の
様でありた。次にこの高分子量歴青物を３倍量の水素化
アントラセン油に混合溶解した後、内径１０ｍ、長さ１
００ｍの加熱管を溶融塩浴中に浸漬した構造を持つ管式
加熱炉において温度４４０℃、圧力５０ｋｌｉＦ／（−
ＪＱ、原料チャージ量６、５ ｋｇ／ ｈｒの条件で加
熱処理することにより連続的に水素化し、この処理液を
直ちにフラッシュ蒸留塔に送り常圧下、４００℃でフラ
ッシュ蒸留して水素化ピッチを得た。水素化ピッチの収
率は高分子量歴青物に対して８６．８％であり、軟化点
１３９℃（ＪＩＳ環球法）、キシレン不溶分５６．２％
、キノリン不溶分０．２％であった。The insoluble components obtained by washing were heated under reduced pressure to remove xylene and obtain high molecular weight bituminous components. The yield of this product was 31.0% based on the purified heavy components, 74.7% for xylene insolubles and 0.0% for quinoline insolubles.
At 2%, the entire surface was isotropic. Also, during this operation, products from each step were sampled and analyzed, and the results are shown in Table 3. Next, after mixing and dissolving this high molecular weight bituminous material in 3 times the amount of hydrogenated anthracene oil,
In a tube heating furnace with a structure in which a 00m heating tube was immersed in a molten salt bath, the temperature was 440℃ and the pressure was 50kliF/(-
JQ, continuous hydrogenation is performed by heat treatment at a raw material charge of 6.5 kg/hr, and the treated liquid is immediately sent to a flash distillation column and flash distilled at 400°C under normal pressure to obtain hydrogenated pitch. Ta. The yield of hydrogenated pitch was 86.8% based on the high molecular weight bituminous material, the softening point was 139°C (JIS ring and ball method), and the xylene insoluble content was 56.2%.
, the quinoline insoluble content was 0.2%.
さらにこの７に素化ピッチを重合フラスコに入れ常圧下
窒素を８０１ ／ｍｉｎ （水素化ピッチ１時当り）吹
き込みながら、４５０℃の塩浴中で４５〜５５分熱処理
した。得られたメンフェースヒツチの性状は第４表の様
であった。メソフェーズピッチの水素化ピッチに対する
収率は、実験番号１では７４％、実験番号２では７２％
であった。Further, hydrogenated pitch was placed in a polymerization flask and heat treated in a salt bath at 450 DEG C. for 45 to 55 minutes while blowing nitrogen at 801/min (per hour of hydrogenated pitch) under normal pressure. The properties of the obtained memphis hitch were as shown in Table 4. The yield of mesophase pitch to hydrogenated pitch was 74% in experiment number 1 and 72% in experiment number 2.
Met.
また第４表の実験番号２のメソフェーズピッチを径０．
２５ｗｘ、長さ０．７５ｍのノズル孔を持つ紡糸機にて
温度３３０℃、巻取速度７００ｍ／ｍｉｎで紡糸し、空
気中１’Ｃ／ｍｉｎの昇温速度で３２０℃まで昇温し、
３２０℃の温度で２０分加熱することにより不融化し、
続いて窒素雰囲気中１０００℃で炭化し、さらに２５０
０℃で黒鉛化した。得られた炭素線維の特性は第５表に
示す様であった。In addition, the mesophase pitch of experiment number 2 in Table 4 was set to a diameter of 0.
The fibers were spun at a temperature of 330°C and a winding speed of 700 m/min using a spinning machine with a nozzle hole of 25wx and a length of 0.75m, and the temperature was raised to 320°C at a heating rate of 1'C/min in air.
It becomes infusible by heating at a temperature of 320°C for 20 minutes,
Subsequently, it was carbonized at 1000°C in a nitrogen atmosphere, and further heated at 250°C.
It was graphitized at 0°C. The properties of the obtained carbon fibers were as shown in Table 5.
