WO2011048920A1 - Reformed tar, process for production of reformed tar, process for production of raw coke, and process for production of needle coke - Google Patents
Reformed tar, process for production of reformed tar, process for production of raw coke, and process for production of needle coke Download PDFInfo
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- WO2011048920A1 WO2011048920A1 PCT/JP2010/067027 JP2010067027W WO2011048920A1 WO 2011048920 A1 WO2011048920 A1 WO 2011048920A1 JP 2010067027 W JP2010067027 W JP 2010067027W WO 2011048920 A1 WO2011048920 A1 WO 2011048920A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/20—Refining by chemical means inorganic or organic compounds
- C10C1/205—Refining by chemical means inorganic or organic compounds refining in the presence of hydrogen
Definitions
- the present invention relates to a modified tar, a modified tar production method, a raw coke production method, and a needle coke production method.
- Needle coke exhibits an oriented fibrous structure, and has a structure that is easily graphitized with a well-developed carbon hexagonal network surface along the flow pattern.
- Such needle coke is manufactured using petroleum-based or coal-based heavy oil as a raw material. Specifically, the solid content is removed from the pitch, followed by distillation purification, and the purified pitch is coked. It is manufactured through processes such as a step of obtaining coke and a step of calcining raw coke.
- Coal heavy oil includes coal-based high-temperature tar and coal-based low-temperature tar. Coal-based high-temperature tar is produced in a coke oven when coal is dry-distilled at a temperature of 1000 to 1250 ° C.
- Coal-based low-temperature tar is a by-product oil produced from a Lurgi-type coal gasification process (500 to 800 ° C.) or a coke oven (about 600 ° C.) under low-temperature carbonization conditions.
- coal-based high-temperature tar is used and obtained by distillation of the coal-based high-temperature tar.
- Raw materials for needle coke production are manufactured based on the pitch.
- coal-based low-temperature tar has an aromatic component as the main component, as is the case with coal-based high-temperature tar.
- the polarity contains heteroatoms such as oxygen, sulfur, and nitrogen in the molecule. It has the feature of containing many molecular components.
- the pitch obtained from coal-based low-temperature tar contains a large amount of polar molecular components.
- the pitch obtained from such coal-based low-temperature tar is heat-treated and coked, only raw coke with an undeveloped flow structure such as a mixed structure with isotropic structures and small units of flow structure is obtained.
- a raw coke having a structure suitable for producing needle coke exhibits a continuous phase called a flow structure, and its size is 100 ⁇ m or more.
- the raw coke obtained from the coal-based low-temperature tar or pitch contains many fine structures called fine mosaic structures (sizes of 10 ⁇ m or less) or coarse mosaic structures (sizes greater than 10 ⁇ m to less than 100 ⁇ m).
- the conventional polar low molecular weight tar cannot be selectively removed from the polar molecular component, which is a component inhibiting the development of the flow structure.
- formation of a flow structure was hindered when heat treatment was performed to obtain raw coke.
- coal-based low-temperature tar cannot be used as a raw material for needle coke production.
- the presence of heteroatoms such as sulfur and nitrogen causes puffing when an artificial graphite material such as a steelmaking electrode is produced using the obtained needle coke.
- the present invention provides a modified tar capable of providing raw coke and needle coke suitable for needle coke production by modifying coal-based low-temperature tar or coal-based pitch obtained from coal-based low-temperature tar. It is to provide.
- the characteristic constitution of the modified tar production method of the present invention is characterized in that coal-based low-temperature tar or 100 mass parts of coal-based pitch obtained by removing light components of coal-based low-temperature tar has hydrogen donating properties. 30 to 300 parts by mass of a solvent is added and the mixture is held at 380 to 450 ° C. for 0.1 to 4 hours under a pressure of 0.3 to 5.0 MPa.
- the hydrogen donating solvent is preferably ethylene bottom oil or FCC decant oil.
- coal-based low-temperature tar or coal-based pitch obtained by removing light components of coal-based low-temperature tar from the coal-based low-temperature tar by distillation or the like is used as the raw material.
- this raw material is mixed with a hydrogen-donating solvent and subjected to heat treatment under pressure, when the component having a heteroatom contained in the raw material is subjected to a reducing action by the hydrogen-donating biosolvent, the raw material is decomposed. Since the hetero atoms are removed from the system by lowering the molecular weight, etc., it is considered that the modified tar is subjected to a modification action and can produce high-quality needle coke.
- the amount of the hydrogen donating solvent added to the coal-based low-temperature tar or coal-based pitch is too small, sufficient reforming action cannot be obtained, and if it is too large, the cost-effectiveness becomes inefficient.
- 30 to 300 parts by mass per 100 parts by mass of the raw material is preferable. More preferably, it is 50 to 100 parts by mass.
- the characteristic configuration of the modified tar of the present invention is obtained by the above-described modified tar production method, wherein the oxygen content is 3.0% by mass or less and the nitrogen content is 1.3% by mass or less, or The number average molecular weight is 100 to 300, which is obtained by the above modified tar production method.
- the modified tar obtained by the above production method has the following characteristics in terms of molecular weight and molecular structure. Therefore, it is considered that it is suitable as a raw material for producing raw coke.
- An example of the average molecular weight calculated from the molecular weight distribution measured by FD-MS (field desorption ionization mass spectrometry) shows that the number average molecular weight (Mn) of coal-based pitch prepared by distilling high-temperature tar is 717, coal The Mn of the pitch derived from the low temperature tar was 538, and the Mn of the modified tar was 169. That is, the molecular weight is smaller than that of the raw material such as coal-based pitch.
- Pitch derived from coal-based high-temperature tar has a C / H (mass ratio, the same applies hereinafter) of about 20 according to elemental analysis and almost no oxygen, so it is composed of polycyclic aromatic molecules with an average of 4 to 6 rings. It is thought that.
- C / H mass ratio
- C / O mass ratio
- three polycyclic aromatic molecules with an average of 2 to 3 rings are oxygen atoms.
- the molecular structure is presumed to be cross-linked. That is, it can be seen that the obtained modified tar has a C / O of 34 or more and a composition with very few heteroatoms.
- the characteristic configuration of the method for producing raw coke according to the present invention is that the modified tar is heat-treated at a temperature at which raw coke is formed.
- a heating rate of, for example, about 5 to 50 ° C./min can be selected, and a flow structure can be easily formed from the modified tar. .
- the characteristic configuration of the needle coke production method of the present invention is that the raw coke obtained by the above-described method for producing raw coke is calcined.
- Raw coke is a high-molecular-weight hydrocarbon in which bound hydrogen and the like remain, but by calcination, removal of volatile components, dehydration, thermal decomposition, combustion removal of easily oxidizable structures, polymerization by solid phase reaction, polymerization, etc. After that, it changes into a stable compound.
- needle coke is manufactured using the above-mentioned raw coke, a good-quality needle coke with sufficiently developed oriented fibrous structure can be obtained.
- a heat treatment apparatus for heating raw coke to 800 ° C. to 1400 ° C. can be used, and industrially a rotary kiln called a calsiner is used.
- the method for producing the raw coke and the method for producing the needle coke, the raw material for producing the electrode for steelmaking, the special carbon material, the high-quality carbon fiber, and the graphite material for the battery It is suitable as.
- the modified tar of the present invention the modified tar production method, the raw coke production method, and the needle coke production method will be described.
- preferred examples will be described. These examples are described in order to more specifically illustrate the present invention, and various modifications can be made without departing from the spirit of the present invention.
- the present invention is not limited to the following description.
- Example 1 A coal-based low-temperature tar which is a by-product oil of the Lurgi-type coal gasification process was used.
- the coal-based low-temperature tar was distilled by a conventional method to remove light components and obtain a coal-based pitch.
- the physical properties of coal-based pitch are as follows. The oxygen content and nitrogen content were determined by elemental analysis.
- FIG. 1 shows a caulking experiment apparatus.
- About 50 g of the sample 2 is put into a Pyrex (registered trademark) test tube 1 having an outer diameter of 40 mm, an inner diameter of 37 mm, and a length of 300 mm.
- a glass tube 3 with an outer diameter of 10 mm and an inner diameter of 8 mm for introducing nitrogen gas into the test tube 1 and a glass tube 4 with an outer diameter of 10 mm and an inner diameter of 8 mm for exhausting nitrogen gas and volatile matter generated from the sample are inserted, and silicon
- the upper part of the test tube is sealed with a rubber stopper 5.
- Coke is embedded in resin, the surface is polished, and then observed with a polarizing microscope having an observation magnification of about 200 times.
- About 10 images are taken into a computer as digital images having an area of 44 ⁇ m ⁇ 34 ⁇ m per observation image, and divided into squares of 2 ⁇ m ⁇ 2 ⁇ m on the computer.
- the divided cells are visually classified into a flow structure, a course mosaic structure, and a fine mosaic structure, and 1250 or more cells (5000 ⁇ m 2 or more) are inspected, and the area ratio of each tissue is obtained by determining the number ratio of the cells. Calculate the percentage.
- the area ratio of the flow structure contained in the raw coke was 100%.
- the obtained raw coke was calcined in the same manner as in Example 1.
- the structure of the obtained calcined product was confirmed by a polarizing microscope, it was found that the coke was a needle coke having an oriented fibrous structure developed as shown in FIG.
- Example 4 The same coal pitch as in Example 1 was directly coked to obtain raw coke.
- tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 14, it was raw coke with insufficient flow tissue development.
- the area ratio of the flow structure contained in the raw coke was 44%.
- the area ratio of the fine mosaic structure was 22%, and the area ratio of the course mosaic structure was 34%.
- the method for producing the raw coke and the method for producing the needle coke, the raw material for producing the electrode for steelmaking, the special carbon material, the high-quality carbon fiber, and the graphite material for the battery It is suitable as.
- Test tube 2 Sample 3 Glass tube 4 Glass tube 5 Rubber stopper 6 Heater 7 Molten salt bath
Abstract
Provided is a reformed tar which can provide both a needle coke and a raw coke suitable for the production of a needle coke. The reformed tar can be produced by adding 30 to 300 parts by mass of a hydrogen-donating solvent to 100 parts by mass of either a low-temperature coal tar or a coal tar pitch obtained by removing a light fraction from a low-temperature coal tar, and then keeping the obtained mixture under a pressure of 0.3 to 5.0MPa at a temperature of 380 to 450°C for 0.1 to 4 hours.
Description
本発明は、改質タール並びに改質タールの製造方法、生コークスの製造方法及びニードルコークスの製造方法に関する。
The present invention relates to a modified tar, a modified tar production method, a raw coke production method, and a needle coke production method.
