CN107311686B - 一种石墨电极的制备工艺 - Google Patents
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Abstract
本发明涉及一种石墨电极的新型制备工艺,以天然石墨(或天然石墨和石墨残极)和添加剂为原料,以液体碳素树脂为结合剂,按照一定配比进行配料,经过常温混碾涂层后,把料晾干或烘干到一定潮湿度后,把料装在模具内,抽真空(加石墨残极的配料也可不用抽真空)和封口后,放入冷等静压成型机内进行成型。成型后脱模的坯体进行放置和加热固化,然后进行防氧化涂层和裸烧或不涂防氧化涂层直接还原气氛下或埋碳条件下烧成,出窑后进行加工即得到石墨电极产品;其具有常温混料和成型,环境显著改善;生产周期由150~160天缩短到30天以内,生产效率大大提高;生产成本显著降低的特点。
Description
技术领域
本发明涉及石墨电极,尤其涉及一种石墨电极的制备工艺。
背景技术
随着社会进步,经济增长方式由粗旷型转变成集约型和高技术型。高能耗高污染的经济增长已经不能适合中国的国情,提高效率和技术,降低成本,降低能耗和无污染已经成为发展经济的主流。
传统石墨电极生产工艺流程是:原料→破粉碎→筛分→配料→热混捏→热成型→一次焙烧→一次浸渍→二次焙烧→二次浸渍→焙烧→石墨化→加工→产品。一般是一浸二焙或二浸三焙工艺。传统石墨电极生产方式是高能耗、高污染行业,并且生产周期长达150~160天,效率低下。已经成为改革的重点和被限制的行业。因此,该行业的生存和发展,必须依赖科技进步,改掉这些不符合社会发展要求的缺点。近年来出现了一些创新,现介绍如下:
200510016897.8“一种超高功率电极的生产方法”主要工艺:原料→破粉碎→筛分→混捏→成型→焙烧→浸渍→焙烧→浸渍→焙烧→石墨化→加工→产品。不同的是挤压机料缸采用了抽真空。这样会提高产品的性能。但是仍然还是传统工艺。生产周期还是需要100多天。热混捏、热成型、浸渍和碳化的环境问题没有得到解决。超高温石墨化的高能耗问题依然存在。
201210576127.9“大直径石墨电极生产工艺”采用石油焦、煤沥青。经过煅烧、破粉碎、混捏、震动成型、焙烧、石墨化、加工成大直径石墨电极。特点是震动成型,工序中抽真空。压力为-0.09~-0.095 MPa.温度控制在125~140 ℃,震动时间80~120秒。这样可以制备直径达1400,体密达1.68~1.74.这提高了产品质量和解决了挤压难以成型大直径电极的问题。但是周期长、环保和高能耗问题依然存在。
200810147891.8和201611114170.8介绍了大直径石墨电极制备方法。他们分别采用了2500t和3500t超大型液压机进行挤压成型。但是仍然采用的传统工艺技术。虽然解决了大型石墨电极的国产化问题。但是还是采用了传统的混捏、挤压、焙烧和石墨化工艺,没有解决周期长、环保和高能耗的问题。
综上一些创新和发明,只是在围绕大直径电极生产而采用了由热挤压成型,变成了震动成型,或增大设备压力挤压成型。在成型过程中抽真空而排出料内的气体,这有利于生产高质量的大直径石墨电极。但没有从根本上改变热混捏、热成型和沥青浸渍的传统的石墨电极生产工艺。没有解决生产周期长、环保和高能耗的问题。
发明内容
本发明旨在改掉传统石墨电极生产过程中的缺陷和现有发明专利的缺陷:周期长、污染、能耗高的缺点。通过下列途径实现:
本发明的工艺技术路线为:天然石墨、添加物和液体炭素结合剂→常温混料→干燥控制湿度→真空装模→等静压成型→固化→涂层→裸烧碳化→加工→涂层处理→产品。
具体步骤为:
选用纯度高的鳞片状天然石墨,其碳含量大于90 %,最好能大于99 %,选用的碳素树脂结合剂是液体改质沥青树脂、呋喃树脂和酚醛树脂之一或它们的混合物。这三种结合剂可以预混合一起加入,也可以单独添加到配料里进行混料。这样可以常温混料,添加剂之一碳纤维或母体纤维可以显著改善石墨电极的抗热震性和强度;添加剂之二金属硅粉可以显著提高材料的抗氧化性和热态强度,对提高石墨电极的使用寿命有好处;添加剂之三氧化铁粉可以显著提高碳素结合剂残碳的石墨化程度,对提高强度和抗氧化性有良好的促进作用,