第２表 コールタール性状
第３表 、生成物の性状
第４表 メソフェーズピッチの性状
畳偏元顕微鏡で観察したときの光学的異方性を示す部分
の面積分率（以下の実施例、比較例においても同じ）第
５表 試作炭素繊維の物性
畳伸長率（以下の実施例、比較例においても同じ）実施
例２
′ 実施例１と同じ精製重質成分を原料として、運転条
件のうち第１工程の管式加熱炉における加熱処理の温度
−１ｔ５２０℃とする以外は実施例１と同一条件で第１
〜第４工程、さらに第４工程から第１工程への循環を行
なう運転な冥施し、第３工程から溶剤不溶性成分を得た
。この不溶性成分を２倍量のキシレンに分散した後遠心
分離するという洗浄操作を２回くりかえし、得られた不
溶性成分を減圧下に加熱してキシレンを除去し、高分子
量歴青物を得た。このもののキシレン不溶分は８３．５
％、キノリン不溶分は０．２％であった。また、その収
率はもとの精製重質成分に対して３８．９％であった。Table 2 Properties of coal tar Table 3 Properties of the product Table 4 Properties of mesophase pitch Area fraction of the part exhibiting optical anisotropy when observed with a convoluted polarizing microscope (Examples and Comparative Examples below) ) Table 5 Physical properties of trial carbon fiber Tatami elongation rate (same for the following examples and comparative examples) Example 2 ' Using the same purified heavy components as in Example 1 as raw material, the first operating condition was The first process was carried out under the same conditions as in Example 1 except that the temperature of the heat treatment in the tube heating furnace in the process was -1t520°C.
~4th step, further operation to perform circulation from the 4th step to the 1st step, and a solvent-insoluble component was obtained from the 3rd step. The washing operation of dispersing this insoluble component in twice the amount of xylene and then centrifuging was repeated twice, and the obtained insoluble component was heated under reduced pressure to remove xylene to obtain a high molecular weight bituminous material. The xylene insoluble content of this product is 83.5
%, and the quinoline insoluble content was 0.2%. Moreover, the yield was 38.9% based on the original purified heavy components.
この高分子量歴青物を実施例１と同様にして連続的に水
素化した後、熱処理してメトチー法軟化点３０３℃の紡
糸ピッチを得た。なお、水素化ピッチの高分子量歴青物
に対する収率は９４．６％、紡糸ピッチ（メソフェーズ
ピッチ）の水素化ピッチに対する収率は７６％であった
。This high molecular weight bituminous material was continuously hydrogenated in the same manner as in Example 1, and then heat treated to obtain a spinning pitch having a softening point of 303° C. by the Metochie process. The yield of hydrogenated pitch with respect to high molecular weight bituminous material was 94.6%, and the yield of spinning pitch (mesophase pitch) with respect to hydrogenated pitch was 76%.
この紡糸ピッチはメソフェーズが１００％であり、キノ
リン不溶分４．７％、キシレン可溶分５．３％であった
。また、この紡糸ピッチから前記と同様にして紡糸、不
融化、炭化および黒鉛化して得た炭素繊維の特性は第６
表に示す様であった。This spinning pitch contained 100% mesophase, 4.7% quinoline insoluble content, and 5.3% xylene soluble content. Furthermore, the properties of carbon fiber obtained by spinning, infusibility, carbonization and graphitization from this spinning pitch in the same manner as described above are as follows.
It was as shown in the table.
第６表 試作炭素繊維の物性
比較例１
実施例１で用いた精製重質成分を原料とし、この重質成
分の第１工程への送入量を１２ｋＪ／ｈｒ として管式
加熱炉における加熱処理を実施した。このとき第４工程
で得られる可溶性成分を第１工程に循環しない以外は実
施例１と同一条件で第１〜第４工程の運転を行なっ【、
第３工程から溶剤不溶性成分を回収し、これをキシレン
でもう一度洗浄して高分子量歴青物を得た。Table 6 Comparative example of physical properties of prototype carbon fiber 1 Heat treatment in a tube heating furnace using the purified heavy components used in Example 1 as raw materials and feeding the heavy components into the first step at a rate of 12 kJ/hr was carried out. At this time, the first to fourth steps were operated under the same conditions as in Example 1, except that the soluble component obtained in the fourth step was not recycled to the first step.
The solvent-insoluble components were recovered from the third step and washed once again with xylene to obtain a high molecular weight bituminous material.
