CN109072087B - 具有添加剂的新型焦炭 - Google Patents

具有添加剂的新型焦炭 Download PDF

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CN109072087B
CN109072087B CN201780008743.5A CN201780008743A CN109072087B CN 109072087 B CN109072087 B CN 109072087B CN 201780008743 A CN201780008743 A CN 201780008743A CN 109072087 B CN109072087 B CN 109072087B
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graphite
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奥斯温·厄廷格
黑里贝特·瓦尔特
马丁·克莱斯特
约翰·戴梅
威廉·弗雷斯
弗兰克·希尔特曼
赖纳·施密特
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Sofia Bidico Co ltd
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Abstract

本发明涉及包含添加剂的焦炭，其特征在于所述添加剂累积在屈服点处或累积在由屈服点包围的区域中。为了均匀分布，在填充时间期间将添加剂连续地加入延迟焦化装置。加料可通过用惰性气体(氮)以粉末吹入来进行，或者也可通过使分散在浆料中来进行，所述浆料由反应组分和部分焦化装置进料流(减压渣油、pytar、滗析油或煤焦油馏分)组成。根据实施方式的有利形式，添加剂的直径为0.05mm至5mm、优选1mm至3mm。有利地，添加剂选自于由乙炔焦炭、流化焦、柔性焦炭、球状焦炭、炭黑、不可石墨化碳(木炭)、非石墨无烟煤、碳化硅、碳化钛、二硼化钛或它们的混合物所组成的组。通过所述添加剂的添加使热膨胀系数(CTE)增加了10倍，这取决于添加剂的尺寸和量。

Description

具有添加剂的新型焦炭
技术领域
本发明涉及包含添加剂的新型焦炭及其用途。
背景技术
焦炭(例如石油焦炭和煤焦油沥青焦炭)可使用延迟焦化法来生产，但是这些焦炭由不同的原材料生产。为了生产石油焦炭，将精炼残余物(减压渣油、油浆、滗析油、热焦油、乙烯焦油)供应至延迟焦化装置，其中，在450℃-550℃的温度下，获得所谓的生石油焦炭，随后在1100℃-1500℃下在煅烧步骤中该生石油焦炭可转化为煅烧石油焦炭。
当生产煤焦油沥青焦炭时，将从冶金焦炭和铸造焦炭的生产获得的煤焦油进行蒸馏，并将获得的煤焦油沥青供应至延迟焦化装置，其中，在450℃-550℃的温度下，获得生煤焦油沥青焦炭，随后在1100℃-1500℃下在煅烧步骤中该生煤焦油沥青焦炭可转化为煅烧煤焦油沥青焦炭。
已知通过向延迟焦化装置中添加碳纤维能够实现焦炭的结构改善(US726284B2)。另外，已知在生产碳产品时，通过添加添加剂能够影响碳产品(例如，如石墨电极或阴极块)的性质。因此，例如可改善使用寿命(DE102010029538A1)。
例如，在铝工业中，为了对于液态铝实现更好的润湿，在生产阴极块时将二硼化钛(TiB2)作为添加剂添加。例如，US6258224描述了在以层构建的阴极块的上层中添加TiB2。同样地，CN101158048描述了含有20％-60％TiB2的碳复合材料。US6428885描述了具有含二硼化钛的保护涂层的支撑体。
TiB2在高温下以高能耗生产。当生产具有改善的润湿性质的碳产品时，需要将粗粒焦炭和细粒TiB2混合均匀，技术支出相当大。这可通过材料的不同粒径分布和密度来解释，因为这些材料需要易于分离。
