CN103748057B - 用于阴极防蚀的二硼化钛颗粒剂 - Google Patents

用于阴极防蚀的二硼化钛颗粒剂 Download PDF

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CN103748057B
CN103748057B CN201280040927.7A CN201280040927A CN103748057B CN 103748057 B CN103748057 B CN 103748057B CN 201280040927 A CN201280040927 A CN 201280040927A CN 103748057 B CN103748057 B CN 103748057B
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titanium diboride
granule
particulate agent
binder
prepare
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CN103748057A (zh
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马丁·恩格勒
格奥尔·维克托
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3M Innovative Properties Co
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Abstract

本发明涉及二硼化钛颗粒剂，所述二硼化钛颗粒剂包含二硼化钛原生粒子的聚集体，其中所述二硼化钛颗粒剂具有圆形形状并且耐断裂。本发明还涉及一种用于制备此类二硼化钛颗粒剂的方法，所述二硼化钛颗粒剂在覆盖Al熔盐电解中电解池的石墨阴极或修复电解池的所述阴极底部小孔方面的用途，以及同样地用于修复电解池的所述阴极底部小孔的方法。

Description

用于阴极防蚀的二硼化钛颗粒剂
技术领域
本发明涉及用于防止碳或石墨阴极在铝熔盐电解中发生腐蚀以及用于修复电解池阴极小孔的二硼化钛颗粒剂。
背景技术
在铝熔盐电解中，电解池包括由铁片或钢片制成的电解槽，其底部衬有隔热系统。在该电解槽中，由耐火内衬材料密封的若干个阴极块彼此相邻排列，形成电解池底部。在电流作用下，电解槽中的熔盐在熔融槽中转化为铝。该反应通常在高于950℃的温度下进行。
阴极块由含碳材料制成，其可以部分或全部为石墨，以满足耐热性和耐化学性要求并确保获得所需的导电性。这些材料通过混合原材料后进行挤出或振动压实而形成。为此，可以使用沥青、煅烧无烟煤和/或石墨的混合物，然后在约1200℃下焙烧。由这些混合物制成的半石墨阴极通常被称为碳阴极。还可使用加或不加石墨的沥青和焦炭的混合物。在这种情况下，这些材料在约800℃下焙烧，然后通过在约2400℃下退火实现石墨化。以这种方式制得的这些石墨阴极被称为石墨阴极。
常用的碳阴极仅具有适当的电特性和热特性，其无法满足现代电解池的操作条件要求，对于那些具有高电流强度的电解池尤其如此。对减少能源消耗(尤其是在现有系统中)的需求促进了石墨阴极的使用。
在2400℃以上对石墨阴极进行石墨退火处理使得提高其导电性和导热性成为可能，从而创造有助于优化电解池运行的条件。由于阴极电阻降低，其消耗的能源减少。另外，引入电解池的电流强度可以增加，从而有可能提高铝产量。阴极的高导热性使得可通过增加放电电流而产生过量的热。另外，石墨阴极电解池比碳阴极电解池的电不稳定性更低，即，它们具有更低的电位波动速率。
然而，已经发现石墨阴极电解池比碳阴极电解池的使用寿命要短。这是由于石墨阴极块的腐蚀速率显著高于碳阴极块的腐蚀速率。
