CN1243662C - 生产合成硅酸盐的流化床反应 - Google Patents

生产合成硅酸盐的流化床反应 Download PDF

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CN1243662C
CN1243662C CNB028053583A CN02805358A CN1243662C CN 1243662 C CN1243662 C CN 1243662C CN B028053583 A CNB028053583 A CN B028053583A CN 02805358 A CN02805358 A CN 02805358A CN 1243662 C CN1243662 C CN 1243662C
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J·A·赫克曼
S·A·茨卡勒利
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Abstract

公开了一种方法，其中在球磨中与磨料和冷粘着粘结剂一起处理粗二氧化硅、氧化钙和氧化镁源。然后这种材料与水一起聚集形成产品，所述产品在升温条件下例如在流化床反应器中反应从而产生合成硅酸盐。

Description

生产合成硅酸盐的流化床反应
                         背景
在基于陶瓷和玻璃的工业中，使用合成硅酸盐作为前体材料是已知的。由现有方法所获得的益处已经通过生产如在美国专利申请序列号08/708,246、09/001,335以及相关申请中所描述的合成硅酸盐小球得到证实。这类方法应用多种设备和材料，包括盘式造粒机、粘结剂材料、粗二氧化硅和催化剂。虽然这些方法代表了本领域的进步，但它们仍存在问题和局限性。一些问题包括在盘式造粒机和其它设备的操作中过多地应用人力，以及在过程中使用以旋转窑为基础的粘结剂作为必要材料。现有方法包括原料如水、二氧化硅、氧化钙和氧化镁源的未反应物质的形成，然后它们反应形成所希望的合成硅酸盐。这类未反应物质被称为“生”球，在反应前可以是未被干燥或已干燥的。当在反应前在温度攀升区域这些生球经受旋转窑内的应力时，需要粘结剂来阻止生球分解。另外，当较粗的二氧化硅用作原料时，需要应用催化剂来提供完全和均一的反应。因此，在生产这种合成硅酸盐材料的单元操作中及整个过程中仍需要改进。
本发明的一个目的是减少生产合成硅酸盐材料所应用的设备操作过程中的人力。
本发明的另一个目的是在针磨中应用粗二氧化硅。
本发明的又一个目的是在不应用催化剂时应用硅砂达到更高的反应程度。
本发明的再一个目的是在不应用粘结剂时在高温下阻止聚集物的分解。
这些和其它目的通过本发明来实现。
                             概述
本发明是一种生产合成硅酸盐的方法。所述方法在球磨中混合粗二氧化硅、氧化钙、氧化镁、磨料和冷粘着(cold-strength)粘结剂，随后聚集并反应产生合成硅酸盐。通过这种方法所达到的具体优点在于降低了人力及粘结剂和催化剂材料的成本。
                        附图的描述
图1描述了本发明方法的一个常用实施例。
图2描述了本发明方法的一个具体实施例。
                      本发明的实施方案
本发明的一种实施方案为一种方法，所述方法包括如下步骤：第一步，在球磨中将粗二氧化硅、氧化钙和氧化镁源、磨料和冷粘着粘结剂混合在一起；第二步，在聚集混合器中使第一步的材料与水混合；以及第三步，使混合器中所产生的材料反应。
粗二氧化硅包括沙子，优选至少90％质量颗粒的粒度范围为约100微米至约1000微米，更优选为约150微米至约600微米，甚至更优选为约250微米至约600微米。这种沙子可以为沉积二氧化硅或天然的沙子或选矿沙，并且可以包括杂质，这些杂质对工匠来说可能是希望或不希望处理或要脱除的。这些沙子的颗粒可以为各种粒度分布。例如，所述分布可以为至少80％质量的颗粒等于或大于250微米，剩余颗粒小于250微米。这种分布可以根据工匠所打算的用途而不同。所述粒度分布可以为单峰、双峰或任何其它多种多峰形式。另外，所述分布可以具有顶部或底部截止值(cut-off set)。
可以应用各种氧化钙源；优选为水合氧化钙源。这种来源包括白云石石灰、锻烧石灰石或任何各种商购来源，但不局限于此。类似地，可以应用各种氧化镁源，优选为水合氧化镁源。这种来源包括白云石石灰、氧化镁或任何各种商购来源，但不局限于此。所述氧化钙和氧化镁源可以包括例如石灰石和白云石。这些材料的粒度范围优选为约25微米至约100微米。这些来源的水合度可以为100％质量，但是也可以更低，只要存在足够的水合达到本发明的目的即可。
用于本发明的磨料可以有助于保持设备清洁，并利于材料流过研磨设备。这些磨料包括在本发明所应用设备中本领域中常用的研磨固体材料。
