CN112266248B - 一种利用低质石墨原料制备石墨坩埚的方法 - Google Patents
一种利用低质石墨原料制备石墨坩埚的方法 Download PDFInfo
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Abstract
本发明公开了一种利用低质石墨原料制备石墨坩埚的方法,该方法以残损石墨坩埚废料和石墨电极材料生产过程中的石墨尾料为原料,经过粉碎后比例混合,混合后获得第一石墨粉末混合物,并与煤沥青混合后湿混,并在湿混过程中利用超声分散来降低沥青粘度,然后制粒,并进行真空石墨化处理,将石墨化后的物料与石墨坩埚废料粉碎得到第二再生石墨粉,再与煅烧石油焦、天然石墨粉干混后与低软化点的沥青湿混后模压制坯并焙烧成型。本发明能有效对残损石墨坩埚废料和石墨电极材料进行回收,制备具有较佳质量和寿命的石墨坩埚。
Description
技术领域
本发明涉及残损石墨原料的再生利用技术领域,具体涉及一种利用低质石墨原料制备石墨坩埚的方法。
背景技术
石墨坩埚具有良好的热导性和耐高温性,在高温使用过程中,热膨胀系数小,对急热、急冷具有一定抗应变性能。对酸,碱性溶液的抗腐蚀性较强,具有优良的化学稳定性。石墨坩埚,因具有以上优良的性能,所以在冶金、铸造、机械、化工等工业部门,被广泛用于金属冶炼、锂电池负极材料提纯、多晶硅材料冶炼、铸锭等作业过程中,并有着较好的技术经济效果。
目前,石墨坩埚的主体原料是结晶形天然石墨或者人造石墨,也有将主体原料与其他改性材料混合后成型制成,其在生产过程中需要经过将原料进行多次高温处理,整个过程工序复杂、能耗大,生产周期长,难于满足实际的使用需求,同时由于不可控的各种因素,会产生较多量的石墨碎块以及残损石墨坩埚。
另外,石墨碳素产品的常见应用还有石墨电极,石墨电极材料在制备时需要将含碳量在90%以上的石墨经多次粉碎,使得石墨粉平均粒度、密度以及比表面积持续降低,来获得用于制备石墨电极的石墨粉原料,其产品中约能产生25~30%的石墨尾料,这些石墨尾料只能用于涂料、防火材料、低等级润滑材料,铅笔等低质量应用中,造成了极大的资源浪费。
如果能将上述两类低质石墨原料进行回收利用,特别是石墨电极材料生产过程中的石墨尾料进行利用,能有效提高石墨材料的利用率,降低相关企业的生产成本和能耗。
发明内容
本发明所解决的技术问题在于提供一种利用低质石墨原料制备石墨坩埚的方法,以解决上述技术背景中的缺陷。
本发明所解决的技术问题采用以下技术方案来实现:
一种利用低质石墨原料制备石墨坩埚的方法,具体包括以下操作步骤:
S1选择残损石墨坩埚废料作为原料,将残损石墨坩埚废料用破碎机破碎后进行粉碎得到再生石墨粉,控制粉碎后的再生石墨粉的粒径小于2mm,得到到第一再生石墨粉。
S2将石墨电极材料生产过程中的石墨尾料与步骤S1制得的第一再生石墨粉按照质量比3:1~4:1的比例进行干混,混合后获得第一石墨粉末混合物,将第一石墨粉末混合物与煤沥青按照质量比2:1~5:2的比例进行加热湿混,在湿混时长还剩45min时,利用超声设备辅助分散至湿混结束。
S3将步骤S2中制得的湿混料利用模具造粒,制成粒径小于2cm的颗粒物或者边长小于2cm的块状物料,将上述块状物料置于石墨化炉中依次进行真空分段加热焙烧:
1400~1700℃的温度条件下焙烧120~150h;
2000~2300℃的温度条件下焙烧50~60h;
焙烧完成后自然降温冷却。
S4将冷却后的焙烧物料与残损石墨坩埚废料按照2:1的比例混合后通过粉碎机进行粉碎得到第二再生石墨粉。
S5将80~90wt%的第二再生石墨粉与5~15wt%的煅烧石油焦以及5~10wt%的天然石墨粉进行干混,混合获得第二石墨粉末混合物,将第二石墨粉末混合物加入软化点在50~70℃的沥青,控制沥青与第二石墨粉末混合物的质量比为3:1~4:1,进行加热湿混。