因此，石墨阴极块耐腐蚀性较差是其缺点，并且目的是提高石墨阴极块的耐腐蚀性，从而延长其使用寿命。
阴极块除了总体磨损程度严重以外，在阴极底部形成局部的锥形小孔也是一个严重的问题。这些小孔在阴极表面沿电流条方向增大。如果接触到电流条，这将导致铝中的铁含量急剧增加并最终损坏电解池。
现有技术
可采用多种方法减少阴极块的磨损。
WO 00/29644描述了一种用于在阴极表面原位形成二硼化钛的方法，其结果是阴极的耐腐蚀性和抗氧化性得到提高。
WO 00/36187描述了一种用于制备多层阴极的方法，其中含有金属硼化物的至少一层覆盖石墨阴极。除了金属硼化物以外，层还包含碳。该方法应当还能提高阴极的耐腐蚀性和抗氧化性。
使用二硼化钛-石墨混合物作为阴极上的保护层以提高其耐腐蚀性，尽管这种方法很少使用，但它也是业内已知的方法。该保护层相比于纯石墨阴极的优点在于，其被铝润湿的可能性显著提高，相应地减小阳极-阴极之间的间距的可能性显著提高，从而减少了电解池的功耗或显著提高了生产率。上述硼化钛-石墨混合物的一个严重缺点在于多层阴极需要使用大量昂贵的TiB2(一层25-50％的厚度最高至100mm)和昂贵的制备工艺，例如共挤出法或额外的振动压实工艺。另外，层中互补部分仍然由被腐蚀攻击的石墨或碳基粘结剂制成。如果从层中将其移除，则TiB2也将从化合物中剥离。
公开“Simplifying Protection System to Prolong Cell Life,”MaryamMohamed Al Jallaf,Margaret Hyland,Barry Welch,Ali Al Zaroumi,Light Metals2011,1079-1084(“用于延长电解池使用寿命的简化保护系统”，Maryam Mohamed AlJallaf、Margaret Hyland、Barry Welch和Ali Al Zaroumi，《轻金属》，2011年，第1079-1084页)描述了使用二硼化钛保护阴极的另一种方法。此文中，向电解池中引入裂片状或角状非圆形颗粒剂形式的TiB2，其中颗粒剂在电解池中电流的作用下分散于阴极表面。优选地，TiB2聚集在由腐蚀形成的现有凹陷中。通过使用颗粒剂，可通过填充二硼化钛颗粒剂得到防蚀的阴极表面。颗粒剂填充物的涂层厚度相比于TiB2石墨混合物显著减小，如上文所述，阴极无需采取特殊的制备工艺。该方法的缺点在于颗粒状材料较软。其压缩强度极小，容易在机械应力如压力和摩擦作用下破碎和粉化。由此产生的小颗粒TiB2将在定期通过虹吸取出熔融铝的过程中随其离开电解池，从而在铝中引入颗粒状杂质。这样将会降低产品强度并引起故障，尤其是在铣削工艺中。颗粒剂破碎的另一个缺点在于影响可得到的堆积密度。通过优化的颗粒剂粒径分布，可以使各个颗粒剂之间的自由空间减小，从而得到较高的堆积密度，但破碎的颗粒剂将会减小TiB2与自由空间的比率。
U.S.3,766,025描述了一种用于修复阴极中小孔的方法，其中使用颗粒状材料填充这些小孔。该材料可以为氧化铝、碳化硅或氮化硼，优选为α-氧化铝。其中未描述颗粒剂的制造方法。该方法的一个缺点在于填充物缺乏导电性。用不导电的材料填充阴极小孔将导致电解池生产率下降，从而使铝的生产成本提高。通常用于修复阴极小孔的氧化铝还存在这样的缺点，即相比于熔融冰晶石，其耐腐蚀性不尽如人意。
为了修复阴极中的小孔，通常需要大量加入所用的填充物或以运输包装作为纸质容器。该方法的缺点在于修复所用的填充物无法准确定位，当其落入电解池底时，它们不仅分布于小孔内，还将分布于未损坏的分解池底。
发明目的
因此，本发明的目的在于提供一种材料，使用该材料可改善用于制备铝的熔盐电解所用的电解池中碳阴极或石墨阴极的腐蚀和氧化稳定性，同时能够克服现有技术的缺点。
本发明的目的还在于提供一种用于修复电解池中阴极小孔的填充材料，其相比于现有技术所用的那些填充材料能够提高电解池的生产率，并且相比于熔融冰晶石具有更高的耐腐蚀性。