用于本发明的冷粘着粘结剂可以为任何可在环境温度下应用的合适粘结剂。这些粘结剂包括铝酸钙水泥、苛性氧化镁粘结剂、有机粘结剂如木质素以及等效粘结剂，但不局限于此。
所述球磨的操作方式应使流出材料优选约80％质量比约150微米更细，更优选比约75微米更细。操作所述球磨从而使加入磨的材料达到高度均匀。另外，控制操作条件从而达到材料表面的有效强化，并且控制材料粒度的减小，以用于下游反应器中的反应。所述表面强化是为了使反应位没有杂质或至少减少反应位的杂质，而这些杂质将会妨碍下游反应器中材料的反应。这种强化优选进行到一定程度，从而使进行下游反应所需要的催化剂量减少。这种减少优选为至少50％质量，更优选为至少90％质量，甚至更优选基本不再需要催化剂。另外，按一种方式操作球磨从而产生具有一定粒度和特征的产品，从而增加聚集混合器的进料。这样增加进料应产生均匀的聚集物，从而反应进行至很高的完成程度，从而至少75％质量，更优选至少85％质量的反应物进行化学转化。
所述混合器可以为任何适合于处理这里所描述的进料材料的混合器类型。这种混合器应该聚集进料材料形成出口材料，其中所述进料材料包括球磨产品和水，而出料材料优选至少50％质量为1毫米至35毫米，更优选为至少75％质量为1毫米至35毫米。一种优选的混合器为针磨混合器或湍流器混合器。通过水和球磨产品的加入速率以及控制轴的旋转来控制混合器的操作，从而达到上述聚集程度。所述混合器可以与球磨组合操作，从而产生对所选择的反应器设备来说适合的产品。例如，可以控制聚集程度从而允许使用旋转窑或流态化固体窑或流化床反应器作为反应器设备。这种球磨和混合器如针型混合器的组合应用能更大程度地控制流化床的反应器进料，而在所述流化床中不用粘结剂即形成硅酸盐。上述通过这种组合而获得的聚集物将符合在流化床反应器中成功形成合成硅酸盐的关键粒度需求。
可用于本发明的反应器可以为任何高温固态反应器如旋转窑和流化床反应器，但不局限于此。这类反应器的例子可以在US 5,876,679和US 3,904,375以及其中所引用的参考文献中找到，所有这些文献均在这里作为参考引入。这种流化床反应器的反应时间明显要少于旋转窑中常用的反应时间。一种优选的流化床反应器为具有陶瓷内衬的。在本发明中，这种反应器的优点是其操作成本明显低于旋转窑，并且操作温度也明显较低。由于上述通过组合球磨和混合器所达到的表面强化及其它益处，使这种温度的降低成为可能。球磨、混合器和流化床反应器的组合可以达到比现有过程更高的反应程度，需要更少的时间，并引起更低的材料应力。
本发明的一种实施方案为图1所示方框图代表的过程。向水合器1中加入白云石石灰，从而产生水合的白云石石灰。然后将这种石灰产品加入到球磨2中，并向所述球磨中与冷粘着粘结剂和磨料一起加入沙子。所述球磨2在环境温度下操作足够长的时间，从而在混合过程中实现高度均匀，同时使沙子粒度减小并更新沙子表面。操作球磨2从而产生一种产品，其中流出所述磨的颗粒75％质量以上的粒度小于75微米。然后将这种球磨产品与水一起加入到混合器3中，操作所述混合器3，从而产生主要粒度为1毫米至35毫米的聚集物，其水含量为约15％质量。然后将这种聚集材料在足够高的温度下加入到干燥器4中，并保持足够长的时间以基本除去所有自由水。然后将干燥的聚集物通过筛子5进行筛分，从而除去小于1,000微米的细颗粒。然后将剩余的材料加入到在约1,250-1,350℃的温度下操作的反应器6中。氧化钙、氧化镁和二氧化硅材料发生反应，从而产生所希望的合成硅酸盐材料。从反应器6中作为产品收集溢流出的材料。在反应器6之后进行任选的筛分或粉碎操作。
下列实施例用于描述本发明的一种实施方案，并不构成对本发明的限制。参考图2来描述所例举的过程。
通过加入43.25质量份的白云石石灰、50.95份的沙子、0.94份50％的苛性碱溶液、2.5份氧化铝和17.64份水而在水合器1中形成一批料，所述水加入量代表水合所结合的水以及作为蒸汽从水合器中损失的水。充分混合各组分，然后加入到球磨2中。所述球磨2应用一种高铬介质内衬，并按连续模式操作。沙子、粘结剂和磨料以连续过程加入。从这种连续过程中，产生一种粒状材料，其中90％质量颗粒的当量球直径为75微米或更小。然后将这种材料加入到针型混合器3中，并向其中加入足够的水，从而使所产生的产品含有17％质量水分。所述针型混合器3按连续过程操作，从而使来自球磨3的材料聚集。然后将针型混合器3的聚集产品加入到在温度为150℃下操作的旋转干燥器4中。将所述聚集物干燥至水分含量低于1.5％质量。然后将干燥器产品加入到筛子5中，操作该筛子从而从来自旋转干燥器4的产品中除去细颗粒。由筛子5所产生的产品的粒度分布中减去这些细颗粒，从而造成9％质量大于35毫米，76.5％质量为600微米至35毫米，以及14.5％质量小于600微米。将这种筛分产品加入到流化床窑6中。所述流化床在约1300℃下操作，并且聚集物充分反应，从而产生仅有约10-15％质量未反应二氧化硅的产品。