このものの収率は精製重質成分に対して７．８％であっ
た。また、このもののキシレン不溶分は７０．９％、キ
ノリン不溶分は０．３％であった。The yield of this product was 7.8% based on the purified heavy components. Moreover, the xylene insoluble content of this product was 70.9%, and the quinoline insoluble content was 0.3%.
この高分子量歴青物を実施例１と同一条件で連続的に水
素化し、さらに熱処理してメトツー法軟化点２９９℃の
メソフェーズピッチを得た。This high molecular weight bituminous material was continuously hydrogenated under the same conditions as in Example 1, and further heat treated to obtain mesophase pitch having a softening point of 299°C by the metso method.
このものの組織はメソフェーズ１００％であり、キシレ
ン可溶分５．８％、キノリ／不溶分５．５％であった。The structure of this product was 100% mesophase, with a xylene soluble content of 5.8% and a xylene/insoluble content of 5.5%.
このメソフェーズピッチを実施例１と同様にして紡糸、
不融化後１０００℃で炭化して炭素繊維を製造し、その
物性を測定したところ繊維径は８．１μ、強度２８２ゆ
／−１弾性率１７．３ｔｏｎ／ｍｌ、伸度１．６３％で
あった。This mesophase pitch was spun in the same manner as in Example 1,
After infusibility, carbon fiber was produced by carbonization at 1000°C, and its physical properties were measured. The fiber diameter was 8.1 μ, the strength was 282 Y/-1, the elastic modulus was 17.3 ton/ml, and the elongation was 1.63%. Ta.
比較例２
比重１．３０２．キシレン不溶分３０．３％、キノリン
不溶分０．７％、軟化点９１℃（ＪＩＳ環球法）の性状
を持つ市販のピッチを４ｍ（５ｍｅｓｈ）以下の大きさ
に粉砕したもの１．５ ｋｇに２倍量のキシレン３ｋＩ
ｉを加え、攪拌しなからキシレンの沸点温度で６時間煮
沸溶解した。−晩放冷後、この混合物を遠心分離して不
溶性成分を採取し。Comparative Example 2 Specific gravity 1.302. A commercially available pitch with a xylene insoluble content of 30.3%, a quinoline insoluble content of 0.7%, and a softening point of 91°C (JIS ring and ball method) was ground to a size of 4 m (5 mesh) or less and weighed 1.5 kg. Double amount of xylene 3kI
i was added and dissolved by boiling at the boiling point temperature of xylene for 6 hours without stirring. - After cooling overnight, the mixture was centrifuged to collect insoluble components.
これにさらに３ｋｇのキシレンを加え、上記と同様圧し
て攪拌しながら６時間煮沸溶解した。放冷後、遠心分離
して不溶性成分を回収し、さらに３ゆのキシレンを用い
て上記同様の操作をもう一度実施した。得られた不溶性
成分を今度はアセトン中に分散した後グラスフィルター
でろ過することにより不溶性成分の洗浄を行なった。An additional 3 kg of xylene was added to this, and the mixture was boiled and dissolved for 6 hours while stirring under pressure in the same manner as above. After cooling, the insoluble components were recovered by centrifugation, and the same operation as above was carried out once again using 3 units of xylene. The obtained insoluble components were then dispersed in acetone and then filtered through a glass filter to wash the insoluble components.
これを減圧乾燥し【得た不溶性成分すなわち高分子量歴
青物はもとのど、チに対して３９．０％であり、キシレ
ン不溶分は８９．１％であった。This was dried under reduced pressure, and the obtained insoluble component, that is, a high molecular weight bituminous material, was 39.0% based on the original amount of chi, and the xylene insoluble content was 89.1%.
このものを水素化アントラセン油の３倍量に混合溶解し
たところかなりの不溶分が認められ、管式加熱炉による
連続的な水素化を実施することができなかった。そこで
、この混合物をオートクレーブに入れ、自生圧下に温度
４４０℃で６０分加熱処理することにより水素化した。When this product was mixed and dissolved in three times the amount of hydrogenated anthracene oil, a considerable amount of insoluble matter was found, and continuous hydrogenation using a tube heating furnace could not be carried out. Therefore, this mixture was placed in an autoclave and hydrogenated by heat treatment at a temperature of 440° C. for 60 minutes under autogenous pressure.