由不同的粒径导致的进一步缺点在于，当加工碳产品时或由于磨损，在表面上产生区域，该区域仅含有粗粒焦炭的碳以及岛(该岛含有TiB2和任选的灰尘与粘合剂基质)。由于岛的形成，这导致表面不能很好地被铝润湿。最终，由于碳产品上的机械应力和化学应力，导致使用寿命缩短。
发明内容
因此，本发明的目的是提供焦炭，所述焦炭使由该焦炭生产的碳产品的使用寿命增加。
该目的通过含有添加剂的焦炭得以实现，其特征在于所述添加剂累积在屈服点(Flieβgrenzen)处或累积在由屈服点包围的区域中。
在本发明的范围内，屈服点应当理解为是指在焦化期间，中间相(Mesophase)凝固时产生的光学非各向异性区域之间的边界。
术语“中间相”定义系统的液相和固相之间的独特有序状态。当从液相转变为固相时，在热解期间发生从无序的各向同性相向有序的各向异性相的转变。
根据本发明，认识到由于添加剂累积在屈服点处或者在由屈服点包围的区域中，能够对焦炭的性质进行定制，其中例如通过添加剂的合适选择可影响润湿性和耐磨性。相应地，这种影响给由该焦炭生产的碳产品带来较长的使用寿命。
有利地，所述焦炭选自于由以下所组成的组：石油焦炭、煤焦油沥青焦炭；或者煤气化的残余物、煤氢化的残余物或从费-托合成获得的焦炭的残余物；或者由石油和煤焦油沥青残余物的混合物获得的石油/煤焦油沥青焦炭混合物；或者上述焦炭的任意混合物。
根据本发明，累积在屈服点处或在由屈服点包围的区域中的添加剂可累积在屈服点处或者嵌入由屈服点包围的区域中，或者累积在屈服点处和嵌入由屈服点包围的区域中二者可皆有。
在屈服点处的添加剂颗粒包括与屈服点接触的所有添加剂颗粒。
在屈服点处或者在由屈服点包围的区域中累积应理解为是指百分比为至少70的添加剂颗粒排列在屈服点处或者在由屈服点包围的区域中。如果添加剂颗粒的百分比少于70，则不会影响焦炭的性质。
添加剂颗粒的百分比应理解为是指样品中的添加剂颗粒的百分比比例。
添加剂颗粒的累积通过具有相关的能量色散X射线光谱仪(EDX)的扫描电子显微镜或光学显微镜来确定。
有利地，所述添加剂选自于由以下所组成的组：乙炔焦炭、流化焦、柔性焦炭(flexi coke)、球状焦炭、炭黑、不可石墨化碳(木炭)、非石墨无烟煤、碳化硅、碳化钛、二硼化钛或它们的混合物。
乙炔焦炭是在不饱和烃、尤其是乙炔的生产过程中作为副产物产生的焦炭，随后不管哪种不饱和烃的生产过程中产生的焦炭均称为乙炔焦炭。乙炔焦炭具有细粒的且与洋葱皮的层类似的结构。
根据本发明，非石墨无烟煤应理解为是指通过低于2000℃的温度处理所获得的无烟煤。
在本发明的范围内，流化焦应理解为是指高沸点烃级分的焦化产品(根据流化焦化工艺生产的来自矿物油或碳加工的重质残余物)。流化焦具有各向同性结构。可去除的挥发性组分的质量分数为6％。
在本发明的范围内，柔性焦炭应理解为是指用流化床法例如由Exxon Mobile开发的柔性焦化法(一种使用流化床反应器的热裂解方法)中生产的焦炭。使用该方法，获得具有球形到椭圆形构型的焦炭颗粒，其构型设计类似于洋葱皮的层。
在本发明的范围内，球状焦炭应理解为是指通过延迟焦化生产的焦炭。该焦炭的颗粒具有球形形态。
炭黑应理解为是指由球形初级颗粒组成的工业上生产的细粒碳。
木炭是不可石墨化的固态产品，其在天然或合成的有机材料的炭化工艺过程中产生(Polymeric Carbons von Gwyn Morgan Jenkins,Kiyoshi Kawamura,1967，“Coals oflowest rank(lignite)are said to possess a polymeric structure[...].Onpyrolysis,coals of low rank form isotropic chars(polymeric carbon),bituminouscoals produce textured crystalline cokes,while anthracites,although notcoking in the normal sense,eventually yield graphites at sufficiently hightemperatures”)。
