WO2017159769A1 - 人造黒鉛電極の製造方法 - Google Patents
人造黒鉛電極の製造方法 Download PDFInfo
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- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
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Definitions
- the present invention relates to a method for producing an artificial graphite electrode, and more particularly to a method for producing an electrode for electric steelmaking used when electric furnace steel is produced by electric steelmaking.
- An artificial graphite electrode is made of coal-based or petroleum-based needle coke as an aggregate, and is solidified with a binder pitch as a binder, and is widely used as an electrode for electric steelmaking.
- Such an artificial graphite electrode is usually produced by pulverizing needle coke to a predetermined particle size, then combining (kneading) with a binder pitch, then extruding, and then firing and graphitizing. If necessary, after the firing treatment, the impregnation pitch is impregnated, and after the secondary firing treatment, graphitization is performed.
- the kneading process of needle coke and binder pitch is important to affect various performances of artificial graphite electrode, such as thermal expansion coefficient (CTE) and irreversible expansion phenomenon (puffing) in graphitization. It is a difficult process.
- the kneading step the kneader is kneaded at a temperature equal to or higher than the softening point of the binder pitch. Then, in the next extrusion process, in order to maintain the electrode quality and productivity at a predetermined level, the extrusion rate is adjusted by adjusting the amount of binder pitch added during kneading, or by the molding pressure of the extrusion process. adjust.
- the amount of binder pitch used is related to the pore volume of needle coke, and the larger the pore volume of needle coke, the greater the required amount of binder pitch.
- the amount of binder pitch used is related to the extrusion molding process after kneading with a kneader, and in order to perform extrusion at a constant extrusion speed, it is necessary to increase the amount of binder pitch when the pore volume of needle coke is large. Therefore, when needle coke with a large pore volume is sufficiently kneaded with the increased binder pitch, it cannot be molded unless the molding pressure is raised, and depending on the capabilities of the extrusion molding machine, it may exceed the limit and cannot be molded. There is also. The volatile matter generated from a large amount of binder pitch during firing increases, and the electrode may crack.
- Patent Document 1 discloses that finely powdered coal tar pitch (secondary binder) having a softening point of 150 ° C. or higher and fixed carbon of 65 to 75% as a part of a binder component is premixed with needle coke, and the mixture is used as the remainder of the binder component. It is disclosed that it is extruded together with a coal tar pitch (stationary binder) having a softening point of 85 to 105 ° C. and fixed carbon of 55 to 60%, followed by firing and graphitization by a conventional method. In this case, it is essential to mix in advance a secondary binder having a softening point of 150 ° C. or higher, which is different from that of the stationary binder.
- secondary binder having a softening point of 150 ° C. or higher and fixed carbon of 65 to 75% as a part of a binder component is premixed with needle coke, and the mixture is used as the remainder of the binder component. It is disclosed that it is extrude
- Patent Document 2 discloses a method for producing a graphite electrode using a coal-based needle coke having a true specific gravity of 2.150 or more obtained by calcination at 1500 to 1700 ° C. in order not to use a large amount of binder pitch. It is disclosed that a binder pitch having a softening point of 100 to 150 ° C. is used as a binder. In this case, a binder pitch of 100 to 150 ° C. having a softening point higher than usual is indispensable as the binder pitch, and needle coke also has a high calcination temperature.
- JP-A 63-74661 Japanese Patent Laid-Open No. 5-28998
- the present invention is to provide a method for producing an artificial graphite electrode that enables kneading and subsequent extrusion molding without increasing the amount of binder pitch used even with needle coke having a large pore volume. .
- the present inventor made the step of kneading the binder pitch into the needle coke having pores into at least two-stage divided kneading, and the binder pitch in the divided kneading
- the inventors have found that the above-mentioned problems can be solved by setting the addition amount and the kneading time within a predetermined range, and the present invention has been completed.