ニードルコークスは配向繊維状組織を示し、流れ模様に沿って、炭素六角網面が良く発達した黒鉛化しやすい組織を有している。このようなニードルコークスは、石油系、石炭系の重質油を原料として製造され、具体的には、ピッチから固形分を除去した後、蒸留精製する工程、精製されたピッチをコーキングして生コークスを得る工程、生コークスをか焼する工程等のプロセスを経て製造される。
石炭系の重質油には、石炭系高温タールと石炭系低温タールとがある。石炭系高温タールは、コークス炉において、石炭を１０００～１２５０℃の温度で乾留すると、炉内で生成する熱的に不安定な化合物が分解、重合、その他の反応が進行する中で、石炭に対し約３％程度が、ガスとともに液状物として炉外に取り出されるものである。石炭系低温タールは、ルルギ式石炭ガス化プロセス（５００～８００℃）や、低温乾留条件のコークス炉（約６００℃）などから生成する副生油である。 Needle coke exhibits an oriented fibrous structure, and has a structure that is easily graphitized with a well-developed carbon hexagonal network surface along the flow pattern. Such needle coke is manufactured using petroleum-based or coal-based heavy oil as a raw material. Specifically, the solid content is removed from the pitch, followed by distillation purification, and the purified pitch is coked. It is manufactured through processes such as a step of obtaining coke and a step of calcining raw coke.
Coal heavy oil includes coal-based high-temperature tar and coal-based low-temperature tar. Coal-based high-temperature tar is produced in a coke oven when coal is dry-distilled at a temperature of 1000 to 1250 ° C. On the other hand, about 3% is taken out of the furnace as a liquid together with the gas. Coal-based low-temperature tar is a by-product oil produced from a Lurgi-type coal gasification process (500 to 800 ° C.) or a coke oven (about 600 ° C.) under low-temperature carbonization conditions.
石炭系の重質油には、石炭系高温タールと石炭系低温タールとがある。石炭系高温タールは、コークス炉において、石炭を１０００～１２５０℃の温度で乾留すると、炉内で生成する熱的に不安定な化合物が分解、重合、その他の反応が進行する中で、石炭に対し約３％程度が、ガスとともに液状物として炉外に取り出されるものである。石炭系低温タールは、ルルギ式石炭ガス化プロセス（５００～８００℃）や、低温乾留条件のコークス炉（約６００℃）などから生成する副生油である。 Needle coke exhibits an oriented fibrous structure, and has a structure that is easily graphitized with a well-developed carbon hexagonal network surface along the flow pattern. Such needle coke is manufactured using petroleum-based or coal-based heavy oil as a raw material. Specifically, the solid content is removed from the pitch, followed by distillation purification, and the purified pitch is coked. It is manufactured through processes such as a step of obtaining coke and a step of calcining raw coke.
Coal heavy oil includes coal-based high-temperature tar and coal-based low-temperature tar. Coal-based high-temperature tar is produced in a coke oven when coal is dry-distilled at a temperature of 1000 to 1250 ° C. On the other hand, about 3% is taken out of the furnace as a liquid together with the gas. Coal-based low-temperature tar is a by-product oil produced from a Lurgi-type coal gasification process (500 to 800 ° C.) or a coke oven (about 600 ° C.) under low-temperature carbonization conditions.
従来、石炭系タールを使用してニードルコークスを製造する場合において、特許文献１、２に示すように、通常、前記石炭系高温タールが用いられており、石炭系高温タールを蒸留して得られたピッチを基にニードルコークス製造用の原料が製造されている。
一方、石炭系低温タールは、石炭系高温タールと同様に芳香族成分が主成分であるが、石炭系高温タールと比較して、酸素、硫黄、窒素などのヘテロ原子を分子中に含んだ極性分子成分を多く含むという特徴を有する。また、石炭系低温タールから得られたピッチにも極性分子成分を多く含む。そのため、このような石炭系低温タールから得られたピッチを熱処理してコーキングしても等方性組織が入り混じった組織や流れ組織の単位が小さい等の流れ組織が未発達の生コークスしか得られない。具体的にはニードルコークスを製造するために適した組織の生コークスは流れ組織と呼ばれる連続相を示しており、そのサイズは１００μｍ以上である。一方、上記石炭系低温タールあるいはピッチから得られる生コークスはファインモザイク組織（サイズ１０μｍ以下）もしくはコースモザイク組織（サイズ１０μｍ超～１００μｍ未満）と呼ばれる微細な組織を多く含む。また、反応性が高く高粘度化しやすいという特徴も同時に有するので、生コークスを得るために熱処理する際、上記のように流れ組織の形成が阻害されてしまう。従って、そのような生コークスを使用してニードルコークスを製造しようとしても、配向繊維状組織が発達した良質なニードルコークスが得られにくい状況であった。 Conventionally, in the case of producing needle coke using coal-based tar, as shown in Patent Documents 1 and 2, usually, the coal-based high-temperature tar is used and obtained by distillation of the coal-based high-temperature tar. Raw materials for needle coke production are manufactured based on the pitch.
On the other hand, coal-based low-temperature tar has an aromatic component as the main component, as is the case with coal-based high-temperature tar. However, compared with coal-based high-temperature tar, the polarity contains heteroatoms such as oxygen, sulfur, and nitrogen in the molecule. It has the feature of containing many molecular components. Also, the pitch obtained from coal-based low-temperature tar contains a large amount of polar molecular components. Therefore, even if the pitch obtained from such coal-based low-temperature tar is heat-treated and coked, only raw coke with an undeveloped flow structure such as a mixed structure with isotropic structures and small units of flow structure is obtained. I can't. Specifically, a raw coke having a structure suitable for producing needle coke exhibits a continuous phase called a flow structure, and its size is 100 μm or more. On the other hand, the raw coke obtained from the coal-based low-temperature tar or pitch contains many fine structures called fine mosaic structures (sizes of 10 μm or less) or coarse mosaic structures (sizes greater than 10 μm to less than 100 μm). Moreover, since it has the characteristics that it is highly reactive and easily increases in viscosity, the formation of a flow structure is inhibited as described above when heat treatment is performed to obtain raw coke. Therefore, even if an attempt is made to produce needle coke using such raw coke, it is difficult to obtain good quality needle coke with developed oriented fibrous structure.
一方、石炭系低温タールは、石炭系高温タールと同様に芳香族成分が主成分であるが、石炭系高温タールと比較して、酸素、硫黄、窒素などのヘテロ原子を分子中に含んだ極性分子成分を多く含むという特徴を有する。また、石炭系低温タールから得られたピッチにも極性分子成分を多く含む。そのため、このような石炭系低温タールから得られたピッチを熱処理してコーキングしても等方性組織が入り混じった組織や流れ組織の単位が小さい等の流れ組織が未発達の生コークスしか得られない。具体的にはニードルコークスを製造するために適した組織の生コークスは流れ組織と呼ばれる連続相を示しており、そのサイズは１００μｍ以上である。一方、上記石炭系低温タールあるいはピッチから得られる生コークスはファインモザイク組織（サイズ１０μｍ以下）もしくはコースモザイク組織（サイズ１０μｍ超～１００μｍ未満）と呼ばれる微細な組織を多く含む。また、反応性が高く高粘度化しやすいという特徴も同時に有するので、生コークスを得るために熱処理する際、上記のように流れ組織の形成が阻害されてしまう。従って、そのような生コークスを使用してニードルコークスを製造しようとしても、配向繊維状組織が発達した良質なニードルコークスが得られにくい状況であった。 Conventionally, in the case of producing needle coke using coal-based tar, as shown in
On the other hand, coal-based low-temperature tar has an aromatic component as the main component, as is the case with coal-based high-temperature tar. However, compared with coal-based high-temperature tar, the polarity contains heteroatoms such as oxygen, sulfur, and nitrogen in the molecule. It has the feature of containing many molecular components. Also, the pitch obtained from coal-based low-temperature tar contains a large amount of polar molecular components. Therefore, even if the pitch obtained from such coal-based low-temperature tar is heat-treated and coked, only raw coke with an undeveloped flow structure such as a mixed structure with isotropic structures and small units of flow structure is obtained. I can't. Specifically, a raw coke having a structure suitable for producing needle coke exhibits a continuous phase called a flow structure, and its size is 100 μm or more. On the other hand, the raw coke obtained from the coal-based low-temperature tar or pitch contains many fine structures called fine mosaic structures (sizes of 10 μm or less) or coarse mosaic structures (sizes greater than 10 μm to less than 100 μm). Moreover, since it has the characteristics that it is highly reactive and easily increases in viscosity, the formation of a flow structure is inhibited as described above when heat treatment is performed to obtain raw coke. Therefore, even if an attempt is made to produce needle coke using such raw coke, it is difficult to obtain good quality needle coke with developed oriented fibrous structure.
また、硫黄、窒素などのヘテロ原子がニードルコークス中に多く存在すると、ニードルコークスを使用して製鋼用電極などの人造黒鉛材料を製造する際にパッフィングが起こることが知られている。パッフィングとは黒鉛化工程における不可逆的な異常熱膨張現象をいい、これが発生すると固有抵抗値、機械的強度などの特性の劣化を招くので、この発生を抑える必要がある。
特許文献３には、予めキノリン不溶分を除いたコールタール系重質油と石油系重質油とを窒素及び硫黄分を一定量以下になる割合に混合して、生コークスにした後、２段階のか焼を行うことにより、パッフィングの発生が改善されるニードルコークスが提供されることが報告されている。 In addition, it is known that when there are many heteroatoms such as sulfur and nitrogen in needle coke, puffing occurs when an artificial graphite material such as a steelmaking electrode is produced using needle coke. Puffing refers to an irreversible abnormal thermal expansion phenomenon in the graphitization process. If this phenomenon occurs, it causes deterioration of properties such as specific resistance value and mechanical strength. Therefore, it is necessary to suppress this occurrence.
InPatent Document 3, coal tar heavy oil and petroleum heavy oil from which quinoline-insoluble components have been removed in advance are mixed in a ratio of nitrogen and sulfur to a certain amount or less to obtain a raw coke. It has been reported that performing step calcination provides needle coke with improved puffing.
特許文献３には、予めキノリン不溶分を除いたコールタール系重質油と石油系重質油とを窒素及び硫黄分を一定量以下になる割合に混合して、生コークスにした後、２段階のか焼を行うことにより、パッフィングの発生が改善されるニードルコークスが提供されることが報告されている。 In addition, it is known that when there are many heteroatoms such as sulfur and nitrogen in needle coke, puffing occurs when an artificial graphite material such as a steelmaking electrode is produced using needle coke. Puffing refers to an irreversible abnormal thermal expansion phenomenon in the graphitization process. If this phenomenon occurs, it causes deterioration of properties such as specific resistance value and mechanical strength. Therefore, it is necessary to suppress this occurrence.