根据另一有利的实施方式，在由焦炭生产的碳产品的石墨化过程中所述添加剂也可通过“原位形成”起始形成。对此，焦炭含有B2O3或B4C以及TiO2作为前体。在由焦炭生产的碳产品的石墨化过程中，二硼化钛的原位形成具有所形成的添加剂分散均匀的优点。在阴极块中，其具有以下优点：例如润湿性得以改善，因此使用寿命也增加。此外，可省去用于生产均匀的焦炭/二硼化钛混合物的高成本混合工艺。二硼化钛的“原位形成”具有以下优点：可省去高成本且较昂贵的二硼化钛生产方法。
在本发明的保护范围内，优选直径为0.1μm-49μm的添加剂，特别优选直径为1μm-3μm。存在于该区域的直径使用激光衍射来确定(ISO13320-2009)。
在具有0.1μm-49μm的添加剂直径时，当使供应至延迟焦化装置的进料材料反应达到获得焦炭的程度时，中间相形成被破坏，所述焦炭具有与其中中间相形成未被破坏的焦炭完全不同的性质。这些性质涉及焦炭硬度、可实现的材料强度(Materialfestigkeit)、导热性和导电性、热膨胀以及这些性质的各向同性。可能受到影响的另一性质为表面的润湿性；例如，在“导流槽”中期望的是对于熔融铝，使润湿性增加，而对于金属坩埚旨在使润湿性降低。可对润湿性的程度进行定制。通过添加添加剂使热膨胀系数(CTE)增加了10倍，这取决于添加剂的量和尺寸。
CTE是热膨胀的特征值，并且描述了在温度变化时，在其尺寸变化方面材料的行为。CTE根据DIN 51909(2009-05)进行测量。此外，通过破坏中间相获得的焦炭具有比没有添加剂时生产的焦炭高多至2-3倍的硬度。
焦炭的硬度由所谓的Hardgrove指数(HGI)描述，并根据DIN 51742(2001-07)确定。
根据本发明，焦炭中添加剂的比例为0.5wt％至8wt％、优选1wt％至4wt％。当添加剂的比例大于8wt％时，焦炭的硬度不会有进一步的增加。当小于0.5wt％时，添加剂不会对中间相形成的破坏具有任何影响。如果例如焦炭由焦炭颗粒和添加剂组成并且添加剂的比例为4wt％，则焦炭颗粒的比例为96wt％。
根据本发明另一有利的实施方式，所述添加剂的直径为0.05mm-5mm、优选1mm-3mm。在该范围内的直径使用筛分分析(DIN I66165-2016；方法F)进行确定。用这些直径的添加剂实现了在由屈服点包围的区域中的嵌入。当直径低于0.05mm时，如上所述中间相形成被破坏，并在屈服点处发生添加剂的累积。当直径大于5mm时，由于添加剂的直径大于由屈服点包围的区域的直径，在由屈服点包围的区域中没有嵌入。当生产多粒(polygranulareren)碳和石墨材料时，使用这样的混合物。
添加剂嵌入由屈服点包围的区域中导致CTE增加2-3倍，这取决于添加剂的类型、尺寸和量。同样地，所得的焦炭的硬度增加了2-3倍。通过添加剂可生产在性质方面定制的焦炭。这导致较高的硬度和较高的CTE，从而由该焦炭生产的产品具有较长的使用寿命。
根据本发明，添加剂的比例为1wt％至40wt％，优选5wt％至20wt％。当添加剂的比例大于20wt％时，通过将添加剂嵌入由屈服点包围的区域中并不能实现硬度的进一步增加。当添加剂少于1wt％时，嵌入的添加剂不对焦炭的性质具有任何影响。
如果例如焦炭由焦炭和添加剂组成并且添加剂的比例为20wt％，则焦炭的比例为80wt％。
根据另一实施方式，优选的是添加剂以直径为0.1μm-49μm的添加剂和直径为0.05mm-5mm的添加剂的混合物形式存在。
