CN113661151A - 高密度人造石墨电极的制造方法 - Google Patents
高密度人造石墨电极的制造方法 Download PDFInfo
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Abstract
本发明提供一种高密度人造石墨电极的制造方法,其不大幅改变所使用的针状焦炭的粒度、比例,或者不增加粘结剂沥青的量,或者不以高成型压力进行挤出成型。上述高密度人造石墨电极的制造方法是向针状焦炭混炼粘结剂沥青后,进行挤出成型,接着,通过煅烧和石墨化处理,由此制造人造石墨电极的方法,使用如下针状焦炭:通过对所使用的粉碎针状焦炭中至少一部分的粉碎针状焦炭进行焦炭形状的变更处理,由此使包络周长/周长的比与变更前的数值相比增大1%以上。这里,包络周长为将粉碎的针状焦炭的凸部的顶点以最短的距离连接时的一周的长度,周长为粒子的一周的长度。
Description
技术领域
本发明涉及高密度人造石墨电极的制造方法,特别是在通过电气炼钢制造电炉钢时使用的高密度电气炼钢用电极的制造方法。
背景技术
人造石墨电极以煤系或石油系针状焦炭为骨料,并用作为粘结材料的粘结剂沥青将该骨料固定,被广泛用作电气炼钢用电极。这样的人造石墨电极通常如下制造:将针状焦炭筛分并进一步进行粉碎而制备成规定粒度后,与粘结剂沥青混炼,接着进行挤出成型,然后,进行煅烧和石墨化处理。
近年来,随着大型高负荷电炉的普及,在直流电炉和交流电炉中,人造石墨电极的直径为24~32英寸正成为主流。如果人造石墨电极进行大型化,则电极使用中的半径方向的温度差变大,因此容易产生因热冲击所致的裂纹。作为裂纹的原因之一,考虑了电极内部的组织结构、特别是空隙的形态等。
在专利文献1中,从人造石墨电极切出样品,根据剖面的图像解析,由骨料间形成的空隙的周长和面积算出形状系数这样的参数,并公开了空隙的状态与不易产生裂纹的人造石墨电极的关系。
在人造石墨电极的制造方法中,将针状焦炭与粘结剂沥青混炼,刚挤出成型后的成型体的质量会决定人造石墨电极的最终品质。另外,人造石墨电极存在与外周部相比,中心部的密度低的趋势,特别是直径越大,该趋势越强。因此,为了极力减小骨料间形成的空隙,多在粉碎针状焦炭后进行分级,选择各种粒度的针状焦炭,并以期望的配合量使用。
在非专利文献1中公开了骨料的填充密度与成型体的密度有密切关系,为了提高密度而使用骨料自身的密度高的骨料,并调整为提高填充密度那样的粒度分布。此时使用的针状焦炭组合使用20~40目(0.8~0.4mm)的粒、20~150目(0.8~0.1mm)的粉末、10μm以下的微粉,或者使用炭黑代替10μm以下的微粉。
现有技术文献
专利文献
专利文献1:日本特开2002-246171号公报
非专利文献
非专利文献1:碳,1977,No.91P138-144
发明内容
如上所述,在现有技术中,为了防止伴随大径化的人造石墨电极的热冲击所致的裂纹,在人造石墨电极的制造方法中,为了减少骨料间形成的空隙,在粉碎针状焦炭后,通过分级来筛选粒度,然后,将多种粒度的针状焦炭组合而与粘结剂沥青混炼。这些是根据组合各种粒径来填埋间隙以提高填充密度的想法而实施的。
但是,针状焦炭的晶体结构以针状生长,在粉碎时成为长形的形态,且产生来自晶体结构的细小凹凸。因此,即使为了提高作为骨料的针状焦炭的填充密度而将组合多种粒度的粉碎品组合,也会残留由形态来源产生的空隙。
因此,本发明的目的在于提供一种人造石墨电极的制造方法,其通过与现有技术不同的方法来制造密度高的人造石墨电极。即,提供一种能够在不如现有技术中公开的那样大幅改变所使用的针状焦炭的粒度、比例,或者不增加粘结剂沥青的量,或者不以高成型压力进行挤出成型的情况下得到高密度人造石墨电极的制造方法。
本发明人为了解决上述的课题反复进行了深入研究,结果发现通过使用对用作骨料的粉碎针状焦炭的一部分或全部进行追加处理,作为骨料的针状焦炭变更处理为特定形状的针状焦炭,能够解决上述问题,完成了本发明。
