CN1788109B - 铝电解槽用高膨胀捣固糊 - Google Patents

铝电解槽用高膨胀捣固糊 Download PDF

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CN1788109B
CN1788109B CN2004800129981A CN200480012998A CN1788109B CN 1788109 B CN1788109 B CN 1788109B CN 2004800129981 A CN2004800129981 A CN 2004800129981A CN 200480012998 A CN200480012998 A CN 200480012998A CN 1788109 B CN1788109 B CN 1788109B
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ramming paste
anode
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A·A·米尔希
W·陈
L·拉维涅
E·贝热龙
J·贝热龙
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Rio Tinto Alcan International Ltd
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Abstract

一种用于铝还原电解槽阴极的新捣固糊，其是一种高膨胀冷捣固糊，由沥青、轻油稀释剂和聚集体的混合物制成，所述聚集体包括无烟煤和碎阳极残极或煅烧焦炭的混合物。由于含有碎阳极残极或煅烧焦炭，捣固糊的钠膨胀指数得以提高，比常规捣固糊高约四倍。这种新的高膨胀冷捣固糊也可以含有一定量的耐火硬质材料，如TiB2。

Description

铝电解槽用高膨胀捣固糊
技术领域
本发明涉及一种改进的铝电解还原槽阴极用捣固糊(rammingpaste)。
背景技术
在含有溶解氧化铝的熔融冰晶石电解液中通过电流，可以方便地在电解槽中制备金属铝。电解槽通常是一个衬有碳的大池或槽，该衬作为阴极体系的一部分。大碳块延伸至电解液顶部内而作为阳极。熔融金属铝集中在槽底形成金属垫。电解槽一般具有胶接碳块制成的底部内衬层，其中水平放置的钢阴极棒从槽的对边延伸过来。这些阴极棒通过铸铁连接到阴极收集块上，而上述收集块固定在侧壁内衬中。
大多数商用铝还原电解槽采用预制的碳块作为电解槽内衬和阴极工作面。这些碳块提供高工作强度、高密度、而且电阻率低于连续捣固糊型内衬。将上述碳块制成不透液的容器，在碳块之间的接缝处填充捣固糊而形成表面。捣固糊的密封效果是决定电解槽寿命和能量效率的一个重要因素，它在很大程度上取决于电解渗透至电解槽底部内的程度和速度。
阳极一般由碎石油焦和液态沥青制成，制成矩形块并烘烤。上述阳极块连接在棒上，悬垂至电解槽内，在铝熔炼过程中于该位置慢慢消耗。几周后必须更换阳极块，连接在棒上的被清除的剩余部分称为阳极残极(anode butt)。所述阳极残极一般重复利用。
常规阴极块由无烟煤聚集体与沥青粘结剂混合制成。为提高导电率，可以将石墨组分取代。如上所述，用捣固糊来填充独立的阴极块之间的空间、形成接缝，并且连接侧壁与阴极块。一般热捣固糊由无烟煤填充物和煤焦油粘结剂组成。冷(室温)捣固糊粘结剂通常包括稀释剂以降低其软化点。
为了用捣固糊形成接缝，将糊加到接缝空间内并进行压制，如使用气锤。在多个层中形成接缝，直至与阴极块顶部齐平的最顶层表面。可以通过压制该糊，以相似的方式形成侧壁、包括整体斜面。
由于金属渗入接缝，会发生早期的电解槽损坏，如果使用钠膨胀指数极低的石墨化阴极块，该问题可能会更为严重。由于这个问题，需要有一种能固定周边接缝(大接缝)和阴极块之间的接缝的高膨胀冷捣固糊。
电解槽可能发生的另一个问题是，磁-流体动力学作用(MHE)导致偶尔发生过度的金属运动，阴极内衬特别是整体边斜面量和阴极块之间的接缝会发生快速腐蚀和损坏。