In
以上、従来石炭系低温タールから、流れ組織の発達を阻害する成分である極性分子成分を選択的に除去できない状況にあった。また、反応性が高く高粘度化しやすいという特徴によっても生コークスを得るために熱処理する際、流れ組織の形成が阻害されてしまう状況にあった。そのため、石炭系低温タールをニードルコークス製造用の原料として使用できない状況にあった。
また、硫黄、窒素などのヘテロ原子の存在は、得られたニードルコークスを使用して製鋼用電極などの人造黒鉛材料を製造する際にパッフィングの発生を招くことになる。 As described above, the conventional polar low molecular weight tar cannot be selectively removed from the polar molecular component, which is a component inhibiting the development of the flow structure. In addition, due to the feature of high reactivity and high viscosity, formation of a flow structure was hindered when heat treatment was performed to obtain raw coke. For this reason, coal-based low-temperature tar cannot be used as a raw material for needle coke production.
In addition, the presence of heteroatoms such as sulfur and nitrogen causes puffing when an artificial graphite material such as a steelmaking electrode is produced using the obtained needle coke.
また、硫黄、窒素などのヘテロ原子の存在は、得られたニードルコークスを使用して製鋼用電極などの人造黒鉛材料を製造する際にパッフィングの発生を招くことになる。 As described above, the conventional polar low molecular weight tar cannot be selectively removed from the polar molecular component, which is a component inhibiting the development of the flow structure. In addition, due to the feature of high reactivity and high viscosity, formation of a flow structure was hindered when heat treatment was performed to obtain raw coke. For this reason, coal-based low-temperature tar cannot be used as a raw material for needle coke production.
In addition, the presence of heteroatoms such as sulfur and nitrogen causes puffing when an artificial graphite material such as a steelmaking electrode is produced using the obtained needle coke.
本発明は、上記実情に鑑み、石炭系低温タールあるいは石炭系低温タールから得られる石炭系ピッチを改質することにより、ニードルコークスの製造に適した生コークス及びニードルコークスを提供できる改質タールを提供することにある。
In view of the above circumstances, the present invention provides a modified tar capable of providing raw coke and needle coke suitable for needle coke production by modifying coal-based low-temperature tar or coal-based pitch obtained from coal-based low-temperature tar. It is to provide.
〔構成〕
上記目的を達成するための本発明の改質タールの製造方法の特徴構成は、石炭系低温タールまたは石炭系低温タールの軽質分を除去して得られた石炭系ピッチ１００質量部に水素供与性溶剤を３０～３００質量部加えて、０．３～５．０ＭＰａの加圧下、３８０～４５０℃で０．１～４時間保持する点にある。
また、前記水素供与性溶剤が、エチレンボトムオイルまたはＦＣＣデカントオイルであることが好ましい。 〔Constitution〕
In order to achieve the above object, the characteristic constitution of the modified tar production method of the present invention is characterized in that coal-based low-temperature tar or 100 mass parts of coal-based pitch obtained by removing light components of coal-based low-temperature tar has hydrogen donating properties. 30 to 300 parts by mass of a solvent is added and the mixture is held at 380 to 450 ° C. for 0.1 to 4 hours under a pressure of 0.3 to 5.0 MPa.
The hydrogen donating solvent is preferably ethylene bottom oil or FCC decant oil.
上記目的を達成するための本発明の改質タールの製造方法の特徴構成は、石炭系低温タールまたは石炭系低温タールの軽質分を除去して得られた石炭系ピッチ１００質量部に水素供与性溶剤を３０～３００質量部加えて、０．３～５．０ＭＰａの加圧下、３８０～４５０℃で０．１～４時間保持する点にある。
また、前記水素供与性溶剤が、エチレンボトムオイルまたはＦＣＣデカントオイルであることが好ましい。 〔Constitution〕
In order to achieve the above object, the characteristic constitution of the modified tar production method of the present invention is characterized in that coal-based low-temperature tar or 100 mass parts of coal-based pitch obtained by removing light components of coal-based low-temperature tar has hydrogen donating properties. 30 to 300 parts by mass of a solvent is added and the mixture is held at 380 to 450 ° C. for 0.1 to 4 hours under a pressure of 0.3 to 5.0 MPa.
The hydrogen donating solvent is preferably ethylene bottom oil or FCC decant oil.
〔作用効果〕
原料としては、石炭系低温タールあるいは石炭系低温タールから石炭系低温タールの軽質分を蒸留によって除去するなどにより得られた石炭系ピッチが用いられる。この原料に、水素供与性溶剤を混合して加圧下で熱処理を施すと、前記原料中に含まれるヘテロ原子を有する成分が、前記水素供与生溶剤によって還元作用を受ける際に、その原料が分解されて低分子化するなどしてヘテロ原子が系外に除去されるため、改質作用を受け、品質の高いニードルコークスが製造可能な改質タールとなるものと考えられる。 [Function and effect]
As the raw material, coal-based low-temperature tar or coal-based pitch obtained by removing light components of coal-based low-temperature tar from the coal-based low-temperature tar by distillation or the like is used. When this raw material is mixed with a hydrogen-donating solvent and subjected to heat treatment under pressure, when the component having a heteroatom contained in the raw material is subjected to a reducing action by the hydrogen-donating biosolvent, the raw material is decomposed. Since the hetero atoms are removed from the system by lowering the molecular weight, etc., it is considered that the modified tar is subjected to a modification action and can produce high-quality needle coke.
原料としては、石炭系低温タールあるいは石炭系低温タールから石炭系低温タールの軽質分を蒸留によって除去するなどにより得られた石炭系ピッチが用いられる。この原料に、水素供与性溶剤を混合して加圧下で熱処理を施すと、前記原料中に含まれるヘテロ原子を有する成分が、前記水素供与生溶剤によって還元作用を受ける際に、その原料が分解されて低分子化するなどしてヘテロ原子が系外に除去されるため、改質作用を受け、品質の高いニードルコークスが製造可能な改質タールとなるものと考えられる。 [Function and effect]
As the raw material, coal-based low-temperature tar or coal-based pitch obtained by removing light components of coal-based low-temperature tar from the coal-based low-temperature tar by distillation or the like is used. When this raw material is mixed with a hydrogen-donating solvent and subjected to heat treatment under pressure, when the component having a heteroatom contained in the raw material is subjected to a reducing action by the hydrogen-donating biosolvent, the raw material is decomposed. Since the hetero atoms are removed from the system by lowering the molecular weight, etc., it is considered that the modified tar is subjected to a modification action and can produce high-quality needle coke.
このとき、原料としては、石炭系低温タールから予め軽質分が除去された石炭系ピッチを用いることが好ましい。
At this time, as a raw material, it is preferable to use a coal-based pitch obtained by removing light components from a coal-based low-temperature tar in advance.
また、上記石炭系低温タールまたは石炭系ピッチに添加する水素供与性溶剤の量は、少なすぎると充分な改質作用が得られず、多すぎると、費用対効果の面で非効率的になり、コスト高となるため、原料１００質量部に対して３０～３００質量部が好ましい。より好ましくは、５０～１００質量部である。
In addition, if the amount of the hydrogen donating solvent added to the coal-based low-temperature tar or coal-based pitch is too small, sufficient reforming action cannot be obtained, and if it is too large, the cost-effectiveness becomes inefficient. In order to increase the cost, 30 to 300 parts by mass per 100 parts by mass of the raw material is preferable. More preferably, it is 50 to 100 parts by mass.
上記改質反応は、石炭系低温タールまたは石炭系ピッチと水素供与性溶剤との混合物を、加圧下、所定時間加熱することにより効率的に行うことが出来る。加圧は、窒素ガスの導入量もしくは排気ガス量の制御によって行うことができ、０．３～５．０ＭＰａの加圧下とすることにより、経済的な加圧条件で反応性を十分高くすることが出来るので好ましい。尚、さらに好ましくは、１．５～２．５ＭＰａである。また加熱条件としては、温度が低すぎると水素化反応が進まず、高すぎると水素化反応と併行して極性成分などの反応性の高い成分の選択的な熱重合反応が始まる。また、改質物中に異方性が生じ始めるので、３８０～４５０℃とすることが好ましい。反応時間は、上記原料の性状、温度、圧力条件で変化するものの、０．１～４時間保持することによって行えば良い。
The above reforming reaction can be efficiently performed by heating a mixture of coal-based low-temperature tar or coal-based pitch and a hydrogen-donating solvent for a predetermined time under pressure. Pressurization can be performed by controlling the amount of nitrogen gas introduced or the amount of exhaust gas, and by setting the pressure to 0.3 to 5.0 MPa, the reactivity should be sufficiently high under economical pressure conditions. Is preferable. More preferably, it is 1.5 to 2.5 MPa. As heating conditions, if the temperature is too low, the hydrogenation reaction does not proceed. If the temperature is too high, a selective thermal polymerization reaction of a highly reactive component such as a polar component starts in parallel with the hydrogenation reaction. Further, since anisotropy begins to occur in the modified product, the temperature is preferably 380 to 450 ° C. The reaction time varies depending on the properties of the raw material, temperature, and pressure, but may be maintained by holding for 0.1 to 4 hours.
水素供与性溶剤としては、中軽質油を使用することが簡便かつ効率的である。中軽質油としては、エチレンボトムオイル、ＦＣＣデカントオイル、エキストラクトオイル、アントラセンオイル、テトラリン、ジヒドロアントラセン、テトラヒドロキノリンなどから選ばれる少なくとも一種以上の中軽質油を主成分とするものを用いることができるが、これらの複数種を含有しても良い。また、他に種々の粘度調整の機能を損なわない溶媒や添加物を含有していてもかまわない。
このうち、効果及び経済性を考慮するとエチレンボトムオイル及びＦＣＣデカントオイルが特に好ましい。 As the hydrogen-donating solvent, it is convenient and efficient to use medium light oil. As the medium light oil, an oil mainly composed of at least one medium light oil selected from ethylene bottom oil, FCC decant oil, extract oil, anthracene oil, tetralin, dihydroanthracene, tetrahydroquinoline and the like can be used. However, you may contain these multiple types. In addition, other solvents and additives that do not impair various functions of viscosity adjustment may be contained.