即,本发明为一种高密度人造石墨电极的制造方法,其特征在于,将针状焦炭粉碎,混炼粘结剂沥青后,进行挤出成型,接着,进行煅烧和石墨化处理,由此制造人造石墨电极,将针状焦炭粉碎后,对粉碎针状焦炭的一部分或全部进行焦炭形状的变更处理,由此使形状变更处理后的针状焦炭的包络周长/周长的比(EA/LA)以形状变更处理前的数值(E0/L0)为基准增大1%以上。
在此,包络周长为将针状焦炭粒子的凸部的顶点以最短的距离连接时的一周的长度,周长为粒子的一周的长度。
粒子的包络周长与周长通过图像解析装置来测定。
上述制造方法中,针状焦炭优选真密度为2.00以上,CTE为1.30×10-6/℃以下,含氮量为0.6wt%以下,含硫量为0.6wt%以下。
此时,CTE是制作标准的测试件,测定室温~500℃的平均热膨胀系数而算出的。氮量依据JIS M 8819而测定。硫量依据JIS M 8813而测定。
上述制造方法中,在粉碎针状焦炭中,进行形状的变更处理的针状焦炭优选粒度为500μm以下。
上述制造方法中,粘结剂沥青优选软化点为70℃~150℃、β树脂量为15~30wt%。
此时,β树脂量通过JIS K2425的溶剂分析法而测定,以甲苯不溶成分与喹啉可溶成分的差表示。
根据本发明,能够在不大幅改变所使用的针状焦炭的粒度、比例,或者不增加粘结剂沥青的量,或者不以高成型压力进行挤出成型的情况下制造高密度的人造石墨电极。因此,本发明也能够充分适用于与大型高负荷电炉对应的大型人造石墨电极(例如直径24~32英寸)的制造。
另外,本发明即使在不改变针状焦炭和粘结剂沥青的量、比例的情况下,也能够比现有条件降低挤出成型工序的压力而生产密度高的人造石墨电极,也能够有助于大量的节能。
具体实施方式
本发明的制造方法的特征在于,使用如下针状焦炭:通过对与粘结剂沥青混炼的针状焦炭粉碎物的全部或一部分进行焦炭形状的变更处理,由此使形状变更处理后的针状焦炭的包络周长/周长的比(EA/LA)以形状变更处理前的数值(E0/L0)为基准增大1%以上。
此时,变更形状的粉碎针状焦炭可以以全部作为对象,也可以仅对其一部分进行变更处理。可以对粉碎针状焦炭的1wt%以上、优选5wt%以上、更优选20wt%以上进行变更处理。进行形状变更处理的粉碎针状焦炭的粒径没有特别限定,但细粒更为有效,可以对例如粒径500μm以下的粉碎针状焦炭进行变更处理。优选为130μm以下的粉碎针状焦炭,进一步优选为75μm以下的粉碎针状焦炭。
对通过进行焦炭形状的变更处理而使形状变更处理后的粉碎针状焦炭的包络周长/周长的比(EA/LA)以形状变更处理前的数值(E0/L0)为基准增大1%以上的方法进行说明。
将块状的针状焦炭用粉碎机、例如颚式破碎机、锤式破碎机、辊式破碎机或双辊式破碎机粉碎至微粒后,按粒度进行分级。进一步用辊磨机、球管磨机进行微粉碎,然后按粒度进行分级。
对经分级的微粒、微粉粒的针状焦炭的一部分或全部进行焦炭形状的变更处理。在该形状变更处理中,只要能够进行期望的形状变更处理,就可以利用各种装置。为了形状变更处理,可以使用例如市售的球状化装置,球状化装置市售有气流式、机械式、高速搅拌式,可以任意地选择。
应予说明,对形状进行了变更处理的针状焦炭的微粒、微粉粒的包络周长和周长的测定使用能够测定微粒、微粉粒的包络周长和周长的形状图像解析装置、或粒子分布图像解析装置、或图像解析粒度分布计进行。
本发明的特征在于,进行了焦炭形状变更处理的粉碎针状焦炭的包络周长/周长(EA/LA)以进行形状变更处理前的数值(E0/L0)为基准增大1%以上。由此,能够显著提高成型体的堆积密度(BD),进而显著提高煅烧后、石墨化后的堆积密度。鉴于堆积密度、成型压力,上述比率优选增大3%以上,更优选增大5%以上。
应予说明,这样的形状变更率(R)也可以由以下的数学式表示。
在包络周长/周长的变更处理前后的变更率(R)为小于1%的差的情况下,大量残留来自针状焦炭的晶体结构的针状形态。因此,在组合多种粒度的针状焦炭而与粘结剂沥青混炼并进行挤出成型而得的成型体中残留起因于来自针状焦炭的晶体结构的针状形态而产生的空隙,成为因热冲击所致的裂纹的原因。
使用的针状焦炭没有特别限定,可以使用煤系的针状焦炭、石油系针状焦炭。
针状焦炭的真密度为2.120~2.170g/cm3,优选为2.125~2.165g/cm3,进一步优选为2.130~2.160g/cm3。