以天然鳞片状石墨80~95 %,碳素复合结合剂5~10 %,添加剂0.05~5 %进行配料,在混碾机或高速混料机里进行混料,混料时间20~50 min,使树脂结合剂完全涂覆到石墨表面。混好的料进行干燥(包括自然干燥),干燥温度最好为40~60 ℃,使之挥发掉一定挥发分,控制好料的湿度,一般控制料内挥发分为0.5~2 %。然后装模,并经过真空抽气和封闭模套。真空度应该在-0.09~-0.098 MPa。然后把装好的模套放置在等静压成型机的油缸里,盖上等静压盖子,以80~400 MPa的压力进行等静压成型,成型保压时间80~600秒。泄压速度要慢,以≤80 MPa/min的泄压速度进行泄压为好。取出成型坯体后,进行自然放置和固化。自然放置时间大于24 h,而固化制度为:从常温到200 ℃,以升温速度为1~5 ℃/h,200 ℃保温48 h以上。固化出来的半成品涂防氧化涂料,并升温到1200 ℃以上进行碳化处理或不涂防氧化涂层直接还原气氛下或埋碳条件下1200 ℃以上烧成。其碳化制度为:常温~200 ℃:升温速度为6~10 ℃/h;200~700 ℃:升温速度2~6 ℃/h;700~1200 ℃:升温速度10~15 ℃/h;1200 ℃,保温24 h以上,然后,以20~50 ℃/h速度进行冷却至室温。这种半成品要经过机加工和涂0.3~1 mm厚的导电防氧化涂料,晾干24 h后即得产品。
本发明产品与有关石墨电极标准进行比较见下表:
本发明制备的石墨电极各项指标都达到或优于普通功率、高功率和超高功率石墨电极的标准。
与现有技术相比,本发明还具有以下优点:
1)采用天然石墨,它的导电性好,不用石墨化,这样解决了高能耗和石墨电极导电性的问题;2)采用液体炭素结合剂,这样不用热混捏、热成型,解决了环境污染问题;3)采用等静压成型,可以解决石墨电极质量和大直径石墨电极的问题;4)采用防氧化涂层技术,解决了埋碳烧成和生产效率低下问题。同时也提高了产品质量;5)采用添加剂纤维,可以显著提高石墨电极的强度和抗热震性。采用金属硅添加物,可以进一步提高石墨电极的强度和抗氧化性。添加氧化铁粉,可以促进结合剂炭石墨化,降低电阻率,提高石墨电极的导电性和抗氧化性能;6)防氧化涂层可以大大提高石墨电极的抗氧化性;导致使用寿命提高20%以上;即显著提高了石墨电极的质量。
附图说明
图1为石墨电极的工艺技术路线。
具体实施方式
下面结合实施例,对本发明作进一步详细的描述,但本发明的实施方式不限于此,不能以下述实施例来限定本发明的保护范围。下述实施实例中所使用的实验方法如无特殊说明,均为常规方法;所使用的材料、试剂等,如无特殊说明,均可从商业途径得到。
实施例1
一种石墨电极的制备工艺,具体步骤如下:
(1)选用碳含量为99.5 %和粒度为-100目的鳞片状天然石墨,其质量加入量为88.5 %,长度为5~7 mm的碳纤维,其质量加入量为0.2 %,粒度320目纯度为98 %的金属硅粉,其质量加入量为3 %,粒度为0.010 mm纯度为98 %的氧化铁粉,其质量加入量为0.3 %,残炭量为40 %,粘度为10 Pa.S的液体改性沥青,其质量加入量为5 %,残炭量为45 %,粘度为3 Pa.S的呋喃树脂,其质量加入量为3 %;
(2)先把碳纤维、硅粉和氧化铁粉预混合好,然后与石墨一起放在湿碾机里进行干混合5 min,然后添加预混合好的碳素结合剂到混碾机里进行混料,混料时间40 min,使树脂结合剂涂覆好石墨表面;混好的料进行干燥,干燥温度为50 ℃,时间10 h,控制料内挥发分为0.5~1 %之间;然后装模,装满模后,封闭模套时抽气,真空度达到-0.09~-0.098MPa,保持时间为2 min;
(3)然后把装好的模套放置在等静压成型机的油缸里,盖上等静压盖子,以120MPa的压力进行等静压成型,成型保压时间100 s,以25 MPa/min的泄压速度进行泄压;