Of these, ethylene bottom oil and FCC decant oil are particularly preferable in view of effects and economy.
このうち、効果及び経済性を考慮するとエチレンボトムオイル及びＦＣＣデカントオイルが特に好ましい。 As the hydrogen-donating solvent, it is convenient and efficient to use medium light oil. As the medium light oil, an oil mainly composed of at least one medium light oil selected from ethylene bottom oil, FCC decant oil, extract oil, anthracene oil, tetralin, dihydroanthracene, tetrahydroquinoline and the like can be used. However, you may contain these multiple types. In addition, other solvents and additives that do not impair various functions of viscosity adjustment may be contained.
Of these, ethylene bottom oil and FCC decant oil are particularly preferable in view of effects and economy.
〔構成〕
また、本発明の改質タールの特徴構成は、上記改質タールの製造方法により得られ、酸素含有量が３．０質量％以下、窒素含有量は１．３質量％以下である点、もしくは、上記改質タールの製造方法により得られ、数平均分子量が１００～３００である点にある。 〔Constitution〕
Further, the characteristic configuration of the modified tar of the present invention is obtained by the above-described modified tar production method, wherein the oxygen content is 3.0% by mass or less and the nitrogen content is 1.3% by mass or less, or The number average molecular weight is 100 to 300, which is obtained by the above modified tar production method.
また、本発明の改質タールの特徴構成は、上記改質タールの製造方法により得られ、酸素含有量が３．０質量％以下、窒素含有量は１．３質量％以下である点、もしくは、上記改質タールの製造方法により得られ、数平均分子量が１００～３００である点にある。 〔Constitution〕
Further, the characteristic configuration of the modified tar of the present invention is obtained by the above-described modified tar production method, wherein the oxygen content is 3.0% by mass or less and the nitrogen content is 1.3% by mass or less, or The number average molecular weight is 100 to 300, which is obtained by the above modified tar production method.
〔作用効果〕
上記製造方法で得られた改質タールは、分子量及び分子構造において、以下のような特徴を有する。そのため、生コークスの製造原料として好適なものとなっていると考えられる。 [Function and effect]
The modified tar obtained by the above production method has the following characteristics in terms of molecular weight and molecular structure. Therefore, it is considered that it is suitable as a raw material for producing raw coke.
上記製造方法で得られた改質タールは、分子量及び分子構造において、以下のような特徴を有する。そのため、生コークスの製造原料として好適なものとなっていると考えられる。 [Function and effect]
The modified tar obtained by the above production method has the following characteristics in terms of molecular weight and molecular structure. Therefore, it is considered that it is suitable as a raw material for producing raw coke.
ＦＤ－ＭＳ（電界脱離イオン化質量分析）により測定した分子量分布から計算される平均分子量の一例を示すと、高温タールを蒸留して調製した石炭系ピッチの数平均分子量（Ｍｎ）は７１７、石炭系低温タール由来のピッチのＭｎは５３８、改質タールのＭｎは１６９であった。つまり、分子量において、原料の石炭系ピッチ等に比べて小さくなっている。
An example of the average molecular weight calculated from the molecular weight distribution measured by FD-MS (field desorption ionization mass spectrometry) shows that the number average molecular weight (Mn) of coal-based pitch prepared by distilling high-temperature tar is 717, coal The Mn of the pitch derived from the low temperature tar was 538, and the Mn of the modified tar was 169. That is, the molecular weight is smaller than that of the raw material such as coal-based pitch.
石炭系高温タール由来のピッチでは、元素分析によるとＣ／Ｈ（質量比、以下同様）が約２０であり、かつ酸素がほとんどないため、平均で４～６環の多環芳香族分子で構成されていると考えられる。一方、石炭系低温タール由来のピッチでは、元素分析によるとＣ／Ｈが約１３、Ｃ／Ｏが約１４であることから、平均２～３環の多環芳香族分子３個が酸素原子により架橋結合しているような分子構造と推察される。つまり、得られた改質タールは、Ｃ／Ｏが３４以上になり、ヘテロ原子のきわめて少ない組成となっていることがわかる。
Pitch derived from coal-based high-temperature tar has a C / H (mass ratio, the same applies hereinafter) of about 20 according to elemental analysis and almost no oxygen, so it is composed of polycyclic aromatic molecules with an average of 4 to 6 rings. It is thought that. On the other hand, in the pitch derived from coal-based low-temperature tar, C / H is about 13 and C / O is about 14 according to elemental analysis, so three polycyclic aromatic molecules with an average of 2 to 3 rings are oxygen atoms. The molecular structure is presumed to be cross-linked. That is, it can be seen that the obtained modified tar has a C / O of 34 or more and a composition with very few heteroatoms.
したがって、改質タールでは数平均分子量及び酸素量が大きく減少しているため、上記低温タール由来のピッチに関して、架橋結合が切断され、平均２～３環の芳香族分子に側鎖として酸素が存在するような分子構造となっているものと考えられ、これは、生コークスの生成に際して流れ組織が成長するのに適した構造といえる。
Therefore, since the number average molecular weight and oxygen content of the modified tar are greatly reduced, the cross-linking bond is broken with respect to the pitch derived from the low-temperature tar, and oxygen exists as a side chain in the average two to three ring aromatic molecules. It can be said that this is a structure suitable for the growth of a flow structure during the production of raw coke.
〔構成〕
さらに、本発明の生コークスの製造方法の特徴構成は、上記改質タールを、生コークス化する温度で熱処理する点にある。 〔Constitution〕
Furthermore, the characteristic configuration of the method for producing raw coke according to the present invention is that the modified tar is heat-treated at a temperature at which raw coke is formed.
さらに、本発明の生コークスの製造方法の特徴構成は、上記改質タールを、生コークス化する温度で熱処理する点にある。 〔Constitution〕
Furthermore, the characteristic configuration of the method for producing raw coke according to the present invention is that the modified tar is heat-treated at a temperature at which raw coke is formed.
〔作用効果〕
コーキング処理は、例えば、ディレードコーカー（遅延コークス化コーカー）等のコーキング炉を熱処理炉として用いて熱処理する。このとき、本発明の改質タールは、４３０～６００℃に達すると、流れ組織が形成され、ニードルコークス製造に適した生コークスを得ることができる。ここで、ディレードコーカーを用いると、数秒で所望の温度まで昇温することができ（４８００℃／分）、このように充分速い昇温速度であっても、上記改質タールでは、充分流れ組織が発達し、良好な生コークスが得られる。昇温能力がディレードコーカーほど高くない熱処理炉を用いる場合は、例えば５～５０℃／分程度の昇温速度を選択することができ、容易に上記改質タールから流れ組織を形成することができる。 [Function and effect]
In the coking process, heat treatment is performed using a coking furnace such as a delayed coker (delayed coke coker) as a heat treatment furnace. At this time, when the modified tar of the present invention reaches 430 to 600 ° C., a flow structure is formed, and raw coke suitable for needle coke production can be obtained. Here, when a delayed coker is used, the temperature can be raised to a desired temperature in a few seconds (4800 ° C./min). Develops and good raw coke is obtained. When using a heat treatment furnace whose heating capability is not as high as that of a delayed coker, a heating rate of, for example, about 5 to 50 ° C./min can be selected, and a flow structure can be easily formed from the modified tar. .
コーキング処理は、例えば、ディレードコーカー（遅延コークス化コーカー）等のコーキング炉を熱処理炉として用いて熱処理する。このとき、本発明の改質タールは、４３０～６００℃に達すると、流れ組織が形成され、ニードルコークス製造に適した生コークスを得ることができる。ここで、ディレードコーカーを用いると、数秒で所望の温度まで昇温することができ（４８００℃／分）、このように充分速い昇温速度であっても、上記改質タールでは、充分流れ組織が発達し、良好な生コークスが得られる。昇温能力がディレードコーカーほど高くない熱処理炉を用いる場合は、例えば５～５０℃／分程度の昇温速度を選択することができ、容易に上記改質タールから流れ組織を形成することができる。 [Function and effect]
In the coking process, heat treatment is performed using a coking furnace such as a delayed coker (delayed coke coker) as a heat treatment furnace. At this time, when the modified tar of the present invention reaches 430 to 600 ° C., a flow structure is formed, and raw coke suitable for needle coke production can be obtained. Here, when a delayed coker is used, the temperature can be raised to a desired temperature in a few seconds (4800 ° C./min). Develops and good raw coke is obtained. When using a heat treatment furnace whose heating capability is not as high as that of a delayed coker, a heating rate of, for example, about 5 to 50 ° C./min can be selected, and a flow structure can be easily formed from the modified tar. .
〔構成〕
さらに、本発明のニードルコークスの製造方法の特徴構成は、上述の生コークスの製造方法により得られた生コークスを、か焼処理する点にある。 〔Constitution〕
Furthermore, the characteristic configuration of the needle coke production method of the present invention is that the raw coke obtained by the above-described method for producing raw coke is calcined.
さらに、本発明のニードルコークスの製造方法の特徴構成は、上述の生コークスの製造方法により得られた生コークスを、か焼処理する点にある。 〔Constitution〕
Furthermore, the characteristic configuration of the needle coke production method of the present invention is that the raw coke obtained by the above-described method for producing raw coke is calcined.
〔作用効果〕
つまり、生コークスをか焼すると、生コークスの構造が変化してニードルコークスを製造することができる。生コークスでは、結合水素等が残った高分子量炭化水素であるが、か焼により、揮発成分の除去、脱水、熱分解、易酸化構造の燃焼除去、固相反応による重合、高分子化等を経て安定な化合物へと変化する。ここでは、上述の生コークスを用いてニードルコークスを製造するから、配向繊維状組織が充分発達した良質なニードルコークスを得ることができる。
か焼は、生コークスを８００℃～１４００℃に加熱する熱処理装置が使用でき、工業的にはカルサイナーと呼ばれるロータリーキルンが用いられる。 [Function and effect]
In other words, when the raw coke is calcined, the structure of the raw coke is changed and needle coke can be produced. Raw coke is a high-molecular-weight hydrocarbon in which bound hydrogen and the like remain, but by calcination, removal of volatile components, dehydration, thermal decomposition, combustion removal of easily oxidizable structures, polymerization by solid phase reaction, polymerization, etc. After that, it changes into a stable compound. Here, since needle coke is manufactured using the above-mentioned raw coke, a good-quality needle coke with sufficiently developed oriented fibrous structure can be obtained.
For calcination, a heat treatment apparatus for heating raw coke to 800 ° C. to 1400 ° C. can be used, and industrially a rotary kiln called a calsiner is used.