- the present invention is a method for producing an artificial graphite electrode by kneading a binder pitch into needle coke, then extruding, then firing and graphitizing, and the binder pitch is formed on the needle coke having pores.
- the kneading step is divided into at least two stages of kneading, and the addition amount of the binder pitch and kneading time in the divided kneading have a kneading index represented by the following formula (1) in the range of 0.1 to 0.7.
- A indicates the total amount of binder pitch used in the entire kneading process
- a1 indicates the amount of binder pitch used in the first stage of kneading
- T represents the total kneading time in the kneading step
- t1 represents the first kneading time.
- the usage-amount (wt%) of binder pitch is the quantity (outside number) with respect to the usage-amount of needle coke 100 wt%.
- the needle coke preferably has a true specific gravity of 2.00 or more and a pore volume of 0.10 cc / g to 0.30 cc / g at a pore diameter of 0.01 to 120 ⁇ m.
- the pore physical properties are measured by a mercury intrusion method using a coke particle size of 2 to 5 mm.
- the measurement conditions are a contact angle of 141.2 ° between mercury and needle coke and a surface tension of mercury of 480 dyn / cm.
- the binder pitch is preferably a softening point of 70 ° C. to 150 ° C. and an amount of ⁇ resin of 15 to 30 wt%.
- the amount of ⁇ -resin is measured by a solvent analysis method of JIS K2425, and is indicated by a difference between toluene-insoluble matter and quinoline-soluble matter.
- the present invention even needle coke having many pores can be kneaded and then extruded without increasing the amount of binder pitch used.
- the extrusion speed in the extrusion molding process can be maintained constant, and the electrode quality and productivity can be maintained at a predetermined level. Therefore, when the pressure in the extrusion molding process is the same as before, extrusion molding is possible even if the amount of binder pitch used is smaller than usual. On the other hand, since it is not necessary to increase the amount of binder pitch used, it is possible to reduce the pressure in the extrusion molding process, which can contribute to great energy savings.
- Various performances of the artificial graphite electrode obtained by the production method of the present invention such as bulk density, thermal expansion coefficient and puffing property, are the same or improved as those produced by the conventional method.
- the binder pitch is divided and added twice or more.
- the amount of binder pitch that can be extruded is an upper limit of 35 wt% (the outer number when needle coke is 100 wt%, the same applies hereinafter).
- a binder pitch amount for example, 25 wt%
- a larger amount for example, 27 wt%
- the extrusion speed is constant. It cannot be extruded because it does not become.
- a larger amount of binder pitch than usual is used to keep the molding speed constant, gas is likely to be generated from the binder pitch during firing, leading to the possibility of cracking of the electrode.
- extrusion molding can be performed at the same extrusion speed as before after kneading at 25 wt%.
- the amount of binder pitch used is 25 wt% with respect to 100 wt% of needle coke
- 25 wt% of binder pitch used for example, 10 wt% of binder pitch is added as the first stage kneading.
- the remaining 15 wt% is added as a second stage kneading and kneading is performed for a certain time.
- the amount of binder pitch added and the kneading time in the first stage kneading must be determined so that the kneading index represented by the above formula (1) is in the range of 0.1 to 0.7.
- the first stage of kneading scatters volatile matter from the binder pitch, increases the viscosity of the binder pitch, and forms a solidified layer of the binder pitch on the pore surface (shallow part). . Therefore, the binder pitch added after the second stage is accumulated on the surface of the pores without penetrating into the deep part in the pores by the binder pitch solidified layer formed by the kneading in the first stage.
- the binder pitch accumulated on the pore surface portion can also act as a lubricant during extrusion molding. Therefore, it is considered that subsequent extrusion molding can be performed without increasing the amount of binder pitch used even in needle coke having a large pore volume.
- the kneading index is less than 0.1, the amount of binder pitch to be added in the first stage kneading is small and the kneading time is short, so that the kneading state of the needle coke and the binder pitch in the first stage becomes insufficient. If the kneading index exceeds 0.7, the molding pressure will not be different from the case where the entire amount of the binder pitch is added in one kneading, which is a normal method, and the effect is lost.