Claims (12)

1.一种方法，所述方法包括如下步骤：第一步，在球磨中混合粗二氧化硅、氧化钙和氧化镁源、磨料和冷粘着粘结剂以产生第一混合物；第二步，在聚集混合器中使第一混合物与水混合以产生第二混合物，该第二混合物至少50％质量的颗粒为1-35毫米；以及第三步，将第二混合物加入到反应器中，并加热以实现产生合成硅酸盐的反应。
2.  权利要求1的方法，其中所述粗二氧化硅包括至少90％质量粒度范围为100-1000微米的沙子颗粒。
3.权利要求2的方法，其中所述沙子颗粒的粒度范围为150-600微米。
4.权利要求1-3任一项的方法，其中所述沙子颗粒具有粒度分布，其中至少80％质量的颗粒的当量球直径等于或大于250微米，其余的小于250微米。
5.权利要求1-3任一项的方法，其中所述氧化钙源包括水合氧化钙。
6.权利要求1-3任一项的方法，其中所述氧化镁源包括水合氧化镁。
7.权利要求1-3任一项的方法，其中所述氧化钙源或氧化镁源或两者均由粒度范围为25-100微米的颗粒组成。
8.权利要求1-3任一项的方法，其中所述氧化钙源或氧化镁源或两者均具有100％质量的水合度。
9.权利要求1-3任一项的方法，其中所述冷粘着粘结剂为铝酸钙水泥或碱性氧化镁粘结剂。
10.权利要求1-3任一项的方法，其中至少75％质量的反应物进行化学转化。
11.权利要求1-3任一项的方法，其中所述聚集混合器为针磨混合器。
12.权利要求1-3任一项的方法，其中所述反应器为具有陶瓷内衬的流化床反应器。
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