针状焦炭的CTE为0.8~1.4×10-6/℃,优选为0.85~1.3×10-6/℃,进一步优选为0.9~1.25×10-6/℃。
针状焦炭的表观密度为2.090~2.140g/cm3,优选为2.110~2.135g/cm3,进一步优选为2.125~2.130g/cm3。
针状焦炭中所含的氮量为0.60wt%以下,优选为0.55wt%,进一步优选为0.45wt%以下。针状焦炭中所含的硫量为0.60wt%以下,优选为0.45wt%以下,进一步优选为0.30wt%以下。
作为所使用的粘结材料的粘结剂沥青优选软化点为70~150℃、β树脂为15~30%。如果软化点低于70℃,则粘度变得过低,容易进入针状焦炭的细孔的深部,本发明的表现效果不充分。如果软化点超过150℃,则必须提高进行混炼的捏合机的温度并强制性地降低粘结剂沥青的粘度,因此,在生产效率方面不利。更优选的软化点为80~130℃。
粘结剂沥青可以将相同种类的粘结剂沥青、例如将软化点相同的粘结剂沥青进行至少二阶段的分段混炼,也可以在第一阶段混炼和第二阶段混炼使用不同种类的粘结剂沥青、例如使用软化点不同的粘结剂沥青。通过改变软化点,能够调整粘结剂沥青渗入的针状焦炭的细孔径、粘结剂沥青渗入的量。
应予说明,根据需要,可以在煅烧处理后,使含浸沥青含浸,在二次煅烧处理后进行石墨化处理。
将针状焦炭筛分并进一步粉碎,向其中配合粘结剂沥青等,进行混炼、成型、煅烧、沥青含浸、二次煅烧、在2500℃左右的高温进行石墨化,由此能够得到人造石墨电极。根据本发明的制造方法,能够在不提高成型压力的情况下空隙少且高密度的人造石墨电极。
实施例
以下,利用实施例和比较例对本发明进行更详细的说明,但本发明并不限定于这些实施例。
实施例1~7
作为针状焦炭,使用真密度2.15、用压汞仪测定的细孔容积为0.136cc/g的煤系针状焦炭。
将该针状焦炭用颚式破碎机进行粉碎,将8-16目(Me’)(2.38-1.0mm)过筛后,将筛上和筛下混合,用锤式破碎机进行粉碎,筛分为48-200Me’(325-74μm)和200Me’以下(74μm以下)。
这些粒度中,使用Seishin企业制制的高速搅拌型粉体化装置对200Me’以下的粉体进行形状变更处理。形状处理以相同焦炭的配合比例在4个条件下进行(实施例1、3、4、5)。进而,对于实施例2和实施例6、7,配合未进行形状变更处理的相同粒径的焦炭,对形状变更处理的效果进行比较。
形状变更处理的程度使用Seishin企业制的粒子形状图像解析装置PITA-04进行测定。为了表示进行了何种程度的形状变更处理,将形状变更处理后的200Me’以下的包络周长/周长的比(EA/LA)以形状变更处理前的200Me’以下的包络周长/周长的比(E0/L0)为基准而算出的形状变更率(R)示于表1。
将各自的粒度分布以从粒径大的一方起为40%(8-16Me’)、35%(48-200Me’)、25%(200Me’以下)进行粒度配合后,将该针状焦炭100份与粘结剂沥青(BP)27份混炼。所使用的粘结剂沥青为软化点97℃、β树脂20%。
将挤出成型物在900℃煅烧,其后在2500℃石墨化。
对挤出成型物、900℃煅烧后、石墨化后的样品分别测定堆积密度(BD)。
将它们的果示于表2。
比较例1
不进行利用高速搅拌型粉体球状化装置的表面变更处理,除此以外,与实施例同样地制造石墨电极。将其结果也示于表1和表2。
[表1]
[表2]
产业上的可利用性
根据本发明的制造方法,与为了防止伴随大径化的人造石墨电极的热冲击所致的裂纹、为了减少成为原因的空隙,通过分级而筛选粒度后,组合多种粒度的针状焦炭的情况相比,能够减少空隙,其结果能够有助于将人造石墨电极高密度化,且能够降低挤出成型工序的压力,也能够有助于大量的节能。因此,通过本发明的制造方法制作的人造石墨电极能够适用于与大型高负荷电炉对应的大型人造石墨电极。
Claims (4)