つまり、生コークスをか焼すると、生コークスの構造が変化してニードルコークスを製造することができる。生コークスでは、結合水素等が残った高分子量炭化水素であるが、か焼により、揮発成分の除去、脱水、熱分解、易酸化構造の燃焼除去、固相反応による重合、高分子化等を経て安定な化合物へと変化する。ここでは、上述の生コークスを用いてニードルコークスを製造するから、配向繊維状組織が充分発達した良質なニードルコークスを得ることができる。
か焼は、生コークスを８００℃～１４００℃に加熱する熱処理装置が使用でき、工業的にはカルサイナーと呼ばれるロータリーキルンが用いられる。 [Function and effect]
In other words, when the raw coke is calcined, the structure of the raw coke is changed and needle coke can be produced. Raw coke is a high-molecular-weight hydrocarbon in which bound hydrogen and the like remain, but by calcination, removal of volatile components, dehydration, thermal decomposition, combustion removal of easily oxidizable structures, polymerization by solid phase reaction, polymerization, etc. After that, it changes into a stable compound. Here, since needle coke is manufactured using the above-mentioned raw coke, a good-quality needle coke with sufficiently developed oriented fibrous structure can be obtained.
For calcination, a heat treatment apparatus for heating raw coke to 800 ° C. to 1400 ° C. can be used, and industrially a rotary kiln called a calsiner is used.
したがって、改質タール並びに改質タールの製造方法、生コークスの製造方法及びニードルコークスの製造方法によれば、製綱用電極、特殊炭素材、高品質の炭素繊維、電池用黒鉛材料の製造原料として好適である。
Therefore, according to the modified tar and the method for producing the modified tar, the method for producing the raw coke and the method for producing the needle coke, the raw material for producing the electrode for steelmaking, the special carbon material, the high-quality carbon fiber, and the graphite material for the battery It is suitable as.
以下に、本発明の改質タール並びに改質タールの製造方法、生コークスの製造方法及びニードルコークスの製造方法を説明する。尚、以下に好適な実施例を記すが、これら実施例は、それぞれ、本発明をより具体的に例示するために記載されたものであって、本発明の趣旨を逸脱しない範囲において種々変更が可能であり、本発明は、以下の記載に限定されるものではない。
Hereinafter, the modified tar of the present invention, the modified tar production method, the raw coke production method, and the needle coke production method will be described. In the following, preferred examples will be described. These examples are described in order to more specifically illustrate the present invention, and various modifications can be made without departing from the spirit of the present invention. The present invention is not limited to the following description.
〔実施例１〕 ルルギ式石炭ガス化プロセスの副生油である石炭系低温タールを用いた。石炭系低温タールを、常法により蒸留し、軽質分を除去して石炭系ピッチを得た。石炭系ピッチの物性は、下記のとおりである。なお、酸素含有量及び窒素含有量は元素分析によって求めた。
[Example 1] A coal-based low-temperature tar which is a by-product oil of the Lurgi-type coal gasification process was used. The coal-based low-temperature tar was distilled by a conventional method to remove light components and obtain a coal-based pitch. The physical properties of coal-based pitch are as follows. The oxygen content and nitrogen content were determined by elemental analysis.
石炭系ピッチ：
軟化点………４７℃
キノリン不溶分………≦０．０１質量％
トルエン不溶分………４．３質量％
酸素含有量………６．１質量％
窒素含有量………１．７質量％ Coal pitch:
Softening point ... 47 ° C
Quinoline insoluble matter ………… ≦ 0.01% by mass
Toluene-insoluble matter: 4.3% by mass
Oxygen content: 6.1% by mass
Nitrogen content: 1.7% by mass
軟化点………４７℃
キノリン不溶分………≦０．０１質量％
トルエン不溶分………４．３質量％
酸素含有量………６．１質量％
窒素含有量………１．７質量％ Coal pitch:
Softening point ... 47 ° C
Quinoline insoluble matter ………… ≦ 0.01% by mass
Toluene-insoluble matter: 4.3% by mass
Oxygen content: 6.1% by mass
Nitrogen content: 1.7% by mass
石炭系ピッチに、同量（質量：特記無き場合は以下同様）の水素供与性溶剤としてのエチレンボトムオイルを加えて混合後、ステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は２．３質量％、窒素含有量は１．０質量％であった。
After adding ethylene bottom oil as a hydrogen donating solvent in the same amount (mass: unless otherwise specified) to coal-based pitch and mixing, put in a stainless steel pressure vessel and apply a pressure of 2.0 MPa with nitrogen gas. And heated to 400 ° C. and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 2.3 mass% and a nitrogen content of 1.0 mass%.
得られた改質タールを、コーキング処理して生コークスを得た。
図１にコーキング実験装置を示す。外径４０ｍｍ、内径３７ｍｍ、長さ３００ｍｍのパイレックス(登録商標)製試験管１に約５０ｇの試料２を入れる。試験管１に窒素ガスを導入するための外径１０ｍｍ、内径８ｍｍのガラス管３と窒素ガス及び試料から発生する揮発分を排気する同じく外径１０ｍｍ、内径８ｍｍのガラス管４を挿入し、シリコンゴム栓５で試験管上部を密閉する。窒素ガスを２００ｍｌ／分の流量で流しながらヒータ６で５００℃に加熱し温度保持した溶融塩バス７に浸漬する。浸漬し始めた時刻から３時間後に試験管１を溶融塩バスから取り出して加熱を終了する。 The obtained modified tar was subjected to coking treatment to obtain raw coke.
FIG. 1 shows a caulking experiment apparatus. About 50 g of thesample 2 is put into a Pyrex (registered trademark) test tube 1 having an outer diameter of 40 mm, an inner diameter of 37 mm, and a length of 300 mm. A glass tube 3 with an outer diameter of 10 mm and an inner diameter of 8 mm for introducing nitrogen gas into the test tube 1 and a glass tube 4 with an outer diameter of 10 mm and an inner diameter of 8 mm for exhausting nitrogen gas and volatile matter generated from the sample are inserted, and silicon The upper part of the test tube is sealed with a rubber stopper 5. While flowing nitrogen gas at a flow rate of 200 ml / min, it is immersed in a molten salt bath 7 heated to 500 ° C. by the heater 6 and maintained at a temperature. Three hours after the start of immersion, the test tube 1 is taken out of the molten salt bath and heating is completed.
図１にコーキング実験装置を示す。外径４０ｍｍ、内径３７ｍｍ、長さ３００ｍｍのパイレックス(登録商標)製試験管１に約５０ｇの試料２を入れる。試験管１に窒素ガスを導入するための外径１０ｍｍ、内径８ｍｍのガラス管３と窒素ガス及び試料から発生する揮発分を排気する同じく外径１０ｍｍ、内径８ｍｍのガラス管４を挿入し、シリコンゴム栓５で試験管上部を密閉する。窒素ガスを２００ｍｌ／分の流量で流しながらヒータ６で５００℃に加熱し温度保持した溶融塩バス７に浸漬する。浸漬し始めた時刻から３時間後に試験管１を溶融塩バスから取り出して加熱を終了する。 The obtained modified tar was subjected to coking treatment to obtain raw coke.
FIG. 1 shows a caulking experiment apparatus. About 50 g of the
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、図２に示すように全て流れ組織が発達した生コークスが得られていることがわかった。
The structure of the obtained raw coke was observed with a polarizing microscope. As a result, as shown in FIG. 2, it was found that the raw coke with the flow structure developed was obtained.
尚、生コークスに含まれる流れ組織及びモザイク組織の面積割合は以下のようにして求めた。
In addition, the area ratio of the flow structure | tissue and mosaic structure | tissue contained in raw coke was calculated | required as follows.
コークスを樹脂に埋め込み、表面を研磨後、観察倍率約２００倍の偏光顕微鏡にて観察する。観察画像を一枚につき、４４μｍ×３４μｍの面積を有するデジタル画像として約１０枚の画像をコンピューターに取り込み、コンピューター上で２μｍ×２μｍのマス目に分割する。分割したマス目を目視で流れ組織、コースモザイク組織及びファインモザイク組織に分類し、１２５０個以上のマス目（５０００μｍ2以上）を検査し、マス目の個数割合を求めることにより、各組織の面積割合を算出する。
生コークスに含まれる流れ組織の面積割合は１００％であった。 Coke is embedded in resin, the surface is polished, and then observed with a polarizing microscope having an observation magnification of about 200 times. About 10 images are taken into a computer as digital images having an area of 44 μm × 34 μm per observation image, and divided into squares of 2 μm × 2 μm on the computer. The divided cells are visually classified into a flow structure, a course mosaic structure, and a fine mosaic structure, and 1250 or more cells (5000 μm 2 or more) are inspected, and the area ratio of each tissue is obtained by determining the number ratio of the cells. Calculate the percentage.
The area ratio of the flow structure contained in the raw coke was 100%.
生コークスに含まれる流れ組織の面積割合は１００％であった。 Coke is embedded in resin, the surface is polished, and then observed with a polarizing microscope having an observation magnification of about 200 times. About 10 images are taken into a computer as digital images having an area of 44 μm × 34 μm per observation image, and divided into squares of 2 μm × 2 μm on the computer. The divided cells are visually classified into a flow structure, a course mosaic structure, and a fine mosaic structure, and 1250 or more cells (5000 μm 2 or more) are inspected, and the area ratio of each tissue is obtained by determining the number ratio of the cells. Calculate the percentage.
The area ratio of the flow structure contained in the raw coke was 100%.
得られた生コークスを、蓋付き黒鉛製坩堝に入れ、その坩堝をヒータ加熱式の電気炉で、窒素ガス気流中１０００℃（昇温速度５℃／分）で熱処理し、か焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図３に示すように配向繊維状組織の発達したニードルコークスであることがわかった。
The obtained raw coke was put into a graphite crucible with a lid, and the crucible was heat-treated at 1000 ° C. (heating rate 5 ° C./min) in a nitrogen gas stream in a heater heating type electric furnace and calcined. When the structure of the obtained calcined product was confirmed with a polarizing microscope, it was found to be a needle coke having an oriented fibrous structure developed as shown in FIG.
〔実施例２〕
実施例１と同じ石炭系ピッチに、石炭系ピッチの半分の量のエチレンボトムオイルを加えて混合後、実施例１と同様にステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は２．７質量％、窒素含有量は１．３質量％であった。 [Example 2]
After adding and mixing ethylene bottom oil in half the amount of coal-based pitch to the same coal-based pitch as in Example 1, it is placed in a stainless steel pressure vessel as in Example 1, and a pressure of 2.0 MPa is applied with nitrogen gas. And heated to 400 ° C. and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 2.7% by mass and a nitrogen content of 1.3% by mass.