本发明的目的还在于提供一种用于修复电解池的阴极底部小孔的改进方法，其能够将修复材料更有针对性地结合到修复位点中。
发明内容
根据本发明的上述目的通过根据本发明所述的二硼化钛颗粒剂、根据本发明所述的制备此类二硼化钛颗粒剂的方法、根据本发明所述的此类二硼化钛颗粒剂的用途以及根据本发明所述的使用此类二硼化钛颗粒剂的方法而得以实现。
因此，本发明的主题涉及包含二硼化钛原生粒子的聚集体的二硼化钛颗粒剂，其中所述的二硼化钛颗粒剂具有圆形形状并且耐破碎。
本发明还提供了用于制备此类二硼化钛颗粒剂的方法，该方法包括如下步骤：
a)将TiB2粉末与粘结剂材料和/或助剂和/或溶剂混合，
b)制备具有所需粒径的TiB2颗粒剂生团粒，
c)任选地干燥和/或脱脂以除去溶剂和/或助剂，以及
d)热处理TiB2颗粒剂生团粒以制备TiB2颗粒剂。
本发明的另一个主题为使用根据本发明所述的二硼化钛颗粒剂覆盖用于制备铝的熔盐电解中所用的电解池中的碳或石墨阴极。
本发明的另一个主题为使用根据本发明所述的二硼化钛颗粒剂修复用于制备铝的熔盐电解中所用的阴极电解池底部的小孔。
本发明的另一个主题为修复用于制备铝的熔盐电解中所用的电解池阴极底部小孔的方法，其包括如下步骤：
a)由根据本发明所述的TiB2颗粒剂和铝制备二硼化钛-铝复合成形团粒；
b)在电解池运行过程中，将所述成形团粒引入待修复的阴极小孔内。
与常规的二硼化钛-石墨混合物相比，根据本发明所述的二硼化钛颗粒剂的优点在于，阴极的功能化表面上完全不存在石墨，减少了腐蚀引起的磨损，从而延长了阴极的使用寿命。仅由二硼化钛组成的阴极涂层能够使涂层厚度小于二硼化钛-石墨混合物的涂层厚度。在电解池中安装阴极后，通过将二硼化钛颗粒剂引入到阴极上能够省去常规的二硼化钛-石墨混合物所需要的复杂的共挤出或额外的振动压实工艺，从而可使阴极的总制造成本大大降低。
与已知的软质TiB2颗粒剂相比，根据本发明所述的二硼化钛颗粒剂的优点在于其机械稳定性更高，即耐磨损和耐破碎性更强，使其在运输过程中更加稳定，并且在受到压力或摩擦作用时不会破碎。
因此极大避免了在定期虹吸取出铝的过程中将带出电解池的细颗粒物的形成，从而使铝的性质不再受到不利影响，并且可以减少铣削故障和强度损失。
硬质且耐压缩的颗粒剂的另外一个优点在于，通过定向混合不同的颗粒剂或颗粒组分形成致密层可以在电解池使用寿命期限内维持预设的较高的堆积密度，从而更好地防止阴极发生腐蚀引起的磨损。
根据本发明所述的颗粒剂的另外一个优点在于，它们具有圆形形状，从而能够更好地分布于阴极表面上。
与用于选择性修复磨损阴极的常规颗粒剂相比，根据本发明所述的二硼化钛颗粒剂的优点在于它们具有导电性，因此不会对电解池的生产率和铝的制备成本产生不利影响。它们与常规使用的Al2O3相比的优点还在于，TiB2具有比熔融冰晶石更高的耐腐蚀性。
至于根据本发明所述的用于修复选定位点处发生磨损的阴极(即，修复阴极中的小孔)的方法，其中二硼化钛颗粒剂以TiB2-Al锭的形式进行使用，其可以将二硼化钛颗粒剂具体定位于修复位点，而不会扩散到较大的表面区域。致密的TiB2-Al锭落入阴极的小孔中，并悬浮到小孔中，即，铝熔体和TiB2颗粒剂保留在损坏区域中，从而能够实现优于常规方法的填充效果。
具体实施方式
根据本发明所述的TiB2颗粒剂的机械稳定性高，且与已知的软质颗粒剂相比，具有更高的压缩强度和硬度。这使其耐磨损且耐破碎，并且在转移以及将颗粒剂引入Al电解池的熔融槽以覆盖阴极时具有良好的运输和尺寸稳定性，即，在这些步骤中，颗粒剂形式和结构得到维持。
以压缩测试中破碎的最大力来测量，根据本发明所述的TiB2颗粒剂的压缩强度优选为至少5N、更优选为至少7N、更优选为至少9N，并且特别优选为至少12N。压缩强度的测量按照DIN 51 104进行。与DIN 51 104的不同之处在于，由于颗粒剂的强度小于烧结陶瓷的强度，因此不需要使用中间板(参见DIN图2中的3和章节5.2)。并且与DIN 51 104的不同之处还在于，无需计算相对于表面的断裂应力，并且压缩强度表示为破碎颗粒剂的最大负荷(破碎力)。