1.一种高密度人造石墨电极的制造方法,其特征在于,将针状焦炭粉碎,混炼粘结剂沥青后,进行挤出成型,接着进行煅烧和石墨化处理,由此制造人造石墨电极,将针状焦炭粉碎后,对粉碎针状焦炭的一部分或全部进行焦炭形状的变更处理,由此使形状变更处理后的针状焦炭的包络周长/周长的比即EA/LA以形状变更处理前的数值即E0/L0为基准增大1%以上,
这里,包络周长为将针状焦炭粒子的凸部的顶点以最短的距离连接时的一周的长度,周长为针状焦炭粒子的一周的长度。
2.根据权利要求1所述的高密度人造石墨电极的制造方法,其中,针状焦炭的真密度为2.00以上,CTE为1.30×10-6/℃以下,含氮量为0.6wt%以下,含硫量为0.6wt%以下。
3.根据权利要求1或2所述的高密度人造石墨电极的制造方法,其中,在粉碎针状焦炭中,进行形状的变更处理的针状焦炭的粒度为500μm以下。
4.根据权利要求1或2所述的高密度人造石墨电极的制造方法,其中,粘结剂沥青的软化点为70~150℃、β树脂量为15~30wt%。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005179140A (ja) * | 2003-12-22 | 2005-07-07 | Toyo Tanso Kk | 高熱伝導黒鉛材料 |
US20090294326A1 (en) * | 2008-06-03 | 2009-12-03 | Miller Douglas J | Reduced Puffing Needle Coke From Coal Tar Distillate |
CN103011819A (zh) * | 2012-12-27 | 2013-04-03 | 临邑县鲁北炭素有限公司 | 大直径石墨电极生产工艺 |
CN205435878U (zh) * | 2015-12-29 | 2016-08-10 | 湖南摩根海容新材料有限责任公司 | 一种粉体材料整形分级设备 |
CN107206746A (zh) * | 2014-12-03 | 2017-09-26 | 艾克斯温有限责任公司 | 通过三维打印制造致密碳制品的方法 |
EP3431458A1 (en) * | 2016-03-17 | 2019-01-23 | Nippon Steel & Sumikin Chemical Co., Ltd. | Method for manufacturing artificial graphite electrode |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3676535A (en) * | 1969-11-07 | 1972-07-11 | Leslie H Juel | Method and apparatus for controlling orientation of needle-like carbon particles in extruded carbon stock |
US4604184A (en) * | 1983-11-16 | 1986-08-05 | Domtar Inc. | Modified coal-tar pitch |
JP2002246171A (ja) | 2001-02-19 | 2002-08-30 | Tokai Carbon Co Ltd | 耐スポーリング性に優れた製鋼用人造黒鉛電極 |
EP1982956B1 (en) * | 2005-12-27 | 2014-03-12 | Nippon Oil Corporation | Raw coal for making carbonaceous material for electricity storage or needle coke |
US9777221B2 (en) * | 2006-06-29 | 2017-10-03 | Graftech International Holdings Inc. | Method of producing needle coke for low CTE graphite electrodes |
JP2014197496A (ja) * | 2013-03-29 | 2014-10-16 | 戸田工業株式会社 | 球形炭素材 |