このときオートクレーブの最終圧力は１５３に９／ｃｌ
ｌ！ＧＫ達した。オートクレーブを放冷後、内容物を取
り出したところオートクレーブの内壁にコークス状の固
形物がかなり付着していた。また、この処理液をグラス
フィルターでろ過したところ水素化前の高分子量歴青物
に対して約１７％の不溶分が生成していることが認めら
れた。At this time, the final pressure of the autoclave was 153 to 9/cl.
l! GK reached. After the autoclave was left to cool, the contents were taken out and a considerable amount of coke-like solid matter was found adhering to the inner wall of the autoclave. Furthermore, when this treated solution was filtered through a glass filter, it was found that about 17% of insoluble matter was produced relative to the high molecular weight bituminous material before hydrogenation.
次にこのろ液を減圧蒸留して４００℃までの留分を除去
してもとのピッチに対して２９．９％の収率で水素化ピ
ッチを得た。これを実施例１と同様にして熱処理しメト
ツー法軟化点２９８℃のメソフェーズピッチを得た。こ
のものの組織はほぼメソフェーズｌＯＯ％でありまたキ
シレン可溶分９．７％、キノリン不溶分０．１％と均質
なものであった。Next, this filtrate was distilled under reduced pressure to remove fractions up to 400°C to obtain hydrogenated pitch at a yield of 29.9% based on the original pitch. This was heat-treated in the same manner as in Example 1 to obtain a mesophase pitch having a softening point of 298° C. by the metso method. The structure of this product was approximately 100% mesophase, and was homogeneous with a xylene soluble content of 9.7% and a quinoline insoluble content of 0.1%.
このメソフェーズピッチを実施例１と同様にして紡糸し
、不融化後１０００℃で炭化して得た炭素繊維の物性は
繊維径８．４μ、強度２１６に９／−１弾性率１５．６
ｔｏｎ／ｄ、伸度１．３９％であり、メソフェーズピ
ッチが均質であるにもかかわらず得られた炭素繊維の物
性は低いものであった。This mesophase pitch was spun in the same manner as in Example 1, and the physical properties of the carbon fiber obtained by carbonizing it at 1000°C after infusibility were as follows: fiber diameter 8.4μ, strength 216, 9/-1 elastic modulus 15.6.
ton/d and elongation of 1.39%, and although the mesophase pitch was homogeneous, the physical properties of the obtained carbon fiber were poor.
第１図は本発明の一つの実施態様を示す概略図である。
第１図において、１は精製重質成分タンク、３は芳香族
系油タンク、５は管式加熱炉、７は蒸留塔、１０は不溶
分分離機、１１はＢＴＸ溶剤タンク、１４は溶剤回収塔
である。
手 続 補 正 書
１．事件の表示
昭和６２年特許願第２８７１７３号
２、発明の名称
メソフェーズピッチの製造方法
３、補正をする者
事件との関係 特許出願人
名 称 丸善石油化学株式会社
４、代理人
住 所 埼玉県富士見市鶴瀬西３丁目１３番３１号５
、補正命令の日付 （自 発）
６、補正の対象
明細書の１発明の詳細な説明」の欄
７、補正の内容
（１）明細書第５９頁第２行の１精製抽出酸分らの」を
「精製重質成分からの」と訂正する。
（２）回書同頁第３行の「清澄液」を「可溶性成分」と
訂正する。FIG. 1 is a schematic diagram showing one embodiment of the present invention. In Figure 1, 1 is a purified heavy component tank, 3 is an aromatic oil tank, 5 is a tube heating furnace, 7 is a distillation column, 10 is an insoluble separator, 11 is a BTX solvent tank, and 14 is a solvent recovery It is a tower. Procedural amendment 1. Display of the case Patent Application No. 287173 filed in 1987 2 Name of the invention Method for producing mesophase pitch 3 Person making the amendment Relationship to the case Name of the patent applicant Title Maruzen Petrochemical Co., Ltd. 4 Agent address Fujimi City, Saitama Prefecture Tsuruse Nishi 3-13-31-5
, Date of amendment order (voluntary) 6. Column 7, ``Detailed explanation of the invention'' in the specification subject to amendment (1) Contents of the amendment (1) ``1 Purified extracted acid content, etc.'' on page 59, line 2 of the specification. is corrected to "from purified heavy components." (2) "Cleared liquid" in the third line of the same page of the circular is corrected to "soluble component."