根据本发明所述的TiB2颗粒剂优选包含无机粘结剂，该无机粘结剂可基于TiB2颗粒剂的总重量计，适当地以最高至10重量％，特别优选不超过1重量％的量存在。
无机粘结剂优选包括氧化物粘结剂。优选地，氧化物粘结剂包括选自氧化铝(Al2O3)、氢氧化铝(Al(OH)3)和水软铝石(AlO(OH))的Al化合物、SiO2或它们的组合。最优选地，无机粘结剂为Al化合物，有利地为Al2O3。
根据本发明所述的TiB2颗粒剂的粒径可以为1mm至10mm。该粒径优选为2至7mm。此外，优选至少80重量％的TiB2颗粒剂具有至少为2mm的粒径。在这种情况下，粒径通过标准筛分分析确定，因此上述粒径为“过筛粒径”。因此，介于1与10mm之间的过筛粒径是指颗粒剂能够穿过目尺寸为10mm的筛，而不能穿过目尺寸为1mm的筛。
根据本发明所述的颗粒剂的形状不是角状、块状或裂片状，而是圆形；它们可以为“马铃薯形”或卵石形至圆形或球形。
在Al电解所用的条件下，根据本发明所述的颗粒剂为热稳定的。
根据本发明所述的TiB2颗粒剂可通过一种方法制备，该方法包括如下步骤：
a)将TiB2粉末与粘结剂材料和/或助剂和/或溶剂混合，
b)制备具有所需粒径的TiB2颗粒剂生团粒，
c)任选地干燥和/或脱脂以除去溶剂和/或助剂，以及
d)对TiB2颗粒剂生团粒进行热处理(烧结)以制备TiB2颗粒剂。
可以将步骤a)和b)合并并在一个步骤中进行。同样，也可以将步骤c)和d)在一个步骤中进行。
适合在步骤a)中作为用于根据本发明所述的TiB2颗粒剂的原料为具有一定粒度和纯度的TiB2粉末(原生粒子的聚集体)，其具有用于制备烧结组分的典型商业品质。此类TiB2粉末的平均粒度(d50)优选为约2-20μm。
TiB2粉末的粒径(原生粒度分布，BET)对各个工艺步骤(混合、制粒、压实、挤出)的加工行为具有影响，并且在不同的加工技术中需要不同的工艺参数以实现限定的最终产品尺寸。较细小的原料粉末需要使用更多的液体和更长的加工时间以实现一定的粒径。该方法还适用于制备挤出材料或模制化合物。
如果使用形成热稳定性粘结剂的粘结剂材料制备根据本发明所述的TiB2颗粒剂，步骤a)中所用的粘结剂材料为无机粘结剂材料或此类材料的前体，即，在步骤d)中固化TiB2颗粒剂所用的形成无机粘结剂的粘结剂材料(称作粘结剂前体系统)。可以使用氧化物陶瓷粘结剂原材料或在固化TiB2颗粒剂过程中形成氧化物陶瓷的材料。可以使用SiO2基或SiO2形成的粘结剂原材料以及Al2O3基或Al2O3形成的粘结剂原材料。优选使用Al2O3基或Al2O3形成的粘结剂材料，特别优选使用Al2O3形成的粘结剂原材料。
为了获得良好的粘结效果，优选使用纳米级粘结剂材料或在步骤b)至d)的制备条件下形成纳米级粘结剂颗粒的材料(粘结剂前体系统)，因为利用这些粘结剂材料能够在极低浓度且适合的较低温度下获得所需的特性。纳米级粘结剂是指具有<100nm的平均粒度的粘结剂。
SiO2基粘结剂原材料的例子包括热解法二氧化硅、熔融二氧化硅、沉淀二氧化硅和二氧化硅粉。
硅烷和硅氧烷(例如)可以用作SiO2形成的粘结剂前体系统，并且Al(OH)3或AlO(OH)(以举例的方式)可以用作Al2O3粘结剂相的前体。
作为SiO2基粘结剂原材料，市售的SiO2溶胶(水溶性溶胶和醇溶性溶胶)在必要时可以根据初始浓度进行适当稀释，也可直接用作粘结剂溶液进行制粒。合适的市售水基产品的例子为购自NALCO和(巴德克斯特里茨化工厂)(NALCO and(Chemical Plant Bad))的SiO2溶胶。
如果所选的粘结剂原材料尚不是液态形式，优选将其转化为可溶形式，其中可使用有机溶剂和水或有机溶剂与水的混合物作为溶剂。