- the kneading index is preferably in the range of 0.15 to 0.70, more preferably 0.20 to 0.50.
- the at least two-stage divided kneading means that the binder pitch is added in two or more stages, and the operation of the kneader such as a kneader may be continued. Also good.
- the first stage kneading time is preferably 5 minutes or longer, and the second stage kneading time is preferably 3 minutes or longer.
- the second stage kneading is performed.
- the amount of binder pitch used may be the remaining amount after subtracting the amount of binder pitch used in the first stage kneading out of the total amount of binder pitch used for needle coke.
- the remaining time after subtracting the kneading time of the first stage may be used. That is, it is not necessary to greatly change the binder pitch usage and kneading time as a whole.
- about the 2nd stage and after it can also be set as further multistage kneading
- the amount of binder pitch used in the second stage and the kneading time can be reduced.
- the needle coke to be used is not particularly limited, and coal-based needle coke and petroleum-based needle coke can be used.
- the present invention is effective when the amount of fine pores (volume) of needle coke is larger than usual.
- Use of needle coke having a large amount of pores (volume) is advantageous in suppressing puffing.
- the pore volume of needle coke is indicated by an amount measured by a mercury intrusion method using a coke particle size of 2 to 5 mm, and a pore volume with a pore diameter of 0.01 to 120 ⁇ m, preferably 0.10 to 0 .30 cc / g, more preferably 0.10 to 0.25 cc / g, and desirably 0.13 to 0.20 cc / g.
- the pore diameter was calculated with a contact angle of 141.2 ° between mercury and needle coke and a surface tension of 480 dyn / cm of mercury.
- the pore volume is less than 0.10 cc / g, the pore volume is small and the expression effect of the present invention is small. If it exceeds 0.30 cc / g, the amount of binder pitch required is too large, so that it is inferior in suitability as needle coke for producing a graphite electrode.
- the binder pitch as the binder used has a softening point of 70 to 150 ° C. and ⁇ resin of 15 to 30%.
- the softening point is less than 70 ° C., the viscosity becomes too low and the inner part of the fine hole of the needle coke easily enters, so that the effect of the present invention becomes insufficient.
- the softening point exceeds 150 ° C., the temperature of the kneader to be kneaded must be raised and the viscosity of the binder pitch must be forcibly lowered, which is disadvantageous in terms of production efficiency.
- a more preferable softening point is 80 to 130 ° C, particularly 90 to 120 ° C.
- the binder pitch may be the same kind of binder pitch, for example, the same softening point may be divided and kneaded in at least two stages, or different binder pitches, for example, different softening points, in the first stage kneading and the second stage kneading. May be used.
- the softening point such as kneading using a binder pitch with a high softening point in the first stage and a binder pitch with a low softening point in the second stage, the pore diameter and binder pitch of the needle coke into which the binder pitch penetrates are changed. The amount to penetrate can be adjusted.
- Example 1 As the needle coke, a coal-based needle coke having a true specific gravity of 2.15 and a pore volume of 0.136 cc / g measured with a mercury porosimeter was used. This needle coke was pulverized with a jaw crusher, and 8-16 mesh (Me ′) was sieved. Then, the upper and lower sieves were mixed, pulverized with a hammer crusher, and sieved to 48-200Me ′ and 200Me ′ or less. After the particle size distribution of each particle size distribution is 40% (8-16Me '), 35% (48-200Me'), 25% (200Me 'or less) from the larger particle size, this needle coke is mixed with binder pitch.
- the binder pitch used has a softening point of 97 ° C. and a ⁇ resin of 20%. That is, using a kneader, as a whole kneading step, the total amount of binder pitch used is 25 wt% with respect to needle coke 100 wt%, and kneading is performed at 160 ° C. for 20 minutes. In this kneading step, 12.5 wt% of the binder pitch was blended as the first stage and kneaded for 7.5 minutes, and then the remaining 12.5 wt% was blended as the second stage while maintaining the temperature. Kneaded for 5 minutes.