Claims (14)
留、熱処理又は水素化処理して得られる重質成分であっ
て、実質的に単環の芳香族系炭化水素溶剤に不溶の成分
を含まないものであるか、もしくは上記重質油又は重質
成分に単環の芳香族系炭化水素溶剤またはこれと同等の
溶解性を持つ溶剤の該重質油又は重質成分に対して１〜
５重量倍量を加えたときに生成する不溶性成分を分離除
去した後に、溶剤を蒸留除去して得られる精製された重
質油又は重質成分を原料とし、該原料を沸点範囲が２０
０〜３５０℃の間にあり、かつ管式加熱炉における加熱
処理に際し、実質的に単環の芳香族系炭化水素溶剤に不
溶の成分を生成しない芳香族系油の上記原料に対して１
重量倍量以下の存在下又は非存在下に管式加熱炉におい
て加圧下に温度４００〜６００℃の条件で加熱処理して
、実質的にキノリン不溶分を生成させることなく、キシ
レン不溶分を加熱処理物中に３〜３０重量％生成させる
連続的な第１工程と、第１工程で得られた加熱処理物を
３５０℃以下の温度で蒸留又はブラッシングして、軽質
成分の一部を除き、熱分解重質成分を得る連続的な第２
工程と、該熱分解重質成分に単環の芳香族系炭化水素溶
剤又はこれと同等の溶解性を持つ溶剤を該熱分解重質成
分に対して１〜５重量倍量加え、生成する不溶性成分を
分離回収して高分子量歴青物を得る連続的な第３工程と
、第３工程で不溶分を除去した清澄液から溶剤を蒸留除
去して単環の芳香族系炭化水素溶剤に可溶の成分を得る
連続的な第４工程とから成る水素化用原料調整工程にお
いて、第４工程で得られる可溶性成分の全部又は一部を
第１工程に循環しながら第１〜第４工程を連続的に実施
することにより、第３工程から高分子量歴青物を得、該
高分子量歴青物を水素供与性溶媒の存在下に加熱処理す
ることにより水素化した後、溶媒を除去して実質的に等
方性の水素化ピッチを得、これをさらに加熱処理するこ
とによりメソフェーズピッチとすることを特徴とする高
性能炭素繊維製造用メソフェーズピッチの製造方法。(1) Coal-based heavy oil, petroleum-based heavy oil, or a heavy component obtained by distilling, heat-treating, or hydrotreating them, which is substantially insoluble in monocyclic aromatic hydrocarbon solvents. or a monocyclic aromatic hydrocarbon solvent or a solvent with an equivalent solubility in the heavy oil or heavy components. 1~
After separating and removing the insoluble components produced when 5 times the amount by weight is added, the purified heavy oil or heavy components obtained by distilling off the solvent is used as a raw material, and the raw material is used as a raw material with a boiling point range of 20
1 for the above raw material of aromatic oil that is between 0 and 350°C and does not produce substantially components insoluble in monocyclic aromatic hydrocarbon solvents during heat treatment in a tube heating furnace.
Heat treatment in a tube heating furnace under pressure at a temperature of 400 to 600°C in the presence or absence of a weight equal to or less than twice the amount by weight to heat xylene insolubles without substantially producing quinoline insolubles. A continuous first step of producing 3 to 30% by weight in the treated product, and distilling or brushing the heat-treated product obtained in the first step at a temperature of 350 ° C. or less to remove some of the light components, continuous second to obtain pyrolysis heavy components
step, adding a monocyclic aromatic hydrocarbon solvent or a solvent with an equivalent solubility to the pyrolyzed heavy component in an amount of 1 to 5 times the weight of the pyrolyzed heavy component to produce an insoluble A continuous third step in which components are separated and recovered to obtain a high molecular weight bituminous material, and the solvent is distilled off from the clarified liquid from which insoluble matter has been removed in the third step, making it soluble in monocyclic aromatic hydrocarbon solvents. In the hydrogenation raw material preparation step consisting of a continuous fourth step to obtain the components, the first to fourth steps are carried out continuously while circulating all or part of the soluble components obtained in the fourth step to the first step. A high molecular weight bituminous material is obtained from the third step, and the high molecular weight bituminous material is hydrogenated by heat treatment in the presence of a hydrogen-donating solvent, and then the solvent is removed to substantially A method for producing mesophase pitch for producing high-performance carbon fibers, which comprises obtaining isotropic hydrogenated pitch and further heat-treating it to produce mesophase pitch.