(4)取出成型坯体后,进行自然放置时间24 h,然后进行加热固化,其固化制度为:从常温到200 ℃,以升温速度为2 ℃/h,200 ℃保温48 h;固化出来的半成品涂防氧化涂料,并升温到1200 ℃进行裸烧;其烧成制度为:常温~200 ℃:升温速度为6 ℃/h,200~700℃:升温速度5 ℃/h,700~1200 ℃:升温速度10 ℃/h,1200 ℃,保温48 h,然后,以50 ℃/h速度进行冷却至室温;这种半成品要经过机加工和涂0.3~1 mm厚的导电防氧化涂料,晾干24 h后即得产品。
该产品的性能为:电阻率6.4 μΩm,抗折强度12.3 MPa,体积密度1.85 g/cm3,弹性模量13.2 GPa,热膨胀系数1.4×10-6 /℃。
实施例2
一种石墨电极的制备工艺,具体步骤如下:
(1)选用碳含量为98%和粒度为-100目的鳞片状天然石墨,其质量加入量为85.5%,长度为5~7 mm的碳纤维,其质量加入量为0.1 %,粒度320目纯度为98%的金属硅粉,其质量加入量为5 %,粒度为0.010 mm纯度为98 %的氧化铁粉,其质量加入量为0.4 %,残炭量为40 %,粘度为10 Pa.S的液体改性沥青,其质量加入量为6 %,残炭量为45 %,粘度为3 Pa.S的酚醛树脂,其质量加入量为3 %;
(2)先把碳纤维、硅粉和氧化铁粉预混合好,然后与石墨一起放在湿碾机里进行干混合5 min,然后添加预混合好的碳素结合剂到混碾机里进行混料,混料时间40 min,使树脂结合剂涂覆好石墨表面;混好的料进行干燥,干燥温度为50 ℃,时间10 h,控制料内挥发分为0.5~1 %之间;然后装模,装满模后,封闭模套时抽气,真空度达到-0.09~-0.098 MPa,保持时间为2 min;
(3)然后把装好的模套放置在等静压成型机的油缸里,盖上等静压盖子,以250MPa的压力进行等静压成型,成型保压时间140 s;以20 MPa/min的泄压速度进行泄压;
(4)取出成型坯体后,进行自然放置时间24 h,然后进行加热固化,其固化制度为:从常温到200 ℃,以升温速度为2 ℃/h,200 ℃保温50 h;固化出来的半成品埋碳条件下1200 ℃进行碳化;其烧成制度为:常温~200 ℃:升温速度为10 ℃/h,200~700 ℃:升温速度4 ℃/h,700~1400 ℃:升温速度15 ℃/h,1400 ℃,保温50 h,然后,以50 ℃/h速度进行冷却至室温;这种半成品涂0.3~1 mm厚的导电防氧化涂料,晾干24 h后即得产品。
该产品的性能为:电阻率5.5 μΩm,抗折强度15.3 MPa,体积密度1.95 g/cm3,弹性模量13.4 GPa,热膨胀系数1.3×10-6 /℃。
实施例3
一种石墨电极的制备工艺,具体步骤如下:
(1)选用碳含量为99 %和粒度为+80目的鳞片状天然石墨,其质量加入量为90.65%,长度为5~7 mm的碳纤维,其质量加入量为0.15 %,粒度320目纯度为98 %的金属硅粉,其质量加入量为2 %,粒度为0.010 mm纯度为98%的氧化铁粉,其质量加入量为0.2 %,残炭量为40 %,粘度为10 Pa.S的液体改性沥青,其质量加入量为5 %,残炭量为45 %,粘度为3Pa.S的酚醛树脂,其质量加入量为2 %;
(2)先把碳纤维、硅粉和氧化铁粉预混合好,然后与石墨一起放在湿碾机里进行干混合5 min,然后添加预混合好的碳素结合剂到混碾机里进行混料,混料时间40 min,使树脂结合剂涂覆好石墨表面;
(3)混好的料进行干燥,干燥温度为50 ℃,时间10 h,控制料内挥发分为0.5~1 %之间;然后装模,装满模后,封闭模套时抽气,真空度达到-0.09~-0.098 MPa,保持时间为5min;然后把装好的模套放置在等静压成型机的油缸里,盖上等静压盖子,以300 MPa的压力进行等静压成型,成型保压时间200 s;以15 MPa/min的泄压速度进行泄压;