実施例１と同じ石炭系ピッチに、石炭系ピッチの半分の量のエチレンボトムオイルを加えて混合後、実施例１と同様にステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は２．７質量％、窒素含有量は１．３質量％であった。 [Example 2]
After adding and mixing ethylene bottom oil in half the amount of coal-based pitch to the same coal-based pitch as in Example 1, it is placed in a stainless steel pressure vessel as in Example 1, and a pressure of 2.0 MPa is applied with nitrogen gas. And heated to 400 ° C. and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 2.7% by mass and a nitrogen content of 1.3% by mass.
つづいて、得られた改質タールを、実施例１と同様な方法でコーキング処理して生コークスを得た。
得られた生コークスの組織を偏光顕微鏡により観察した。その結果図４に示すようにほとんど全て流れ組織が発達した生コークスが得られていることがわかった。生コークスに含まれる流れ組織の面積割合は９２％であった。ファインモザイク組織の面積割合が８％であった。 Subsequently, the obtained modified tar was coked in the same manner as in Example 1 to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, as shown in FIG. 4, it was found that almost all the raw coke with the flow structure developed was obtained. The area ratio of the flow structure contained in the raw coke was 92%. The area ratio of the fine mosaic structure was 8%.
得られた生コークスの組織を偏光顕微鏡により観察した。その結果図４に示すようにほとんど全て流れ組織が発達した生コークスが得られていることがわかった。生コークスに含まれる流れ組織の面積割合は９２％であった。ファインモザイク組織の面積割合が８％であった。 Subsequently, the obtained modified tar was coked in the same manner as in Example 1 to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, as shown in FIG. 4, it was found that almost all the raw coke with the flow structure developed was obtained. The area ratio of the flow structure contained in the raw coke was 92%. The area ratio of the fine mosaic structure was 8%.
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図５に示すように、配向繊維状組織の発達したニードルコークスであることがわかった。
Furthermore, the obtained raw coke was calcined in the same manner as in Example 1. When the structure of the obtained calcined product was confirmed by a polarizing microscope, it was found that the coke was a needle coke having an oriented fibrous structure developed as shown in FIG.
エチレンボトムオイルの添加量は、原料１００質量部に対して５０質量部であっても充分な量であることがわかった。
It was found that the addition amount of ethylene bottom oil was sufficient even if it was 50 parts by mass with respect to 100 parts by mass of the raw material.
〔実施例３〕
実施例１と同じ石炭系ピッチに、同量のＦＣＣデカントオイルを加えて混合後、実施例１と同様にステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は２．２質量％、窒素含有量は１．１質量％であった。 Example 3
After adding and mixing the same amount of FCC decant oil to the same coal-based pitch as in Example 1, it is put into a stainless steel pressure vessel as in Example 1, and a pressure of 2.0 MPa is applied with nitrogen gas to 400 ° C. Heated and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 2.2% by mass and a nitrogen content of 1.1% by mass.
実施例１と同じ石炭系ピッチに、同量のＦＣＣデカントオイルを加えて混合後、実施例１と同様にステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は２．２質量％、窒素含有量は１．１質量％であった。 Example 3
After adding and mixing the same amount of FCC decant oil to the same coal-based pitch as in Example 1, it is put into a stainless steel pressure vessel as in Example 1, and a pressure of 2.0 MPa is applied with nitrogen gas to 400 ° C. Heated and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 2.2% by mass and a nitrogen content of 1.1% by mass.
つづいて、得られた改質タールを、実施例１と同様な方法でコーキング処理して生コークスを得た。
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、図６に示すように全て流れ組織が発達した生コークスが得られていることがわかった。生コークスに含まれる流れ組織の面積割合は１００％であった。 Subsequently, the obtained modified tar was coked in the same manner as in Example 1 to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, as shown in FIG. 6, it was found that the raw coke with the flow structure developed was obtained. The area ratio of the flow structure contained in the raw coke was 100%.
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、図６に示すように全て流れ組織が発達した生コークスが得られていることがわかった。生コークスに含まれる流れ組織の面積割合は１００％であった。 Subsequently, the obtained modified tar was coked in the same manner as in Example 1 to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, as shown in FIG. 6, it was found that the raw coke with the flow structure developed was obtained. The area ratio of the flow structure contained in the raw coke was 100%.
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図７に示すように、配向繊維状組織の発達したニードルコークスであることがわかった。
Furthermore, the obtained raw coke was calcined in the same manner as in Example 1. When the structure of the obtained calcined product was confirmed with a polarizing microscope, it was found to be a needle coke having an oriented fibrous structure developed as shown in FIG.
つまり、エチレンボトムオイルに代えＦＣＣデカントオイルを用いても、実施例１と同様に良質の改質タールが得られることがわかった。
That is, it was found that even when FCC decant oil was used instead of ethylene bottom oil, a good quality modified tar was obtained as in Example 1.
〔比較例１〕
実施例１と同じ石炭系ピッチに、石炭系ピッチの５分の１の量のエチレンボトムオイルを加えて混合後、実施例１と同様にステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は３．２質量％、窒素含有量は１．６質量％であった。 [Comparative Example 1]
To the same coal-based pitch as in Example 1, ethylene bottom oil in an amount one-fifth of the coal-based pitch was added and mixed, and then placed in a stainless steel pressure vessel in the same manner as in Example 1, and 2.0 MPa with nitrogen gas. Was heated to 400 ° C. and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 3.2% by mass and a nitrogen content of 1.6% by mass.
実施例１と同じ石炭系ピッチに、石炭系ピッチの５分の１の量のエチレンボトムオイルを加えて混合後、実施例１と同様にステンレス製の圧力容器に入れ、窒素ガスにより２．０ＭＰａの圧力を与えて４００℃まで加熱し、その温度で４時間保持した。これによって、室温で粘着性のある液体状の改質タールを得た。この改質タールの酸素含有量は３．２質量％、窒素含有量は１．６質量％であった。 [Comparative Example 1]
To the same coal-based pitch as in Example 1, ethylene bottom oil in an amount one-fifth of the coal-based pitch was added and mixed, and then placed in a stainless steel pressure vessel in the same manner as in Example 1, and 2.0 MPa with nitrogen gas. Was heated to 400 ° C. and held at that temperature for 4 hours. As a result, a liquid modified tar sticky at room temperature was obtained. This modified tar had an oxygen content of 3.2% by mass and a nitrogen content of 1.6% by mass.
つづいて、得られた改質タールを、実施例１と同様な方法でコーキング処理して生コークスを得た。
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、ファインモザイクの他コースモザイクが認められた。図８に示すように流れ組織の発達が不十分な生コークスであった。生コークスに含まれる流れ組織の面積割合は６８％であった。ファインモザイク組織の面積割合が２３％であり、コースモザイク組織の面積割合が９％であった。 Subsequently, the obtained modified tar was coked in the same manner as in Example 1 to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 8, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 68%. The area ratio of the fine mosaic structure was 23%, and the area ratio of the course mosaic structure was 9%.
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、ファインモザイクの他コースモザイクが認められた。図８に示すように流れ組織の発達が不十分な生コークスであった。生コークスに含まれる流れ組織の面積割合は６８％であった。ファインモザイク組織の面積割合が２３％であり、コースモザイク組織の面積割合が９％であった。 Subsequently, the obtained modified tar was coked in the same manner as in Example 1 to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 8, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 68%. The area ratio of the fine mosaic structure was 23%, and the area ratio of the course mosaic structure was 9%.
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図９に示すように、配向繊維状組織の発達が不十分なコークスであることがわかった。
Further, the obtained raw coke was calcined in the same manner as in Example 1. When the structure of the obtained calcined product was confirmed by a polarizing microscope, it was found that the coke was insufficient in the development of the oriented fibrous structure as shown in FIG.
水素供与性溶剤の添加量は、２０質量部まで減少すると良質な改質タールが得られず、ほぼ３０質量部程度～３００質量部の範囲で実施例１と同様に良質の改質タールが得られることが示唆された。
When the amount of the hydrogen-donating solvent added is reduced to 20 parts by mass, a good quality modified tar cannot be obtained, and a good quality modified tar is obtained in the range of about 30 parts by mass to 300 parts by mass in the same manner as in Example 1. It was suggested that
〔比較例２〕
実施例１と同じ石炭系ピッチに、石炭系ピッチと同量のエチレンボトムオイルを加えて混合した。この混合物の酸素含有量は３．１質量％、窒素含有量は０．９質量％であった。 [Comparative Example 2]
To the same coal-based pitch as in Example 1, the same amount of ethylene bottom oil as the coal-based pitch was added and mixed. This mixture had an oxygen content of 3.1% by mass and a nitrogen content of 0.9% by mass.
実施例１と同じ石炭系ピッチに、石炭系ピッチと同量のエチレンボトムオイルを加えて混合した。この混合物の酸素含有量は３．１質量％、窒素含有量は０．９質量％であった。 [Comparative Example 2]
To the same coal-based pitch as in Example 1, the same amount of ethylene bottom oil as the coal-based pitch was added and mixed. This mixture had an oxygen content of 3.1% by mass and a nitrogen content of 0.9% by mass.
この混合物を加熱改質処理なしで実施例１と同様な方法で、コーキング処理して生コークスを得た。すなわち、図１に示すコーキング実験装置で、窒素ガスを２００ｍｌ／分の流量で流しながら５００℃にて３時間加熱してコーキング処理を行った。
This mixture was coked in the same manner as in Example 1 without heat reforming to obtain raw coke. That is, in the coking experimental apparatus shown in FIG. 1, the coking process was performed by heating at 500 ° C. for 3 hours while flowing nitrogen gas at a flow rate of 200 ml / min.
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、ファインモザイクの他コースモザイクが認められた。図１０に示すように流れ組織の発達が不十分な生コークスであった。生コークスに含まれる流れ組織の面積割合は６５％であった。ファインモザイク組織の面積割合が９％であり、コースモザイク組織の面積割合が２６％であった。
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図１１に示すように、配向繊維状組織の発達が不十分なコークスであることがわかった。 The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 10, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 65%. The area ratio of the fine mosaic structure was 9%, and the area ratio of the course mosaic structure was 26%.
Further, the obtained raw coke was calcined in the same manner as in Example 1. When the structure of the obtained calcined product was confirmed by a polarizing microscope, it was found that the coke was insufficient in the development of the oriented fibrous structure as shown in FIG.