、管式加熱炉の出口において温度４００〜６００℃、圧
力１〜１００ｋｇ／ｃｍ＾２Ｇである特許請求の範囲第
１項に記載の方法。(2) Conditions for the heat treatment in the tube heating furnace in the first step are a temperature of 400 to 600°C and a pressure of 1 to 100 kg/cm^2G at the outlet of the tube heating furnace. the method of.
度４５０〜５５０℃、圧力２〜５０ｋｇ／ｃｍ＾２Ｇで
ある特許請求の範囲第２項に記載の方法。(3) The method according to claim 2, wherein the heat treatment conditions are a temperature of 450 to 550°C and a pressure of 2 to 50 kg/cm^2G at the outlet of the tube heating furnace.
する循環量が原料の重質油又は重質成分に対して１重量
倍量以上である特許請求の範囲第１項に記載の方法。(4) The method according to claim 1, wherein the circulating amount of the soluble component obtained in the fourth step to the first step is at least 1 times the weight of the heavy oil or heavy component as the raw material. Method.
範囲第４項に記載の方法。(5) The method according to claim 4, wherein the circulating amount is in the range of 2 to 6 times the weight.
が、該高分子量歴青物に対して１〜５重量倍量の水素供
与性溶媒の存在下に、管式加熱炉において、温度４００
〜４６０℃、圧力２０〜１００ｋｇ／ｃｍ＾２Ｇの条件
下に連続的に実施される特許請求の範囲第１項に記載の
方法。(6) Hydrogenation of the high molecular weight bituminous material obtained in the third step is carried out in a tube heating furnace at a temperature of 1 to 5 times the weight of the high molecular weight bituminous material. 400
The method according to claim 1, which is carried out continuously under conditions of ~460[deg.] C. and a pressure of 20 to 100 kg/cm^2G.
を、該高分子量歴青物に対して１〜５重量倍量の水素供
与性溶媒の存在下に、管式加熱炉において、温度４００
〜４６０℃、圧力２０〜１００ｋｇ／ｃｍ＾２Ｇの条件
下に連続的に実施し、続いて水素化処理された処理液を
蒸留塔において、圧力０〜３ｋｇ／ｃｍ＾２Ａ、温度３
００〜５３０℃の条件下に蒸留して、該蒸留塔底から水
素化されたピッチを連続的に得る特許請求の範囲第１項
に記載の方法。(7) Hydrogenation of the high molecular weight bituminous material obtained in the third step is carried out in a tube heating furnace at a temperature of 1 to 5 times the weight of the high molecular weight bituminous material. 400
The hydrogenation treatment was carried out continuously under the conditions of ~460°C and a pressure of 20 to 100 kg/cm^2G, and then the hydrogenated treated liquid was placed in a distillation column at a pressure of 0 to 3 kg/cm^2A and a temperature of 3
The method according to claim 1, wherein hydrogenated pitch is continuously obtained from the bottom of the distillation column by distillation under conditions of 00 to 530°C.
下もしくは常圧下に、不活性ガスの吹き込み又は流通下
に、温度３５０〜５００℃の条件下に実施される特許請
求の範囲第１項に記載の方法。(8) The heat treatment of the hydrogenated high molecular weight bituminous material is carried out at a temperature of 350 to 500°C under reduced pressure or normal pressure, with inert gas blowing or flowing. The method described in Section 1.
ンおよびキシレンからなる群から選択された少なくとも
一種である特許請求の範囲第１項に記載の方法。(9) The method according to claim 1, wherein the monocyclic aromatic hydrocarbon solvent is at least one selected from the group consisting of benzene, toluene, and xylene.
素溶剤である特許請求の範囲第１項に記載の方法。(10) The method according to claim 1, wherein the solvent used in the third step is a monocyclic aromatic hydrocarbon solvent.