Reamey等人的美国专利3871986中公开了一种铝还原电解槽用捣固粘结剂，该粘结剂据称在随后的烘烤中不会收缩。这需要一种特殊的沥青粘结剂，所述沥青粘结剂包括一种水中方块(cube-in-water)软化点在约40℃-约85℃之间的石油沥青，该石油沥青中不可溶于喹啉的物质的含量不高于约1％。
美国专利5961811(Keller)中公开了另一种形式的铝还原电解槽用捣固糊，由碳和活性化合物制成，所述活性化合物如碳化物、氟化物、磷酸盐或氧化物，该活性化合物在电解槽生产铝的工作期间能与钛或锆反应生成二硼化钛或二硼化锆。二硼化钛或二硼化锆的生成量足以提高该含碳材料的熔融铝润湿性能。
在Mirtchi的美国专利6258224中，针对MHE使电解槽中的物质发生运动、从而使制备铝的电解槽的底部砌块发生腐蚀/侵蚀的问题。该专利提供一种多层阴极结构，包括一个含碳阴极基底，在基底上有至少一层含金属硼化物如TiB2的复合耐火材料。首先将基底和TiB2复合材料之间的界面粗糙化(用耙子耙)以克服这两种材料之间的热膨胀差异。
改进铝还原电解槽用捣固糊的另一种尝试记载于de Nora等人的美国专利5676807。de Nora主要考虑到沥青粘结剂的污染问题，根据该发明所述，使用胶体粘结材料如胶体状态的氧化铝来制备捣固糊。
本发明的一个目的是提供一种改进的捣固糊，其具有高膨胀指数，并能用于较冷的环境，如30℃。
本发明的一个进一步目的是提供一种改进的捣固糊，其具有良好的耐蚀性，并能被铝润湿。
发明详述
根据本发明所述，提供一种用于铝电解槽的新颖的高膨胀冷捣固糊，所述冷捣固糊能够容易地由市售材料制备。该冷捣固糊可以用于整体边斜面以及阴极块之间的接缝中。
一般含有无烟煤作为聚集体(aggregate)和沥青作为粘结剂的冷捣固糊，已经发现在其中加入部分碎阳极残极或煅烧焦炭后可使其具有高膨胀性能。所述阳极残极是从电解槽中清除的已消耗阳极的剩余物，所述煅烧焦炭一般是制造该阳极所用类型的煅烧石油焦碳。
因此，根据本发明的一个主要特征，提供一种高膨胀冷捣固糊，包括沥青、轻油稀释剂和聚集体的混合物，所述聚集体包括无烟煤和碎阳极残极或煅烧焦炭的混合物。碎阳极残极或煅烧焦炭的含量以总聚集体重量计一般最高达20％，优选约15-20％。以重量计，沥青的含量一般为约10-15％，轻油的含量最高达10％，如约5-10％，余量为聚集体。
轻油作为沥青的溶剂，降低其软化点，从而使捣固糊在室温软化、有粘性。轻油一般是沸程约210-355℃的轻酚油残渣。
根据本发明的进一步特征，在上述捣固糊中加入部分耐火硬质材料，如碎耐火材料、TiB2、TiO2、B2O3、SiC、Al2O3等，可以使该捣固糊具有耐蚀性和浸润性。这些材料可以增强该捣固糊，同时使其具备浸润性。对于含有硼化物如二硼化钛的捣固糊而言，典型组成以重量计包括30-60％二硼化钛，10-15％沥青，5-10％轻油，余量为聚集体，所述聚集体为无烟煤和碎阳极残极或煅烧焦炭的混合物，其中碎阳极残极或煅烧焦炭的含量以总聚集体重量计最高达20％。下文中将该捣固糊称为“含TiB2糊”。
优选将上述组分一同混合制成糊，混合温度约90-130℃，混合时间约20-50分钟。优选在约20-40℃的温度将该糊施加到阴极块之间的接缝处和施加到上述块和电解槽的侧壁之间的整体斜面。
优选捣固糊作为一系列的层在接缝处施加，各层之间进行捣固以形成致密无孔的接缝。顶层优选由含TiB2糊制成。当施加顶层后，紧邻的下面一层捣固糊不单独地捣固，将这两层捣固在一起。这使得各层之间产生混合从而允许各层之间存在热膨胀差异。含TiB2顶层的厚度一般约2.5-12.5cm，优选约3.75-7.5cm。
该含TiB2捣固糊在疏松形态和压制形态的密度一般都高于标准捣固糊。疏松形态的含TiB2捣固糊的密度一般至少比常规市售捣固糊高25％，而压制形态的密度则一般至少高30％。
据信可以在碎阳极残极或煅烧焦炭中焦炭的混乱结构中发现本发明所述捣固糊的高膨胀性能，所述碎阳极残极或煅烧焦炭为钠渗透和由此发生的钠膨胀构成了更有利的场所。由于所述钠膨胀，获得了高膨胀糊，它可以固定周边接缝(大接缝)和块之间的接缝，从而防止金属和电解液发生渗透。发现用占总聚集体重量的15-20％的碎阳极残极或煅烧焦炭构成聚集体的一部分时，捣固糊的钠膨胀指数比常规捣固糊提高了约4倍。