通过使用不同直径的添加剂的混合物，可在以下性质方面，对焦炭进行定制：焦炭硬度、可实现的材料强度、导热性和导电性、热膨胀以及这些性质的各向同性，其比使用一种直径的添加剂时甚至更加灵活。其结果是由此生产的碳产品具有较长的使用寿命。将直径为0.05mm-5mm的添加剂嵌入由屈服点包围的区域中。然而，由于具有直径小于0.05mm的添加剂的混合物，如上所述中间相形成被破坏，并且在屈服点处发生添加剂的累积。当直径大于5mm时，由于添加剂的直径大于由屈服点包围的区域的直径，在由屈服点包围的区域中没有嵌入。因此，不同直径的添加剂的混合物导致在由屈服点包围的区域中嵌入和在屈服点处累积两种情况，这取决于尺寸。
根据本发明，直径为0.1μm-49μm的添加剂的混合物比例为0.5wt％至8wt％，优选2wt％；而直径为0.05mm-5mm的添加剂的混合物比例为5wt％至20wt％，优选10wt％。
如果直径为0.1μm-49μm的添加剂的比例大于8wt％并且直径为0.05mm-5mm的添加剂的比例大于20wt％，则焦炭性质(例如强度、导热性、导电性和热膨胀)变成背景而添加剂的性质开始占主导。当直径为0.1μm-49μm的添加剂的比例低于2wt％并且直径为0.05mm-5mm的添加剂的比例低于5wt％，添加剂对所获得的焦炭的性质不产生任何影响。
本发明的另一主题是上述所述的焦炭在用于以下方面的用途：炉衬、用于钢生产的石墨电极、用于连接石墨电极的石墨体、用于铝生产的阴极块、核应用、用于强腐蚀性介质领域中的工艺技术的仪器制造、管束换热器、特种石墨(例如用于硅生产、太阳能晶片生产)、用于放电加工和加热元件的电极、滑环密封件、石墨轴承、石墨泵叶轮或石墨坩埚；优选用于：焦炭炉衬、用于钢生产的石墨电极或用于铝生产的阴极块。通过使用这种新型焦炭，根据导流槽概念可生产新的阴极块，其导致在生产铝时节省能源。
然而，原则上，所述焦炭适用于碳和石墨材料的所有用途，其中各向同性、耐磨性、耐化学性、断裂韧性以及润湿性是最重要的。
现在参考随后的附图对本发明的其它特征和优点进行更详细的解释，但不限于此。
附图说明
它们显示在：
图1：来自添加剂累积在屈服点处的焦炭的部分的示意图。
图2：来自添加剂累积在由屈服点包围的区域中的焦炭的部分的示意图。
图3：来自添加剂累积在屈服点处和由屈服点包围的区域中的焦炭的部分的示意图。
图1示出了来自添加剂(1)累积在屈服点(2)处的焦炭的部分的示意图。添加剂(1)的直径选自0.1μm-49μm的范围。
图2示出了来自添加剂(3)累积在由屈服点包围的区域(4)中的焦炭的部分的示意图。添加剂(3)的直径选自0.05mm-5mm的范围。
图3示出了来自添加剂(1)累积在屈服点(2)处和由屈服点包围的区域(4)中的焦炭的部分的示意图。添加剂(1)的直径选自0.1μm-49μm的范围。添加剂(3)的直径选自0.05mm-5mm的范围。
具体实施方式
现在，使用实施例对本发明进行解释，其中，实施例不代表对本发明的任何限制。
实施例1
为了在焦炭材料中后续反应组分的均匀分布，在12小时的填充时间期间，将TiO2和B2O3(各自具有1-3μm的粒径，化学计量比为1:1)连续地加入延迟焦化装置中。加料可通过以惰性气体(氮)来粉末吹制而进行，或者也可通过分散在浆料中而进行，所述浆料由反应组分和部分焦化装置进料流(减压渣油、pytar、滗析油或煤焦油馏分)组成。反应组分的浓度符合终产品中所期望的TiB2的浓度。在该实例中，按以下比例(wt％)加入浆料：浆料(减压渣油)＝84.3wt％；TiO2 8.4wt％；B2O37.3wt％。得到具有以下比例的期望焦炭：焦炭＝61.6wt％；TiO2＝20.5wt％；以及B2O3＝17.9wt％。结果得到具有精细分散的TiB2比例为25.5wt％的合成石墨体，所述合成石墨体根据绿色制造、烘烤和2200℃以上的热整理(thermal finishing)而生产。