醇溶性粘结剂原材料的例子包括纳米SiO2颗粒与硅烷的醇溶性悬浮液，其可以购自EPG公司(产品名称：MTKS)或购自Inomat公司(产品名称：Inosil)。
Al2O3基粘结剂原材料的例子为市售的Al2O3溶胶或溶胶-凝胶，例如Al2O3纳米粒子分散体，其粒度为<100nm。此外，可使用平均粒度(d50)<为1μm的极细的金刚砂粉末。
AlO(OH)溶胶-凝胶(水软铝石溶胶-凝胶)可通过改变最终产品中所需的Al2O3粘结剂组分的浓度以实现各种调整，此外，它在制粒工艺中具有良好的加工特性，特别优选地用作Al2O3形成的粘结剂前体系统。
粘结剂原材料的量有利地按如下方式选择，即不会对二硼化钛颗粒剂的导电性产生不利影响。
在步骤a)中，可任选地向有机粘结剂中加入助剂，例如丙烯酸酯(如Duramax)、纤维素(如Degalan)、多糖和蜡(硬脂精)，以及助压剂和增塑剂，其在步骤d)中的热处理过程中发生分解。
如果不执行干压实，则优选使用溶剂进行制粒。通常，优选使用水进行制粒。也可使用其他液体。
在步骤b)中可使用多种方法来制备根据本发明所述的TiB2颗粒剂，使最终得到的颗粒剂具有圆形形状。
一种可行的方法是造球。在该方法中，将TiB2粉末的塑料陶瓷组合物以及任选地粘结剂原材料的溶液、溶胶或凝胶通过例如使用棒压及相应的筛网插件加工成股线或破碎股线颗粒剂。还可使用捏合机和相连的挤出机以及适当的成形插件进行造球，由此制得股线或破碎股线颗粒剂。具有5mm直径的股线(例如)被切割为5mm的所需长度，或者(例如)被材料的水分碎裂。
根据所用的TiB2粉末的原生粒度分布所需的粘结剂溶液的浓度和含量，可任选地使用其他加工助剂，诸如增塑剂或助压剂。例如，可使用丙烯酸酯(如Duramax)、纤维素(如Degalan)、多糖和蜡(硬脂精)作为加工助剂。用于破碎股线制粒的原材料可适当地包含约30重量％的溶剂，优选为水。
另一种可行的制粒方法是将TiB2粉末和溶剂的混合物以及可任选地粘结剂原材料的溶液经过混合/均化后进行制片，通过模压机及相应的成形插件将其压为球剂、片剂、小块或小片。如有必要，可使用另外的加工助剂，诸如模压剂。用于制片的模压混合物可适当地包含约5重量％的溶剂，优选为水，以及约10重量％的干压助剂。(例如)丙烯酸酯、纤维素、多糖和蜡(诸如硬脂精)可用作模压助剂以实现该目的。
另一种可行的用于制备根据本发明所述的TiB2颗粒剂的步骤b)中的方法为干压实。为此，在步骤a)中将模压助剂(诸如蜡)以及任选地干粘结剂原材料加入TiB2粉末中，并压实。模压助剂可以在步骤d)中除去或此前在步骤c)中单独的脱脂步骤中除去。
用于制备根据本发明所述的TiB2颗粒剂的优选方法为将TiB2粉末积聚为(例如)平均直径5mm的颗粒剂。积聚制粒通常将得到圆形或圆球形颗粒剂。为此，步骤a)和b)可以一起进行，即，在一个步骤中进行混合和制粒。
通过这种方法，可以制备不含粘结剂的TiB2颗粒剂或粘结剂含量很低的TiB2颗粒剂。可使用有机溶剂或水作为溶剂，优选使用水。
考虑到可用的批料粒度和制粒体积，利用积聚制粒可以在同一制粒时间内通过改变粘结剂溶剂的量或粘结剂浓度制得不同粒径，或可在限定的粘结剂-溶剂范围内通过改变制粒时间制得不同颗粒直径。
水软铝石溶胶-凝胶尤其优选用作粘结剂进行积聚制粒，因为该粘结剂具有流变性，在干燥阶段对积聚颗粒剂的稳定效果优于溶胶和分散体。该粘结剂的另一个优点在于它是水基的。
为了实现更好的均化，粘结剂材料有利地以溶解形式使用，在这种情况下优选在步骤c)中对颗粒剂进行干燥。
干燥步骤c)用于除去粘结剂原材料的溶剂以及用于制粒的水或溶剂。如果干燥步骤作为单独的工艺步骤执行，则下一个工艺步骤d)(煅烧、硬化/烧结)将无需提供溶剂。为了防止或最大限度减少破碎和磨损，只能对模制步骤b)中得到的生球剂进行微小的移动或轻微的触摸。干燥步骤可以在(例如)干燥室或对流干燥室中进行，还可以在回转窑或流化床工艺中进行。也可使用其他的干燥系统。
通过步骤d)中的热处理，颗粒剂的硬度和机械强度将得到提高。