S6、湿混完成后将湿混混合料在模压装置中用模具模压成型坩埚毛坯,然后把得到的坩埚毛坯置于焙烧炉中进行焙烧,焙烧完成后进行修坯成型,即得成品石墨坩埚。
作为进一步限定,所述残损石墨坩埚废料为在正常石墨坩埚制备工艺中的烧损坩埚废料、修坯废料以及在搬运、存储过程中产生的未使用过的运损废料。
作为进一步限定,所述步骤S2中,为了获得刚好的混合效果,并减少混合时间,第一石墨粉末混合物与煤沥青进行混合操作时分两次进行:
第一次将煤沥青在沥青熔化槽中进行熔化,然后拌入一半量的第一石墨粉末混合物加入进行湿混,混合均匀后再拌入余量的第一石墨粉末混合物,继续混料,而超声辅助分散在第二次湿混过程中进行。
作为进一步限定,所述步骤S2与所述步骤S4中进行加热湿混时控制湿混温度为140~180℃,湿混时间为1~3h。
作为进一步限定,所述步骤S3中,石墨化炉中进行真空焙烧时炉内保持真空度为1×10-2~3×10-2Pa。
作为进一步限定,所述步骤S5中,为了获得较佳的烧结效果和成型质量,所述第二再生石墨粉的粒径小于3mm,所述煅烧石油焦的粒径控制的2~5mm,所述天然石墨粉的粒径为30~60μm。
作为进一步限定,所述步骤S6中,坩埚毛坯在焙烧炉中进行焙烧处理时,于1200~1400℃的环境中真空焙烧120~150h或者在保护气体氛围中焙烧180~300h。
有益效果:本发明的一种利用低质石墨原料制备石墨坩埚的方法,能有效利用石墨电极材料生产过程中的石墨尾料与残损的石墨坩埚废料作为原料制备石墨坩埚,尤其是能对石墨电极材料生产过程中的石墨尾料进行高价值的回收利用,在与经过石墨化炉真空处理后与煅烧石油焦、天然石墨粉干混,并与低软化点沥青混合后制坯成型,其成型后的石墨坩埚具有不输于新制石墨坩埚的良好的热导性和耐高温性,能在保证成品性能的基础上对废损石墨原料进行有效的回收利用。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐述本发明。
在本发明中,利用未使用过的残损石墨坩埚作为原料,这些石墨坩埚是在制作时修坯失败或者运输、保存过程中磕碰或者摔坏的石墨坩埚,回收前先利用将石墨坩埚表面清理干净,然后将石墨坩埚投入颚式破碎机进行破碎,并将破碎料通过粉碎机进行多次粉碎后粉磨,得到再生石墨粉,备用。
在实施例一中:
将再生石墨粉进行筛选,筛选出其中粒径小于2mm的筛下物,得到第一再生石墨粉,然后将石墨电极材料生产过程中的石墨尾料与第一再生石墨粉按照质量比3:1的质量比进行干混,混合获得第一石墨粉末混合物。
将第一石墨粉末混合物加入符合GB/T2290-94中温沥青标准的煤沥青(河北丰泰源能源科技有限公司)中进行加热湿混捏合,控制第一石墨粉末混合物与煤沥青的质量比为5:2,湿混捏合时控制湿混温度为160℃,湿混时间为2h,湿混过程中,先将煤沥青在沥青熔化槽中进行熔化,先加入一半量的第一石墨粉末混合物利用物理搅拌方式进行湿混搅拌,搅拌1h后加入余量的第一石墨粉末混合物继续搅拌15min时,启用超声设备辅助分散,利用超声波产生的能量去打散沥青聚合物,降低沥青粘度,期间控制超声功率为2400W,超声频率40K,超声辅助处理至湿混结束,此时测定煤沥青的超声降粘比例为12.6%。
而在此过程中,超声辅助处理的操作步骤设置能够将不加任何溶剂的单纯沥青体系的粘度降低,从而提高石墨粉末在沥青体系分布的稳定性,并提高单位体积内石墨粉末的比重,从而在石墨化的过程中将其中低质的石墨电极材料生产过程中的石墨尾料进行固定和提质、提纯。