重質成分および第２工程で得られる熱分解重質成分が、
沸点範囲２００〜３５０℃にある軽質成分を少なくとも
１０重量％以上含み、かつ１００℃における粘度が１０
００センチストークス以下である特許請求の範囲第１項
に記載の方法。(11) The heavy oil or heavy components fed as raw materials to the first step and the pyrolyzed heavy components obtained in the second step,
Contains at least 10% by weight of light components with a boiling point range of 200 to 350°C, and has a viscosity of 10% at 100°C.
2. The method according to claim 1, wherein the particle size is less than or equal to 0.00 centistokes.
不溶分１重量％以下、キシレン不溶分４０重量％以上で
あり、かつ光学的に等方性の高分子量歴青物である特許
請求の範囲第１項に記載の方法。(12) The claim that the high molecular weight bituminous material obtained in the third step has a quinoline insoluble content of 1% by weight or less, a xylene insoluble content of 40% by weight or more, and is an optically isotropic high molecular weight bituminous material. The method described in paragraph 1.
であり、環球法軟化点が１００〜２００℃、キノリン不
溶分が１重量％以下、キシレン不溶分が４０重量％以上
である特許請求の範囲第１項に記載の方法。(13) The hydrogenated pitch is substantially optically isotropic, has a ring and ball softening point of 100 to 200°C, has a quinoline insoluble content of 1% by weight or less, and a xylene insoluble content of 40% by weight or more. A method according to claim 1.
℃以下、偏光顕微鏡で観察したときの光学的異方性を示
す部分の面積分率によるメソフェーズ含有量が９０％以
上、キノリン不溶分が１０重量％以下、そしてキシレン
可溶分が１０重量％以下の特性を有する特許請求の範囲
第１項に記載の方法。(14) Mesophase pitch has a Mettler softening point of 310
℃ or less, the mesophase content as determined by the area fraction of the part exhibiting optical anisotropy when observed with a polarizing microscope is 90% or more, the quinoline insoluble content is 10% by weight or less, and the xylene soluble content is 10% by weight or less A method according to claim 1 having the characteristics of:
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62287173A JPH01129092A (en) | 1987-11-13 | 1987-11-13 | Production of mesophase pitch |
| CA000568935A CA1302934C (en) | 1987-06-18 | 1988-06-08 | Process for preparing pitches |
| DE8888109645T DE3869855D1 (en) | 1987-06-18 | 1988-06-16 | METHOD FOR PRODUCING PECH. |
| EP90109689A EP0393724B1 (en) | 1987-06-18 | 1988-06-16 | Process for preparing mesophase pitches |
| DE9090109689T DE3881058T2 (en) | 1987-06-18 | 1988-06-16 | METHOD FOR MESOPHASE-PECHE PRODUCTION. |
| EP88109645A EP0299222B1 (en) | 1987-06-18 | 1988-06-16 | Process for preparing pitches |
| AU17709/88A AU603223B2 (en) | 1987-06-18 | 1988-06-16 | Process for preparing pitches |
| CN88103678A CN1020621C (en) | 1987-06-18 | 1988-06-18 | Method for preparing asphalt |
| KR1019880007382A KR930005526B1 (en) | 1987-06-18 | 1988-06-18 | Process for preparing pithces |
| US07/504,723 US5091072A (en) | 1987-06-18 | 1990-04-03 | Process for preparing pitches |
| AU60958/90A AU624986B2 (en) | 1987-06-18 | 1990-08-10 | Process for preparing pitches |
| US07/616,836 US5182011A (en) | 1987-06-18 | 1990-11-21 | Process for preparing pitches |
| CN 92112544 CN1032922C (en) | 1987-06-18 | 1992-10-31 | Process for preparing mesophase pitches |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62287173A JPH01129092A (en) | 1987-11-13 | 1987-11-13 | Production of mesophase pitch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01129092A true JPH01129092A (en) | 1989-05-22 |
| JPH048474B2 JPH048474B2 (en) | 1992-02-17 |
Family
ID=17714023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62287173A Granted JPH01129092A (en) | 1987-06-18 | 1987-11-13 | Production of mesophase pitch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01129092A (en) |
-
1987
- 1987-11-13 JP JP62287173A patent/JPH01129092A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH048474B2 (en) | 1992-02-17 |
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