附图简述
图1是三种不同捣固糊作为温度的函数的膨胀曲线。
优选实施方案
实施例1
制备膨胀冷捣固糊，以重量计含有10％沥青，6.3％轻酚油残渣和83.7％聚集体。该聚集体以重量计含有83％无烟煤和17％碎阳极残极。
为进行对比研究，制备一种常规冷捣固糊，其以重量计含有10％沥青，6.3％沸程约210-355℃的轻酚油残渣，余量为无烟煤聚集体。比较这两种捣固糊的性能，同时还与市售的名为Carbone SavoieAMT73S30和Vesuvius CP45的捣固糊进行比较。
性能如下表1所示。可以看出，本发明所述膨胀捣固糊的钠膨胀指数比常规无烟煤基捣固糊高约4倍。
表1捣固糊性能
  新膨胀冷捣固糊   标准冷捣固糊   CarboneSavoieAMT73S30   Vesuvius CP45
  烘烤密度(g/cm<sup>3</sup>)   1.456±0.005(n＝8)   1.482±0.007(n＝12)   1.466±0.006(n＝4)   1.542±0.004(n＝8)
  电阻率(μΩ·m)   60±1(n＝8)   60±1(n＝12)   66±1(n＝4)   58±1(n＝4)
  抗碎强度(MPa)   18.3±0.2(n＝8)   16.5±2.8(n＝12)   18±1(n＝4)   27±1(n＝4)
  拉伸强度(MPa)   1.9±0.2(n＝8)   1.9±0.2(n＝12)   2.2±0.4(n＝4)   3.8±0.3(n＝4)
  热膨胀系数(×10<sup>-6</sup>/℃)   4.48±0.05(n＝8)   4.28±0.08(n＝12)   na   4.14±0.12(n＝4)
  室温下的导热率(W/m℃)   5.51±0.33(n＝8)   5.58±0.47(n＝12)   na   6.39±0.14(n＝4)
  新膨胀冷捣固糊   标准冷捣固糊   CarboneSavoieAMT73S30   Vesuvius CP45
  收缩率**(％)   0.23±0.08(n＝3)   0.27±0.07(n＝3)   0.10±0.06(n＝2)   0.58
  钠膨胀指数(％)   4.9±1(n＝4)   1.1±0.1(n＝6)   0.84±0.09(n＝2)   1.2
  捣固密度(g/cm<sup>3</sup>)   1.611±0.014(n＝15)   1.657±0.016(n＝16)   1.622±0.003(n＝4)   1.644±0.006(n＝4)
结果以平均值±标准偏差表示
n：实验次数
na：无法获得
实施例2
捣固糊另一个非常重要的性质是其收缩的程度。本发明所述捣固糊的收缩率小于Vesuvius CP-45捣固糊。本发明所述膨胀冷糊、常规Alcan冷糊和Vesuvius CP-45糊的典型膨胀/收缩曲线如图1所示。
实施例3
进一步制备含有二硼化钛的捣固糊。该捣固糊的制备过程是：将以重量计7％的轻油、12％的沥青、55％的二硼化钛粉末和26％的聚集体一起混合，所述聚集体由无烟煤和碎阳极残极混合物组成，其中碎阳极残极占总聚集体重量的约17％。在约100-120℃将这些成分混合，混合时间约为45分钟。制成的捣固糊可以用于约25-35℃的工作温度。
这极大地提高了捣固糊的耐蚀性，同时使其具有铝润湿性。
实施例4
进行试验以比较实施例3的TiB2捣固糊与常规捣固糊(VesuviusCP-45)的密度。对疏松材料和压制材料都进行密度试验。
试验中，使用直径5.22cm、高度21.92cm、容积469.29cc的管。对于疏松材料的试验，将管充满至边缘，在台上敲击几次使捣固糊部分沉降。制备压制试样时，用捣固活塞撞击管中的材料200次，使材料压紧，随后测定其密度。
试验结果如下表2所示：
Figure G04812998119970228D000061