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図１１に示すように、配向繊維状組織の発達が不十分なコークスであることがわかった。 The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 10, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 65%. The area ratio of the fine mosaic structure was 9%, and the area ratio of the course mosaic structure was 26%.
Further, the obtained raw coke was calcined in the same manner as in Example 1. When the structure of the obtained calcined product was confirmed by a polarizing microscope, it was found that the coke was insufficient in the development of the oriented fibrous structure as shown in FIG.
〔比較例３〕
実施例１と同じ石炭系ピッチに、石炭系ピッチと同量のＦＣＣデカントオイルを加えて混合した。この混合物の酸素含有量は３．２質量％、窒素含有量は０．９質量％であった。 [Comparative Example 3]
The same amount of FCC decant oil as the coal-based pitch was added to the same coal-based pitch as in Example 1 and mixed. This mixture had an oxygen content of 3.2% by mass and a nitrogen content of 0.9% by mass.
実施例１と同じ石炭系ピッチに、石炭系ピッチと同量のＦＣＣデカントオイルを加えて混合した。この混合物の酸素含有量は３．２質量％、窒素含有量は０．９質量％であった。 [Comparative Example 3]
The same amount of FCC decant oil as the coal-based pitch was added to the same coal-based pitch as in Example 1 and mixed. This mixture had an oxygen content of 3.2% by mass and a nitrogen content of 0.9% by mass.
この混合物を加熱改質処理なしで実施例１と同様な方法で、コーキング処理して生コークスを得た。すなわち、図１に示すコーキング実験装置で、窒素ガスを２００ｍｌ／分の流量で流しながら５００℃にて３時間加熱してコーキング処理を行った。
This mixture was coked in the same manner as in Example 1 without heat reforming to obtain raw coke. That is, in the coking experimental apparatus shown in FIG. 1, the coking process was performed by heating at 500 ° C. for 3 hours while flowing nitrogen gas at a flow rate of 200 ml / min.
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、ファインモザイクの他コースモザイクが認められた。図１２に示すように流れ組織の発達が不十分な生コークスであった。生コークスに含まれる流れ組織の面積割合は７８％であった。ファインモザイク組織の面積割合が２２％であった。
The structure of the obtained raw coke was observed with a polarizing microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 12, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 78%. The area ratio of the fine mosaic structure was 22%.
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図１３に示すように、配向繊維状組織の発達が不十分なコークスであることがわかった。
Furthermore, the obtained raw coke was calcined in the same manner as in Example 1. The structure of the obtained calcined product was confirmed with a polarizing microscope, and as shown in FIG. 13, it was found that the coke was insufficiently developed in an oriented fibrous structure.
〔比較例４〕
実施例１と同じ石炭系ピッチを直接、コーキング処理して生コークスを得た。
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、ファインモザイクの他コースモザイクが認められた。図１４に示すように流れ組織の発達が不十分な生コークスであった。生コークスに含まれる流れ組織の面積割合は４４％であった。ファインモザイク組織の面積割合が２２％であり、コースモザイク組織の面積割合が３４％であった。 [Comparative Example 4]
The same coal pitch as in Example 1 was directly coked to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 14, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 44%. The area ratio of the fine mosaic structure was 22%, and the area ratio of the course mosaic structure was 34%.
実施例１と同じ石炭系ピッチを直接、コーキング処理して生コークスを得た。
得られた生コークスの組織を偏光顕微鏡により観察した。その結果、ファインモザイクの他コースモザイクが認められた。図１４に示すように流れ組織の発達が不十分な生コークスであった。生コークスに含まれる流れ組織の面積割合は４４％であった。ファインモザイク組織の面積割合が２２％であり、コースモザイク組織の面積割合が３４％であった。 [Comparative Example 4]
The same coal pitch as in Example 1 was directly coked to obtain raw coke.
The structure | tissue of the obtained raw coke was observed with the polarization microscope. As a result, a fine mosaic mosaic course was recognized. As shown in FIG. 14, it was raw coke with insufficient flow tissue development. The area ratio of the flow structure contained in the raw coke was 44%. The area ratio of the fine mosaic structure was 22%, and the area ratio of the course mosaic structure was 34%.
さらに、得られた生コークスを実施例１と同様な方法でか焼した。得られたか焼物の組織を偏光顕微鏡により確認したところ、図１５に示すように、配向繊維状組織の発達が不十分なコークスであることがわかった。
Furthermore, the obtained raw coke was calcined in the same manner as in Example 1. When the structure of the obtained calcined product was confirmed with a polarizing microscope, it was found that the coke was insufficiently developed in an oriented fibrous structure as shown in FIG.
（極性分子成分分析）
実施例１で用いた石炭系ピッチ及び得られた改質タールをガスクロマトグラフ質量分析（ＧＣ／ＭＳ）により分析した。ＧＣ／ＭＳ分析では、試料をＴＨＦ（テトラヒドロフラン）で溶解し、１質量％溶液として分析した。ガスクロマトグラフ分析装置（ＧＣ）はＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ製ＨＰ５８９０を用いた。カラム温度は５０～３２０℃（昇温１０℃／分）であった。キャリアガスとしてヘリウムガスを用い流量１ｍｌ／分を流した。質量分析装置（ＭＳ）は日本電子製ＪＭＳ－７００を用いた。電子衝撃によるイオン化エネルギー７０ｅＶ、加速電圧１０ｋＶとした。 (Polar molecular component analysis)
The coal-based pitch used in Example 1 and the resulting modified tar were analyzed by gas chromatography mass spectrometry (GC / MS). In the GC / MS analysis, a sample was dissolved in THF (tetrahydrofuran) and analyzed as a 1% by mass solution. As a gas chromatograph analyzer (GC), HP5890 manufactured by HEWLETT PACKARD was used. The column temperature was 50 to 320 ° C. (temperature increase 10 ° C./min). Helium gas was used as a carrier gas and a flow rate of 1 ml / min was passed. As a mass spectrometer (MS), JEOL JMS-700 was used. The ionization energy by electron impact was 70 eV, and the acceleration voltage was 10 kV.
実施例１で用いた石炭系ピッチ及び得られた改質タールをガスクロマトグラフ質量分析（ＧＣ／ＭＳ）により分析した。ＧＣ／ＭＳ分析では、試料をＴＨＦ（テトラヒドロフラン）で溶解し、１質量％溶液として分析した。ガスクロマトグラフ分析装置（ＧＣ）はＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ製ＨＰ５８９０を用いた。カラム温度は５０～３２０℃（昇温１０℃／分）であった。キャリアガスとしてヘリウムガスを用い流量１ｍｌ／分を流した。質量分析装置（ＭＳ）は日本電子製ＪＭＳ－７００を用いた。電子衝撃によるイオン化エネルギー７０ｅＶ、加速電圧１０ｋＶとした。 (Polar molecular component analysis)
The coal-based pitch used in Example 1 and the resulting modified tar were analyzed by gas chromatography mass spectrometry (GC / MS). In the GC / MS analysis, a sample was dissolved in THF (tetrahydrofuran) and analyzed as a 1% by mass solution. As a gas chromatograph analyzer (GC), HP5890 manufactured by HEWLETT PACKARD was used. The column temperature was 50 to 320 ° C. (temperature increase 10 ° C./min). Helium gas was used as a carrier gas and a flow rate of 1 ml / min was passed. As a mass spectrometer (MS), JEOL JMS-700 was used. The ionization energy by electron impact was 70 eV, and the acceleration voltage was 10 kV.
ヘテロ原子を含む極性分子成分のうち、表１に示す物質が石炭系ピッチでは検出され、改質タールでは検出されなかった。
Among the polar molecular components containing heteroatoms, the substances shown in Table 1 were detected in the coal-based pitch, but not in the modified tar.
ＧＣ／ＭＳ分析より、ナフトール等の含酸素化合物、カルバゾール等の含窒素化合物がよく除去されているのが確認された。
GC / MS analysis confirmed that oxygen-containing compounds such as naphthol and nitrogen-containing compounds such as carbazole were well removed.
（黒鉛化物の構造）
実施例１及び比較例４で得られたか焼物を、工業用のアチソン炉を用いて２８００℃の熱処理を行い、黒鉛化物を得た。
Ｘ線回折測定により得られた黒鉛化物の結晶配向性を測定した。ニードルコークスは流れ組織で形成されているため、モザイク組織と比較して結晶の配向性が高い特徴がある。この結晶配向性はＸ線回折測定により、５４．５°付近に表れる００４回折線ピークと７６．３°付近に表れる１１０回折線ピークの強度比（Ｉ（００４）／Ｉ（１１０））を測定することによって評価できる。この強度比が高いほうが、結晶の配向性が高い。 (Structure of graphitized material)
The calcined products obtained in Example 1 and Comparative Example 4 were heat-treated at 2800 ° C. using an industrial Atchison furnace to obtain graphitized products.
The crystal orientation of the graphitized material obtained by X-ray diffraction measurement was measured. Since needle coke is formed with a flow structure, it has a feature that crystal orientation is higher than that of a mosaic structure. This crystal orientation is measured by an X-ray diffraction measurement of an intensity ratio (I (004) / I (110)) of a 004 diffraction line peak appearing near 54.5 ° and a 110 diffraction line peak appearing near 76.3 °. It can be evaluated by doing. The higher the intensity ratio, the higher the crystal orientation.
実施例１及び比較例４で得られたか焼物を、工業用のアチソン炉を用いて２８００℃の熱処理を行い、黒鉛化物を得た。
Ｘ線回折測定により得られた黒鉛化物の結晶配向性を測定した。ニードルコークスは流れ組織で形成されているため、モザイク組織と比較して結晶の配向性が高い特徴がある。この結晶配向性はＸ線回折測定により、５４．５°付近に表れる００４回折線ピークと７６．３°付近に表れる１１０回折線ピークの強度比（Ｉ（００４）／Ｉ（１１０））を測定することによって評価できる。この強度比が高いほうが、結晶の配向性が高い。 (Structure of graphitized material)
The calcined products obtained in Example 1 and Comparative Example 4 were heat-treated at 2800 ° C. using an industrial Atchison furnace to obtain graphitized products.
The crystal orientation of the graphitized material obtained by X-ray diffraction measurement was measured. Since needle coke is formed with a flow structure, it has a feature that crystal orientation is higher than that of a mosaic structure. This crystal orientation is measured by an X-ray diffraction measurement of an intensity ratio (I (004) / I (110)) of a 004 diffraction line peak appearing near 54.5 ° and a 110 diffraction line peak appearing near 76.3 °. It can be evaluated by doing. The higher the intensity ratio, the higher the crystal orientation.