(4)取出成型坯体后,进行自然放置时间24 h,然后进行加热固化,其固化制度为:从常温到200 ℃,以升温速度为2 ℃/h,200 ℃保温50 h;固化出来的半成品涂防氧化涂料,并升温到1600 ℃进行裸烧;其烧成制度为:常温~200 ℃:升温速度为10 ℃/h,200~700℃:升温速度4 ℃/h,700~1600 ℃:升温速度25 ℃/h,1600 ℃,保温60 h,然后,以50 ℃/h速度进行冷却至室温;这种半成品要经过机加工和涂0.3~1 mm厚的导电防氧化涂料,晾干24 h后即得产品。
该产品的性能为:电阻率4.2 μΩm,抗折强度16.6 MPa,体积密度1.99 g/cm3,弹性模量14.2 GPa,热膨胀系数1.42×10-6 /℃。
综上可知,各项指标都达到甚至优于先关的国家标准。应用于炼钢石墨电极有很好的效果,该天然石墨电极成本低廉,生产周期由150~160天减少到约20天,大大提高了生产效率,环保大大改善。具有非常好的应用前景。
Claims (9)
1.一种石墨电极的制备工艺,其特征在于,具体步骤如下:
(1)以天然石墨、碳素树脂结合剂和添加剂为原料,按一定质量配比进行配料,在常温下进行混料;其中天然石墨85~95%,添加剂0.05~5%,碳素树脂结合剂4~10%;所述碳素树脂结合剂是由改性液体沥青、呋喃树脂和酚醛树脂中的两种以上组合而成,该结合剂的粘度3~16Pa.S,残炭量大于30%;所述添加剂是由碳纤维或母体纤维、硅粉和氧化铁组合而成,其配比为碳纤维或母体纤维:硅粉:氧化铁=2~5:80~90:7~12;所述碳纤维或母体纤维的长度为3~12mm,所述硅的纯度大于97%,颗粒尺寸≤0.088mm;
(2)将混碾好的料进行干燥,挥发掉一定挥发分,控制好料的湿度,控制湿度为100℃挥发分0.5~5%,然后装模,并经过真空和封闭模套,真空压力达到-0.09MPa以下;
(3)把装好的模套放置在等静压成型机的油缸里,盖上盖子,以一定压力在等静压成型机上进行成型;等静压成型的压力大于80 MPa;
(4)成型后,放置和固化;然后涂防氧化涂料,以一定升温速度加热到1200 ℃以上进行裸烧碳化或不涂防氧化涂层直接还原气氛下或埋碳烧成,再经过加工和涂导电防氧化涂料,然后晾干后即得产品。
2.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,所述天然石墨的纯度碳含量≥90%。
3.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,所述碳素树脂结合剂残炭量为40~50%。
4.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,所述碳纤维和母体纤维的长度为5~7mm,所述硅的纯度大于97%,颗粒尺寸≤0.010mm。
5.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,步骤(2)控制湿度为100℃挥发分0.5~2%。
6.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,步骤(3)等静压成型的压力为200 MPa。
7.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,步骤(4)成型后放置24h以上,且以升温速度为2~5℃/h,200℃保温48 h以上进行固化。
8.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,步骤(4)防氧化涂料的厚度为0.3~1mm,且防氧化涂料可导电。
9.如权利要求1所述的一种石墨电极的制备工艺,其特征在于,步骤(4)裸烧碳化的温度制度是:常温~200℃:升温速度为6~10℃/h,200~700℃:升温速度5~8℃/h,700~1200℃:升温速度10~15℃/h,1200℃,保温24h以上。
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