就SiO2基粘结剂而言，温度处理或固化优选在惰性气氛中在至少1400℃的温度下进行。
就Al2O3基粘结剂而言，温度处理或固化优选在惰性气氛中在至少1600℃的温度下进行。
就SiO2形成的粘结剂原材料(粘结剂前体系统)而言，温度处理或固化优选在惰性气氛中在至少900℃的温度下进行。
就特别优选的Al2O3形成的粘结剂原材料(粘结剂前体系统)而言，热处理或固化优选在惰性气氛中在至少800℃、更优选为在至少1100℃的温度下进行。
就特别优选使用的粘结剂原材料水软铝石而言，需要在至少800℃的温度下对TiB2颗粒剂进行脱水，使水软铝石转化为Al2O3。AlO(OH)向Al2O3的转化从800℃开始并在1100℃完成。另外，通过1100℃下的热处理能够显著提高硬度和稳定性。800℃下的温度处理优选应在惰性气氛中进行至少30分钟。惰性气氛能够防止TiB2氧化为TiO2，其在冰晶石/Al中的耐受性较差并且不导电。特别优选地，热处理在惰性气氛中于1100℃下进行至少60分钟。一方面，这样能够除去得到的所有H2O；另一方面，纳米级Al2O3开始烧结，从而使颗粒剂硬化。
800℃下的煅烧和1100℃下的烧结可以分两步进行也可以在一步中完成。
对于不含粘结剂的TiB2颗粒剂，热处理优选在惰性气氛下于至少1100℃的温度下、特别优选于介于1800和2100℃之间的温度下、更优选为约2000℃下进行。
根据本发明所述的不使用粘结剂原材料制备的TiB2颗粒剂为烧结的TiB2颗粒剂。根据本发明所述的使用粘结剂原材料制备的TiB2-颗粒剂在经过步骤d)的温度处理后，其中除了含有TiB2原生粒子以外，还包含无机粘结剂，即SiO2(在使用SiO2基或SiO2形成的粘结剂原材料的情况下)和无机粘结剂Al2O3(在使用Al2O3基或Al2O3形成的粘结剂原材料的情况下)。
为了使用根据本发明所述的TiB2颗粒剂防止铝电解池中碳或石墨阴极发生腐蚀，TiB2颗粒剂应当在电解池填充和初次运行之前或之后施加于阴极底部。TiB2颗粒剂的机械稳定性能够确保颗粒剂填充物的填充和均匀分布，并且圆形形状的颗粒剂相比于球剂和片剂更有利于颗粒剂填充物的填充和均匀分布。
TiB2颗粒剂还可用作修复化合物，修复电解池运行过程中在阴极中形成的小孔。为实现这一目的，在电解池运行过程中，将根据本发明所述的TiB2颗粒剂放入Al电解槽中小孔上方。颗粒剂沉入电解池底部并至少部分地填充待修复的小孔。
为了更好地利用TiB2颗粒剂修复阴极中的小孔，制备了TiB2与铝的二硼化钛-Al复合成形团粒(TiB2-Al锭)。为此，将TiB2颗粒剂倾注或搅拌到液态Al熔体中。或者，将TiB2颗粒剂与铝进行浇铸。为此，将颗粒剂填充到合适的模具或坩埚中并与熔融Al进行浇铸(低压浇铸、重力浇铸、冷硬浇铸)。
所得到的成形团粒由致密颗粒剂、片剂或小球填料构成，其空隙填充以Al熔体或被硬化金属渗透并以这种方式结合在一起。
如果在根据本发明所述的TiB2颗粒剂中引入了无机粘结剂以制备成形团粒，则TiB2颗粒剂的粘结剂或粘结剂涂层将有利于被熔体润湿。
以这种方式得到的填充以TiB2颗粒剂(块、柱体等)的铝成形团粒重约5-20kg。
将TiB2填充的铝成形团粒置于熔融槽中待修复的阴极小孔上方并沉下。在下沉过程中或浸入待修复的小孔后，铝熔化并释放TiB2颗粒剂。
实例和参考例
实例1(不含粘结剂的积聚颗粒剂)
将4.5kg TiB2粉末(d50 11μm)引入Eirich强力混合机中。在搅拌过程中，加入500mL水并进行制粒，共用时10mcin。将所得的湿润的积聚颗粒剂于>80℃下在循环空气干燥柜中干燥12小时。
然后将干燥后的颗粒剂在(流动的)氩气下于1100℃退火1小时。
通过筛分分析测得的粒径分布为0.2mm至5mm的颗粒剂的产率为75％。粒径分布为2mm至5mm的颗粒剂的产率为60％。
所得到的颗粒剂具有圆形形状，并且耐磨损且耐破碎，手指揉搓时不易碎或可压碎。