実施例１及び比較例４において得られた黒鉛化物について強度比を測定した。測定方法は、２００メッシュ以下に粉砕した黒鉛化物を約０．１ｇ計り取り、２０×１６×０．５ｍｍのサンプルを受ける窪みを備えた３５×５０×１ｍｍのガラス製サンプルホルダーに仕込み、平らなガラス板で圧密した。圧密し、表面を平らにした試料を理学電機株式会社製のＸ線広角回折装置（型式：ＲＩＮＴ２５００）にセットし、測定した。測定に用いたパラメータは下記の通りであった。
Strength ratios of the graphitized materials obtained in Example 1 and Comparative Example 4 were measured. The measuring method is to measure about 0.1 g of graphitized material pulverized to 200 mesh or less, and place it in a 35 × 50 × 1 mm glass sample holder with a recess for receiving a 20 × 16 × 0.5 mm sample. Compacted with a glass plate. The sample that was consolidated and flattened was set on an X-ray wide angle diffractometer (model: RINT2500) manufactured by Rigaku Corporation and measured. The parameters used for the measurement were as follows.
管電圧：４０ｋＶ
管電流：２００ｍＡ
ゴニオ半径：１８５ｍｍ 走査軸：２θ／θ
ステップ：０．０２
計数時間：１秒
測定方法：ＦＴ
繰り返し回数：１回 Tube voltage: 40 kV
Tube current: 200 mA
Goniometer radius: 185mm Scan axis: 2θ / θ
Step: 0.02
Counting time: 1 second Measuring method: FT
Repeat count: 1 time
管電流：２００ｍＡ
ゴニオ半径：１８５ｍｍ 走査軸：２θ／θ
ステップ：０．０２
計数時間：１秒
測定方法：ＦＴ
繰り返し回数：１回 Tube voltage: 40 kV
Tube current: 200 mA
Goniometer radius: 185mm Scan axis: 2θ / θ
Step: 0.02
Counting time: 1 second Measuring method: FT
Repeat count: 1 time
得られたデータを解析ソフト（Ｃａｒｂｏｎ Ａｎａｌｙｚｅｒ Ｇ ｓｅｒｉｅｓ（（株）菱化システム））を用いて解析した。
その結果、実施例１にかかる黒鉛化物のＩ（００４）／Ｉ（１１０）は、７．９０であったのに対して、比較例４にかかる黒鉛化物のＩ（００４）／Ｉ（１１０）は、１．１８であった。つまり、本発明のニードルコークスの製造方法により得られたニードルコークスは、黒鉛化した際に、良質な結晶構造を有し、電極材料等の用途で有用な高品質な材料を提供することができることがわかった。 The obtained data was analyzed using analysis software (Carbon Analyzer G series (Ryoka System Co., Ltd.)).
As a result, I (004) / I (110) of the graphitized product according to Example 1 was 7.90, whereas I (004) / I (110) of the graphitized product according to Comparative Example 4 was used. Was 1.18. That is, the needle coke obtained by the needle coke manufacturing method of the present invention has a high-quality crystal structure when graphitized, and can provide a high-quality material useful for applications such as electrode materials. I understood.
その結果、実施例１にかかる黒鉛化物のＩ（００４）／Ｉ（１１０）は、７．９０であったのに対して、比較例４にかかる黒鉛化物のＩ（００４）／Ｉ（１１０）は、１．１８であった。つまり、本発明のニードルコークスの製造方法により得られたニードルコークスは、黒鉛化した際に、良質な結晶構造を有し、電極材料等の用途で有用な高品質な材料を提供することができることがわかった。 The obtained data was analyzed using analysis software (Carbon Analyzer G series (Ryoka System Co., Ltd.)).
As a result, I (004) / I (110) of the graphitized product according to Example 1 was 7.90, whereas I (004) / I (110) of the graphitized product according to Comparative Example 4 was used. Was 1.18. That is, the needle coke obtained by the needle coke manufacturing method of the present invention has a high-quality crystal structure when graphitized, and can provide a high-quality material useful for applications such as electrode materials. I understood.
したがって、改質タール並びに改質タールの製造方法、生コークスの製造方法及びニードルコークスの製造方法によれば、製綱用電極、特殊炭素材、高品質の炭素繊維、電池用黒鉛材料の製造原料として好適である。
Therefore, according to the modified tar and the method for producing the modified tar, the method for producing the raw coke and the method for producing the needle coke, the raw material for producing the electrode for steelmaking, the special carbon material, the high-quality carbon fiber, and the graphite material for the battery It is suitable as.
１ 試験管
２ 試料
３ ガラス管
４ ガラス管
５ ゴム栓
６ ヒータ
７ 溶融塩バス 1Test tube 2 Sample 3 Glass tube 4 Glass tube 5 Rubber stopper 6 Heater 7 Molten salt bath
２ 試料
３ ガラス管
４ ガラス管
５ ゴム栓
６ ヒータ
７ 溶融塩バス 1
Claims (6)
- 石炭系低温タールまたは石炭系低温タールの軽質分を除去して得られた石炭系ピッチ１００質量部に水素供与性溶剤を３０～３００質量部加えて、０．３～５．０ＭＰａの加圧下、３８０～４５０℃で０．１～４時間保持する改質タールの製造方法。 30 to 300 parts by mass of a hydrogen donating solvent is added to 100 parts by mass of coal-based low-temperature tar or light-weight coal-based low-temperature tar, and then pressurized under 0.3 to 5.0 MPa. A method for producing a modified tar which is maintained at 380 to 450 ° C. for 0.1 to 4 hours.
- 前記水素供与性溶剤が、エチレンボトムオイルまたはＦＣＣデカントオイルである請求項１に記載の改質タールの製造方法。 The method for producing a modified tar according to claim 1, wherein the hydrogen donating solvent is ethylene bottom oil or FCC decant oil.
- 請求項１または２に記載の改質タールの製造方法により得られ、酸素含有量が３．０質量％以下、窒素含有量は１．３質量％以下である改質タール。 A modified tar obtained by the method for producing a modified tar according to claim 1, wherein the oxygen content is 3.0% by mass or less and the nitrogen content is 1.3% by mass or less.
- 請求項１または２に記載の改質タールの製造方法により得られ、数平均分子量が１００～３００である改質タール。 A modified tar obtained by the method for producing a modified tar according to claim 1 or 2 and having a number average molecular weight of 100 to 300.
- 請求項３または４に記載の改質タールを、生コークス化する温度で熱処理する生コークスの製造方法。 A method for producing raw coke, wherein the modified tar according to claim 3 or 4 is heat-treated at a temperature for forming raw coke.
- 請求項５に記載の生コークスの製造方法により得られた生コークスを、か焼処理するニードルコークスの製造方法。 A method for producing needle coke in which raw coke obtained by the method for producing fresh coke according to claim 5 is calcined.
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| JP2009243662A JP2011089024A (en) | 2009-10-22 | 2009-10-22 | Modified tar and method for producing modified tar, method for producing raw coke, and method for producing needle coke |
| JP2009-243662 | 2009-10-22 |
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| WO2011048920A1 true WO2011048920A1 (en) | 2011-04-28 |
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| CN102786979A (en) * | 2011-05-16 | 2012-11-21 | 北京三聚创洁科技发展有限公司 | Process for preparing needle coke raw material by using medium and low temperature coal tar and high temperature pitch |
| CN109439367A (en) * | 2018-11-19 | 2019-03-08 | 山西中科化美科技有限责任公司 | It is a kind of to prepare needle coke technique using coal tar |
| CN109517613A (en) * | 2018-11-19 | 2019-03-26 | 山西中科化美科技有限责任公司 | A kind of coal-based needle coke raw material pretreatment process |
| CN115404090A (en) * | 2022-09-22 | 2022-11-29 | 西北大学 | Method for preparing needle coke by compounding coal-based and petroleum-based heavy components |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6392701B2 (en) * | 2015-05-12 | 2018-09-19 | 株式会社神戸製鋼所 | Raw material pitch for carbon fiber production |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61162585A (en) * | 1985-01-11 | 1986-07-23 | Kawasaki Steel Corp | Production of hydrogenation-treated pitch |
| JPS61197688A (en) * | 1985-02-28 | 1986-09-01 | Sumitomo Metal Ind Ltd | Refining of coal-based pitch |
| JPH02145689A (en) * | 1988-11-25 | 1990-06-05 | Mitsubishi Kasei Corp | Production of high-quality coke |
| JPH03250090A (en) * | 1989-06-15 | 1991-11-07 | Isao Mochida | Manufacture of needle coke |
-
2009
- 2009-10-22 JP JP2009243662A patent/JP2011089024A/en not_active Withdrawn
-
2010
- 2010-09-30 WO PCT/JP2010/067027 patent/WO2011048920A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61162585A (en) * | 1985-01-11 | 1986-07-23 | Kawasaki Steel Corp | Production of hydrogenation-treated pitch |
| JPS61197688A (en) * | 1985-02-28 | 1986-09-01 | Sumitomo Metal Ind Ltd | Refining of coal-based pitch |
| JPH02145689A (en) * | 1988-11-25 | 1990-06-05 | Mitsubishi Kasei Corp | Production of high-quality coke |
| JPH03250090A (en) * | 1989-06-15 | 1991-11-07 | Isao Mochida | Manufacture of needle coke |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786984A (en) * | 2011-05-16 | 2012-11-21 | 北京三聚创洁科技发展有限公司 | Process for preparing needle coke raw material by using medium and low temperature coal tar |
| CN102786979A (en) * | 2011-05-16 | 2012-11-21 | 北京三聚创洁科技发展有限公司 | Process for preparing needle coke raw material by using medium and low temperature coal tar and high temperature pitch |
| CN109439367A (en) * | 2018-11-19 | 2019-03-08 | 山西中科化美科技有限责任公司 | It is a kind of to prepare needle coke technique using coal tar |
| CN109517613A (en) * | 2018-11-19 | 2019-03-26 | 山西中科化美科技有限责任公司 | A kind of coal-based needle coke raw material pretreatment process |
| CN109439367B (en) * | 2018-11-19 | 2021-02-05 | 山西中科化美科技有限责任公司 | Process for preparing needle coke by using coal tar |
| CN115404090A (en) * | 2022-09-22 | 2022-11-29 | 西北大学 | Method for preparing needle coke by compounding coal-based and petroleum-based heavy components |
| CN115404090B (en) * | 2022-09-22 | 2023-08-08 | 西北大学 | Method for preparing needle coke by compounding coal-based and petroleum-based components |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011089024A (en) | 2011-05-06 |
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