在屈服点处具有百分比为70的添加剂颗粒。
在该实施例中，添加剂可累积在屈服点处或由屈服点包围的区域中，这取决于添加剂的直径。例如，可改善对于铝熔体而言阴极块的润湿行为。通过控制添加剂的比例可对润湿行为进行定制。
实施例2
将气体锻烧无烟煤在冲击式研磨机上研磨至直径约3μm，并借助于筛分，由此生产出1μm-3μm的颗粒部分。以10wt％将其分散在乙烯焦油中。将该分散体导入温度为490℃的延迟焦化装置中。焦化压力为6.6bar，焦化时间为10小时。在1300℃下煅烧生石油焦炭。得到具有4.5 10-6K-1的CTE和0.09％的灰分含量的各向同性石油焦炭，其中硼含量为0.2ppm。该焦炭适用于高纯度的iso石墨(Isographite)和核电站中的反应堆石墨。
在该实施例中，添加剂以70的添加剂颗粒百分比累积在屈服点处。
实施例3
在460℃下，将基于石油的减压渣油供应至延迟焦化装置中。焦化压力为5.0bar，焦化时间为8小时。在整个焦化期间，将来自减压渣油的10％的焦化装置进料作为分散体与10wt％乙炔焦炭(直径为0.4mm-0.8mm)一起从焦化塔的顶部添加。在煅烧生焦炭后，得到乙炔焦炭的嵌入比例为4wt％的石油焦炭。焦炭的CTE为3.5 10-6K-1。与没有乙炔焦炭沉积物的类似焦炭相比，机械阻力增加了6％。在该实施例中，添加剂以70的添加剂颗粒百分比累积在由屈服点包围的区域中。
在铝熔盐电解中，在石墨阴极中使用这种焦炭将相当于将使用寿命延长1-2年。
附图标记列表
1 直径为0.1μm-49μm的添加剂
2 屈服点
3 直径为0.05mm-5mm的添加剂
4 由屈服点包围的区域

Claims (11)

1.包含添加剂的焦炭，其特征在于，所述添加剂累积在屈服点处和/或累积在由所述屈服点包围的区域中，其中，所述添加剂为二硼化钛。
2.根据权利要求1所述的焦炭，其特征在于，所述焦炭选自于由以下所组成的组：石油焦炭、煤焦油沥青焦炭；或者煤气化的残余物、煤氢化的残余物或从费-托合成获得的焦炭的残余物；或者由石油和煤焦油沥青残余物的混合物获得的石油/煤焦油沥青焦炭混合物；或者上述焦炭的任意混合物。
3.根据权利要求1所述的焦炭，其特征在于，所述添加剂累积在所述屈服点处，或嵌入由所述屈服点包围的区域中，或者所述添加剂累积在所述屈服点处以及嵌入由所述屈服点包围的区域中。
4.根据权利要求1所述的焦炭，其特征在于，所述添加剂的直径为0.1μm-49μm。
5.根据权利要求1所述的焦炭，其特征在于，所述添加剂的直径为0.05mm-5mm。
6.根据权利要求1所述的焦炭，其特征在于，所述添加剂以直径为0.1μm-49μm的添加剂和直径为0.05mm-5mm的添加剂的混合物存在。
7.根据权利要求4所述的焦炭，其特征在于，所述添加剂的比例为0.5wt%至8wt%。
8.根据权利要求5所述的焦炭，其特征在于，所述添加剂的比例为1wt%至40wt%。
9.根据权利要求6所述的焦炭，其特征在于，所述直径为0.1μm-49μm的添加剂的混合物比例为0.5wt%至8wt%，所述直径为0.05mm-5mm的添加剂的混合物比例为5wt%至20wt%。
10.根据权利要求1-9中任一项所述的焦炭在用于以下方面中的用途：炉衬；用于钢生产的石墨电极；用于连接石墨电极的石墨体；用于铝生产的阴极块；核应用；用于强腐蚀性介质领域中的工艺技术的仪器制造；管束换热器；特种石墨；用于放电加工和加热元件的电极；滑环密封件；石墨轴承；石墨泵叶轮；或石墨坩埚。
11.根据权利要求10所述的用途，其特征在于，所述特种石墨为用于硅生产或太阳能晶片生产的特种石墨。
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