JP2015038840A (ja) * | 2013-08-19 | 2015-02-26 | 東海カーボン株式会社 | 燃料電池用セパレータおよび燃料電池用セパレータの製造方法 |
CN104085883B (zh) | 2014-07-09 | 2017-09-15 | 深圳市贝特瑞新能源材料股份有限公司 | 一种锂离子电池用人造石墨负极材料及其制备方法 |
CN105958072B (zh) * | 2016-06-20 | 2019-02-05 | 傅云峰 | 一种天然鳞片石墨基负极材料的制备方法 |
JP6977504B2 (ja) | 2016-11-22 | 2021-12-08 | 三菱ケミカル株式会社 | 非水系二次電池用負極材、非水系二次電池用負極及び非水系二次電池 |
CN107369823B (zh) | 2017-07-25 | 2020-07-07 | 广东海洋大学 | 一种锂离子电池用人造石墨复合负极材料及其制备方法 |
CN108328613B (zh) | 2017-12-15 | 2019-10-25 | 大同新成新材料股份有限公司 | 一种利用针状焦生产石墨负极材料的方法及负极材料 |
CN109687013B (zh) | 2018-12-27 | 2020-07-07 | 江西省汇亿新能源有限公司 | 一种磷酸铁锂电池及其制备方法 |
-
2020
- 2020-03-27 CN CN202080025371.9A patent/CN113661151A/zh active Pending
- 2020-03-27 WO PCT/JP2020/014151 patent/WO2020203825A1/ja active Search and Examination
- 2020-03-27 US US17/439,984 patent/US20220169515A1/en active Pending
- 2020-03-27 EP EP20783392.2A patent/EP3950639A4/en active Pending
- 2020-03-27 JP JP2021512034A patent/JP7457002B2/ja active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005179140A (ja) * | 2003-12-22 | 2005-07-07 | Toyo Tanso Kk | 高熱伝導黒鉛材料 |
US20090294326A1 (en) * | 2008-06-03 | 2009-12-03 | Miller Douglas J | Reduced Puffing Needle Coke From Coal Tar Distillate |
CN103011819A (zh) * | 2012-12-27 | 2013-04-03 | 临邑县鲁北炭素有限公司 | 大直径石墨电极生产工艺 |
CN107206746A (zh) * | 2014-12-03 | 2017-09-26 | 艾克斯温有限责任公司 | 通过三维打印制造致密碳制品的方法 |
CN205435878U (zh) * | 2015-12-29 | 2016-08-10 | 湖南摩根海容新材料有限责任公司 | 一种粉体材料整形分级设备 |
EP3431458A1 (en) * | 2016-03-17 | 2019-01-23 | Nippon Steel & Sumikin Chemical Co., Ltd. | Method for manufacturing artificial graphite electrode |
Non-Patent Citations (1)
Title |
---|
蒋文忠: "《炭素工艺学》", 30 April 2009, 冶金工业出版社 * |
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