Claims (13)

1.一种冷捣固糊，用于连接为制备铝而进行氧化铝电解的电解槽的部件，包括沥青和含碳聚集体的混合物，所述聚集体包含无烟煤，其特征在于所述冷捣固糊包含轻油并且所述聚集体包含碎阳极残极或煅烧焦炭，碎阳极残极或煅烧焦炭的含量以总聚集体重量计最高达20％。
2.如权利要求1所述的冷捣固糊，其中以重量计，碎阳极残极或煅烧焦炭占总聚集体的15-20％。
3.如权利要求1或2所述的冷捣固糊，以重量计包含10-15％的所述沥青。
4.如权利要求1或2所述的冷捣固糊，以重量计包含5-10％的所述轻油。
5.如权利要求4所述的冷捣固糊，其中所述轻油的沸点为210-355℃。
6.如权利要求1或2所述的冷捣固糊，其还进一步包括耐火硬质材料颗粒。
7.如权利要求1所述的冷捣固糊，其以重量计含有30-60％二硼化钛，10-15％沥青，5-10％轻油，余量为所述含碳聚集体。
8.一种制备冷捣固糊的方法，所述冷捣固糊用于连接为制备铝而进行氧化铝电解的电解槽的部件，所述方法包括：将沥青和含碳聚集体相混合形成混合物，所述聚集体含有无烟煤，其特征在于还加入轻油到所述混合物和加入碎阳极残极或煅烧焦炭到用于形成所述混合物的所述聚集体，其中碎阳极残极或煅烧焦炭的含量以总聚集体重量计最高达20％，并且所述混合在90-130℃进行20-50分钟。
9.如权利要求8所述的方法，其中将10-15wt％的沥青、5-10wt％的轻油和余量的含碳聚集体混合，所述聚集体含有无烟煤并且还含有碎阳极残极或煅烧焦炭，其中碎阳极残极或煅烧焦炭占总聚集体重量的15-20％。
10.一种形成电解槽的阴极内衬的工艺，该电解槽为制备铝而进行氧化铝电解，所述内衬由彼此之间具有接缝空间的相邻的含碳块构成，包括如下步骤：在所述接缝空间内导入冷捣固糊，该冷捣固糊包括沥青、轻油和含碳聚集体的混合物，所述含碳聚集体包括无烟煤和碎阳极残极的混合物，其中碎阳极残极占总聚集体重量的15-20％，压制接缝空间内的糊，随后烘烤块体和粘结的接缝，烘烤的温度和时间足以碳化该捣固糊并形成连续的结构。
11.如权利要求10所述的工艺，其中捣固糊作为一系列的层嵌入接缝空间，并在加入的层之间进行捣固。
12.如权利要求11所述的工艺，其中施加顶层，所述顶层包括沥青、轻油、二硼化钛和含碳聚集体的混合物，所述含碳聚集体包括无烟煤和碎阳极残极的混合物，其中碎阳极残极占总聚集体重量的15-20％。
13.如权利要求10所述的工艺，其中将所述冷捣固糊作为一系列的层插入所述接缝内，并且施加顶层，该顶层包括沥青、轻油、二硼化钛和含碳聚集体的混合物，该聚集体包含无烟煤并且还含有碎阳极残极或煅烧焦炭，所述碎阳极残极或煅烧焦炭的含量以总聚集体重量计最高达20％，并且其中所述捣固糊的层在加入的层之间进行捣固，只是当施加顶层之前，不对所述含有所述二硼化钛的顶层下面紧邻的层进行捣固，并将顶层和顶层下面紧邻的层捣固在一起。
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