实例2(含水软铝石粘结剂的积聚颗粒剂)
为了制备水软铝石溶胶-凝胶(粘结剂原材料)，将购自萨索尔公司(Sasol)的Dispersal分散于水中。将分散体加热至>95℃，然后通过加入浓缩HNO3使胶溶。冷却后，得到凝胶(含6重量％的Al2O3)。
将4.5kg TiB2粉末(平均粒度d50 11μm)引入Eirich强力混合机(R02型)中。在搅拌过程中，加入500mL水软铝石溶胶-凝胶(含6重量％的Al2O3)并进行制粒，共用时10分钟。将所得的湿润的颗粒剂于>80℃下在循环空气干燥柜中干燥12小时。
然后将干燥后的颗粒剂在(流动的)氩气下于1100℃退火1小时。
通过筛分分析测得的粒径分布为0.5mm至8mm的颗粒剂的产率为90％。粒径分布为2mm至8mm的颗粒剂的产率为70％。
所得到的颗粒剂具有圆形形状，并且耐磨损且耐破碎，手指揉搓时不易碎或可压碎。
实例3(含水软铝石粘结剂的积聚颗粒剂)
重复实例2，不同的是干燥的颗粒剂并非在1100℃下进行退火，而是在(流动的)氩气下于800℃退火1小时。
所得到的颗粒剂具有圆形形状，并且耐磨损且耐破碎，手指揉搓时不易碎或可压碎。
实例4(不含粘结剂的积聚颗粒剂)
重复实例1，不同的是干燥的颗粒剂并非在1100℃下进行焙烧，而是在(流动的)氩气下于2000℃焙烧1小时。
所得到的颗粒剂具有圆形形状，并且耐磨损且耐破碎，手指揉搓时不易碎或可压碎。
实例5(含水软铝石粘结剂的积聚颗粒剂)
重复实例2，不同的是干燥的颗粒剂并非在1100℃下进行退火，而是在(流动的)氩气下于2000℃退火1小时。
所得到的颗粒剂具有圆形形状，并且耐磨损且耐破碎，手指揉搓时不易碎或可压碎。
实例6(含水软铝石粘结剂的积聚颗粒剂)
将4.5kg TiB2粉末(平均粒度d50 11μm)引入Eirich强力混合机中。在搅拌过程中，加入400mL实例2的水软铝石溶胶-凝胶(含6重量％的Al2O3)并进行制粒，共用时10分钟。将所得的湿润的颗粒剂于>80℃下在循环空气干燥柜中干燥12小时。
然后将干燥后的颗粒剂在(流动的)氩气下于1100℃退火1小时。
通过筛分分析测得的粒径分布为0.2mm至5mm的颗粒剂的产率为95％。粒径分布为2mm至5mm的颗粒剂的产率为80％。
所得到的颗粒剂具有圆形形状，并且耐磨损且耐破碎，手指揉搓时不易碎或可压碎。
参考例1(不含粘结剂的滤饼颗粒剂)
通过搅拌，使1.5kg TiB2粉末(d50 11μm)分散于4升水中。然后滤除悬浮液。将得到的滤饼(包括滤纸)置于循环空气干燥柜中于>80℃下干燥12小时。
使用5mm筛将干燥的滤饼破碎，所得到的部分再用1mm筛进行筛分。粒径分布为1mm至5mm的颗粒剂的产率为5％。
所得到的颗粒剂具有角形或裂片形形状，在手指揉搓时易碎或可压碎，因此不具有耐破碎性。
参考例2(不含粘结剂的积聚颗粒剂)
重复实例1，不同的是干燥后的颗粒剂随后未经过热处理。
所得到的颗粒剂具有圆形形状，但在手指揉搓时易碎或可压碎，因此不具有耐破碎性。
参考例3(含水软铝石粘结剂的积聚颗粒剂)
重复实例2，不同的是干燥后的颗粒剂随后未经过热处理。
所得到的颗粒剂具有圆形形状，但在手指揉搓时易碎或可压碎，因此不具有耐破碎性。
参考例4(不含粘结剂的滤饼颗粒剂)
重复参考例1，不同的是滤饼颗粒剂在(流动的)氩气下于1100℃退火1小时。
所得到的颗粒剂具有角形或裂片形形状，在手指揉搓时易碎或可压碎，因此不具有耐破碎性。
实例7
然后对实例1至5以及参考例1至4所制得的颗粒剂进行压缩强度测定。
按照DIN 51 104对各个颗粒剂团粒的压缩强度进行测定，测试速度为2mm/min(采用Zwick 1472万能试验机，用Softone TestXpert II软件进行机器控制和数据采集)。将测得的颗粒剂(试件)破碎/崩解的最大负荷作为压缩强度。使用由硬化钢制成的平行压片作为试验装置。对尺寸范围为4至5mm的颗粒剂部分进行测量。