- the kneading index was 0.19.
- the molding pressure was adjusted with an extrusion molding machine so that the extrusion speed was constant at 7 cm / min, and the pressure was set as the extrusion pressure.
- CTE was extruded to a size of 20 mm ⁇ ⁇ 100 mm, fired at 900 ° C., and then graphitized at 2500 ° C. to obtain a CTE sample.
- CTE was measured by measuring the average coefficient of thermal expansion from room temperature to 500 ° C. The results are shown in Table 1.
- Examples 2-5 A graphite electrode was produced in the same manner as in Example 1 except that the kneading conditions and molding conditions shown in Table 1 were changed. The results are also shown in Table 1.
- Comparative Example 1 In the same manner as in the conventional method, the graphite electrode is kneaded in the same manner as in the Examples, except that the binder pitch is kneaded into needle coke in two steps, and the total amount is 25 wt. Manufactured. The results are also shown in Table 1.
- FIG. 1 shows the relationship between the kneading index of Examples 1 to 5 and the molding pressure.
- the molding pressure value (13.5 MPa) of Comparative Example 1 is displayed as a reference line.
- Example 1 From the kneaded material of Example 1 and Comparative Example 1, kneaded particles having a diameter of 1 to 2 mm are collected, and tomographic imaging is performed at a resolution of 3 ⁇ m using an X-ray CT apparatus (Marstoken Solution TUX-3200N) to reconstruct a 3D image. did.
- Cross-sectional images were obtained from arbitrary cross-sections of 3D reconstructed images.
- a typical cross-sectional image of Example 1 is shown in FIG. 2, and a typical cross-sectional image of Comparative Example 1 is shown in FIG.
- FIG. 2 the thickness of the binder pitch distributed around the needle coke is almost uniform, whereas in FIG. 3, the thickness of the binder pitch is non-uniform.
- the electrode quality and productivity can be maintained at a predetermined level without increasing the amount of binder pitch used, which can contribute to a great amount of energy saving.
- the obtained artificial graphite electrode is excellent in various performances such as a coefficient of thermal expansion and puffing, so that it is particularly useful as an electrode for electric steelmaking used when electric furnace steel is produced by electric steelmaking.
Abstract
Description