将湿混后的混合物物料利用模具造粒,制成边长小于2cm的块状物料,或者是粒径小于2cm的颗粒物,将造粒物料置于石墨化炉中,进行高温石墨化处理,处理时,将石墨化炉抽真空,并将真空度控制在2×10-2Pa之间,先在1650℃的温度条件下焙烧130h,然后再在2200℃的温度条件下焙烧50h,使得低质的石墨电极材料生产过程中的石墨尾料与第一再生石墨粉以及煤沥青得到接近于理想值的石墨化结构。
而将上述石墨化结构与再生石墨粉按照2:1的比例混合后进行粉碎、磨细处理后筛选,得到粒径小于3mm的第二再生石墨粉,而在该过程中,边长小于2cm的块状物料,或者是粒径小于2cm的颗粒物既方便在石墨化处理过程中快速稳定的成型,也便于在得到石墨化结构后进行快速粉碎。将80wt%的该第二再生石墨粉与15wt%的粒径为2~5mm的煅烧石油焦以及5wt%的粒径为30~60μm的天然石墨粉混合,得到第二石墨粉末混合物,将该第二石墨粉末混合物加入软化点在55~60℃的沥青中,控制沥青与第二石墨粉末混合物的质量比为3:1,进行加热湿混,加热湿混时控制湿混温度为160℃,湿混时间为1h。
湿混完成后将湿混混合料在模压装置中用模具模压成型坩埚毛坯,然后把得到的坩埚毛坯置于焙烧炉中,于1250℃的环境中,在氩气氛围中焙烧180h得到半成品,并将半成品进行修坯后得到成品石墨坩埚成品。
在实施例二中:
将再生石墨粉进行筛选,筛选出其中粒径小于2mm的筛下物,得到第一再生石墨粉,然后将石墨电极材料生产过程中的石墨尾料与第一再生石墨粉按照质量比3:1的质量比进行干混,混合获得第一石墨粉末混合物。
将第一石墨粉末混合物加入符合GB/T2290-94中温沥青标准的煤沥青(河北丰泰源能源科技有限公司)中进行加热湿混捏合,其操作步骤与实施例一一致,其差异仅在于不经过超声处理,进通过强制物理搅拌和混捏进行湿混混合,然后将湿混后的混合物物料造粒,并按照实施例一的步骤依次进行高温石墨化处理、制备第二再生石墨粉、加沥青后加热湿混、模压制坯、焙烧、修坯成型的操作步骤得到石墨坩埚成品。
在实施例三中:
将再生石墨粉进行筛选,筛选出其中粒径小于2mm的筛下物,得到第一再生石墨粉,然后将石墨电极材料生产过程中的石墨尾料与第一再生石墨粉按照质量比3:1的质量比进行干混,混合获得第一石墨粉末混合物。
再按照实施例一的操作步骤进行加工,其与实施例以一的操作步骤差异仅在于在造粒物料置于石墨化炉中进行石墨化操作过程中,仅直接在2200℃的温度条件下真空焙烧180h。然后制备第二再生石墨粉、加沥青后加热湿混、模压制坯、焙烧、修坯成型的操作步骤得到石墨坩埚成品。
利用制得的实施例中的石墨坩埚制备十个,去掉明显具有参数差异的个体,并以未使用过的残损石墨坩埚中同批次的石墨坩埚作为对例进行多晶熔铸循环操作,得出实施例一、实施例二、实施例三、对比例的石墨坩埚具有以下物理属性:
实施例一:平均密度:2.01g/cm3,平均耐火温度1800℃:平均抗压强度38MPa:在不涂装内保护层的情况下进行完整的多晶熔铸循环的使用寿命:14~16次。
实施例二:平均密度:2.12g/cm3,平均耐火温度1780℃:平均抗压强度36MPa:在不涂装内保护层的情况下进行完整的多晶熔铸循环的使用寿命:6~8次。
实施例二:平均密度:1.68g/cm3,平均耐火温度1700℃:平均抗压强度29MPa:在不涂装内保护层的情况下进行完整的多晶熔铸循环的使用寿命:10~12次。
对比例:平均密度:1.82g/cm3,平均耐火温度1800℃:平均抗压强度33MPa:在不涂装内保护层的情况下进行完整的多晶熔铸循环的使用寿命:15~18次。
基于上述内容可以发现,实施例一与对比例的性能基本没有差异,具有类似的热性能,使用寿命也接近与对比例的新制坩埚,且平均抗压强度高于对比例;而实施例二和实施例三由于单一工艺的缺陷,导致其性能降低,其主要表现在耐火性能的下降以及物理强度的降低,同时,使用寿命上也存在缺陷。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (8)