压缩强度测试的结果如表1所示，其表示为使颗粒剂破碎的最大力。
表1

Claims (15)

1.一种用于制备圆形的二硼化钛积聚颗粒剂的方法，其包括如下步骤：
a)将二硼化钛粉末与无机粘结剂原材料和/或助剂和/或溶剂相混合，
b)制备具有所需粒径的圆形的所述二硼化钛积聚颗粒剂生团粒，
c)任选地干燥和/或脱脂以除去溶剂和/或助剂，以及
d)对圆形的所述二硼化钛积聚颗粒剂生团粒进行退火以制备所述二硼化钛积聚颗粒剂，
其中用作粘结剂原材料的材料为纳米级粘结剂材料或在步骤b)至d)的所述制备条件下形成纳米级颗粒的粘结剂前体系统，其中基于所述二硼化钛积聚颗粒剂的总重量计，所述无机粘结剂原材料的量不超过1重量％，且其中所述二硼化钛积聚颗粒剂的粒径为1mm至10mm。
2.根据权利要求1所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中所用的二硼化钛粉末的平均粒度d50为2-20μm。
3.根据权利要求1所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中SiO2形成的粘结剂原材料用作粘结剂前体系统。
4.根据权利要求1所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中Al2O3形成的粘结剂原材料用作粘结剂前体系统。
5.根据权利要求4所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中AlO(OH)溶胶-凝胶用作粘结剂原材料。
6.根据权利要求3所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中步骤d)中的退火在至少900℃的温度下，在惰性气氛下进行。
7.根据权利要求4或5所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中步骤d)中的所述退火在至少800℃的温度下，在惰性气氛下进行。
8.根据权利要求4或5所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中步骤d)中的所述退火在至少1100℃的温度下，在惰性气氛下进行。
9.根据权利要求1所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中步骤a)中不使用粘结剂原材料并且其中步骤d)中的所述退火在至少1100℃的温度下，在惰性气氛下进行。
10.根据权利要求1所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中步骤a)中不使用粘结剂原材料并且其中步骤d)中的所述退火在介于1800与2100℃之间的温度下，在惰性气氛下进行。
11.根据权利要求1所述的用于制备圆形的二硼化钛积聚颗粒剂的方法，其中步骤a)中不使用粘结剂原材料并且其中步骤d)中的所述退火在2000℃的温度下，在惰性气氛下进行。
12.根据权利要求1-11中任一项所述的方法制备的圆形的二硼化钛积聚颗粒剂。
13.根据权利要求12所述的圆形的二硼化钛积聚颗粒剂在涂覆用于制备Al的熔盐电解中所用的电解池中的碳或石墨阴极方面的用途。
14.根据权利要求12所述的圆形的二硼化钛积聚颗粒剂在修复用于制备Al的熔盐电解中所用的电解池的阴极底部小孔方面的用途。
15.一种用于修复用于制备Al的熔盐电解中所用的电解池的阴极底部小孔的方法，其包括如下步骤：
a)由根据权利要求12所述的圆形的二硼化钛积聚颗粒剂和铝制备二硼化钛-铝复合成形团粒；
b)在所述电解池运行过程中，将所述成形团粒置于待修复的所述阴极的小孔内。
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