そこで、本発明は、細孔容積の大きいニードルコークスでも、バインダーピッチの使用量を増加させることなく、混錬、及びその後の押出成型が可能となる人造黒鉛電極の製造方法を提供することにある。
混練指数 = (a1/A) × (t1/T) (1)
ここで、Aは混練工程全体におけるバインダーピッチの全使用量を示し、a1は第一段階の混練におけるバインダーピッチの使用量を示す。Tは混練工程における全混練時間を示し、t1は第一段階の混練時間を示す。
なお、バインダーピッチの使用量(wt%)は、ニードルコークスの使用量100wt%に対する量(外数)である。
この場合、細孔物性は、2~5mmのコークス粒度を用い、水銀圧入法で測定し、その測定条件は、水銀とニードルコークスの接触角141.2°、水銀の表面張力は480dyn/cmとする。
この場合、βレジン量は、JIS K2425の溶剤分析法によって測定され、トルエン不溶分とキノリン可溶分の差で示す。
なお、本発明の製法で得られた人造黒鉛電極の各種性能、例えば、嵩密度、熱膨張係数及びパフィング性は、従来法で製造した場合と同等ないしは改善される。
ニードルコークスの細孔容積は、2~5mmのコークス粒度を用い、水銀圧入法で測定した量で示すが、細孔径が0.01~120μmまでの細孔容積が、好ましくは0.10~0.30cc/g、より好ましくは0.10~0.25cc/g、望ましくは0.13~0.20cc/gである。この場合、細孔径は、水銀とニードルコークスの接触角141.2°、水銀の表面張力480dyn/cmとして計算したものである。細孔容積が0.10cc/gを下回る場合は、細孔容積が少なく本発明の発現効果が少ない。0.30cc/gを超える場合は、必要なバインダーピッチ量が多くなり過ぎるため、黒鉛電極を製造するためのニードルコークスとして適格性に劣る。
バインダーピッチは、同種のバインダーピッチ、例えば軟化点の同じものを少なくとも二段階の分割混練としても良いし、第一段階混練と第二段階混練とで、異種のバインダーピッチ、例えば軟化点の異なるものを使用しても良い。第一段階は高い軟化点のバインダーピッチ、第二段階は低い軟化点のバインダーピッチを使用して混練するなど、軟化点を変えることで、バインダーピッチが浸入するニードルコークスの細孔径やバインダーピッチが浸入する量を調製することができる。
ニードルコークスとして、真比重2.15、水銀ポロシメーターで測定した細孔容積0.136cc/gの石炭系ニードルコークスを用いた。このニードルコークスをジョークラッシャーで粉砕し、8-16メッシュ(Me')を篩とった後、篩上と下を混合し、ハンマークラッシャーで粉砕し、48-200Me'と200Me'以下に篩分けした。それぞれの粒度分布が、粒子径の大きい方から、40%(8-16Me')、35%(48-200Me')、25%(200Me'以下)で粒度配合した後、このニードルコークスをバインダーピッチ(BP)と二段階で混練した。使用したバインダーピッチは、軟化点97℃、βレジン20%である。すなわち、ニーダーを使用して、全混練工程として、ニードルコークス100wt%に対してバインダーピッチの全使用量25wt%を配合し、160℃で20分の混練を行う。この混練工程において、バインダーピッチ量を、第一段階として12.5wt%配合して7.5分混練をした後、温度を維持したまま第二段階として残りの12.5wt%を配合し更に12.5分混練した。この場合の混練指数は0.19であった。
混練後、押出成型機で、押出速度が7cm/分一定になるように、成形圧力を調整し、その圧力を押出圧力とした。また、CTEについては、20mmφ×100mmの大きさに押出成型後、900℃で焼成し、その後2500℃で黒鉛化してCTEサンプルとした。CTEの測定は、室温~500℃の平均熱膨張係数を測定した。
それらの結果を表1に示す。
表1に示す混練条件及び成型条件に変更すること以外、実施例1と同様にして、黒鉛電極を製造した。その結果も同様に表1に示す。
従来法と同様に、ニードルコークスへのバインダーピッチの混練を、二回に分けることなく、一回で全量25wt%配合して混練した後、成型すること以外、実施例と同様にして、黒鉛電極を製造した。その結果も同様に表1に示す。
Claims (4)
- ニードルコークスにバインダーピッチを混練した後、押出成型し、次いで焼成及び黒鉛化処理することにより人造黒鉛電極を製造する方法であって、細孔を有するニードルコークスにバインダーピッチを混練する工程を、少なくとも二段階の分割混練とし、その分割混練におけるバインダーピッチの添加量と混練時間を、下記式(1)で表される混練指数が0.1~0.7の範囲となるようにすることを特徴とする人造黒鉛電極の製造方法。
混練指数 = (a1/A) × (t1/T) (1)
ここで、Aは混練工程全体におけるバインダーピッチの全使用量を示し、a1は第一段階の混練におけるバインダーピッチの使用量を示す。Tは混練工程における全混練時間を示し、t1は第一段階の混練時間を示す。 - ニードルコークスが、真比重2.00以上で、細孔径0.01~120μmにおける細孔容積0.10~0.30cc/gである請求項1記載の人造黒鉛電極の製造方法。
- バインダーピッチが、軟化点70~150℃で、βレジン量15~30wt%である請求項1又は2記載の人造黒鉛電極の製造方法。
- 混練指数が0.15~0.70の範囲である請求項1~3のいずれかに記載の人造黒鉛電極の製造方法。
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