1.一种利用低质石墨原料制备石墨坩埚的方法,其特征在于,具体包括以下操作步骤:
S1选择残损石墨坩埚废料作为原料,将残损石墨坩埚废料用破碎机破碎后进行粉碎得到再生石墨粉,控制粉碎后的再生石墨粉的粒径小于2mm,得到第一再生石墨粉;
S2将石墨电极材料生产过程中的石墨尾料与步骤S1制得的第一再生石墨粉按照质量比3:1~4:1的比例进行干混,混合后获得第一石墨粉末混合物,将第一石墨粉末混合物与煤沥青按照质量比2:1~5:2的比例进行加热湿混,在湿混时长还剩45min时,利用超声设备辅助分散至湿混结束;
S3将步骤S2中制得的湿混料利用模具造粒,制成粒径小于2cm的颗粒物或者边长小于2cm的块状物料,将上述块状物料置于石墨化炉中依次进行真空分段加热焙烧:
1400~1700℃的温度条件下焙烧120~150h;
2000~2300℃的温度条件下焙烧50~60h;
焙烧完成后自然降温冷却;
S4将冷却后的焙烧物料与残损石墨坩埚废料按照2:1的比例混合后通过粉碎机进行粉碎得到第二再生石墨粉;
S5将80~90wt%的第二再生石墨粉与5~15wt%的煅烧石油焦以及5~10wt%的天然石墨粉进行干混,混合获得第二石墨粉末混合物,将第二石墨粉末混合物加入软化点在50~70℃的沥青,控制沥青与第二石墨粉末混合物的质量比为3:1~4:1,进行加热湿混;
S6、湿混完成后将湿混混合料在模压装置中用模具模压成型坩埚毛坯,然后把得到的坩埚毛坯置于焙烧炉中进行焙烧,焙烧完成后进行修坯成型,即得成品石墨坩埚。
2.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述残损石墨坩埚废料为在正常石墨坩埚制备工艺中的烧损坩埚废料、修坯废料以及在搬运、存储过程中产生的未使用过的运损废料。
3.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述步骤S2中,第一石墨粉末混合物与煤沥青进行混合操作时分两次进行:
第一次将煤沥青在沥青熔化槽中进行熔化,然后拌入一半量的第一石墨粉末混合物加入进行湿混,混合均匀后再拌入余量的第一石墨粉末混合物,继续混料,而超声辅助分散在第二次湿混过程中进行。
4.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述步骤S2中进行加热湿混时控制湿混温度为140~180℃,湿混时间为1~3h。
5.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述步骤S3中,石墨化炉中进行真空焙烧时炉内保持真空度为1×10-2~3×10-2Pa。
6.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述步骤S5中,为了获得较佳的烧结效果和成型质量,所述第二再生石墨粉的粒径小于3mm,所述煅烧石油焦的粒径控制的2~5mm,所述天然石墨粉的粒径为30~60μm。
7.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述步骤S6中,坩埚毛坯在焙烧炉中进行焙烧处理时,于1200~1400℃的环境中真空焙烧120~150h。
8.根据权利要求1所述的利用低质石墨原料制备石墨坩埚的方法,其特征在于,所述步骤S6中,坩埚毛坯在焙烧炉中进行焙烧处理时在保护气体氛围中焙烧180~300h。
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