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CN1117039C - 由飘尘制造矿物填料和火山灰产品的方法 - Google Patents

由飘尘制造矿物填料和火山灰产品的方法 Download PDF

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CN1117039C
CN1117039C CN00805198A CN00805198A CN1117039C CN 1117039 C CN1117039 C CN 1117039C CN 00805198 A CN00805198 A CN 00805198A CN 00805198 A CN00805198 A CN 00805198A CN 1117039 C CN1117039 C CN 1117039C
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K·S·阿比尔顿
R·W·斯泰隆
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Abstract

提供了一种由飘尘制造矿物填料和火山灰产品的方法，其中在风力分级器中对飘尘进行干法处理以获得平均粒径为约0.1至5微米的细粒部分和平均粒径为约6至20微米的粗粒部分。然后优选地使细粒部分通过磁选器除去氧化亚铁，任选地用表面改性剂处理形成矿物填料。优选地使粗粒部分通过100目筛形成火山灰产品。

Description

由飘尘制造矿物填料和火山灰产品的方法
本发明涉及一种由飘尘制造工业矿物填料和火山灰产品的万法，且更具体地，涉及一种将原飘尘干法处理成能用作矿物填料和火山灰产品的细粒部分和粗粒部分的方法。
飘尘是煤燃烧产生的一种副产物，包含有细碎的无机产物。全国每年产生大量的飘尘，主要来源于发电厂里燃烧的煤。因为飘尘的体积、颗粒性质和不同的化学组分限制了合格的处理场的数目，所以处理飘尘已成为日益困难的问题。
因此，人们做了许多尝试以寻求飘尘别的、经济的用途。例如，已将飘尘用作混凝土应用中的火山灰材料。然而，飘尘作为火山灰产品的直接使用已被限制，因为飘尘中高的碳含量阻止了混凝土的夹带，从而引起不均匀的硬化。为了使更多的飘尘适于用作火山灰产品，飘尘应该有低的碳含量。
飘尘的另一个有潜力的用途是作为工业矿物填料。矿物填料广泛应用于塑料制品中以改善性能和降低成本。矿物填料一般用于如塑料、混合、注射成型、纸制品等的应用中，包括碳酸钙、高岭土、氢氧化铝、云母、滑石和石英粉。飘尘的化学组成和性能接近于那些市售的填料，会成为理想的替代品。然而，飘尘的粒径比典型市售填料的粒径大得多。过去已使用了如温磨法、泡沫浮选、研磨和湿磁铁消除(wetmagnetic iron removal)的温处理方法减小和控制飘尘的粒径。然而，这些方法是复杂的、昂贵的，且需要多步工艺，因为必须将湿飘尘烘干。另外，如泡沫浮选的方法使用如松节油之类的必须安全处理的试剂。
因此，本领域中仍然需要一种由飘尘制造如矿物填料和火山灰之类的有用产品的方法，并且这种方法是经济的且易于实施。
本发明提供一种将飘尘加工成矿物填料和火山灰产品的方法满足了上述要求，此方法使用低碳含量的飘尘，并利用干法加工的方法，即在加工过程中不需要或不涉及润湿、干燥或再润湿飘尘的方法。所得的填料具有约为0.1至5微米的平均粒径，可用于许多填料应用中，包括塑料、油漆、橡胶、油灰杀虫剂、织物涂料、腻子、密封胶、纸、嵌缝胶、橡胶、沥青和瓦。增强的火山灰具有小于约10至20微米的平均粒径，可用于水泥的制造和替换，也可用于土壤稳定。
根据本发明的一个方面，提供了一种由飘尘制造矿物填料的方法，其包括如下步骤：供给一些碳含量不超过约0.1至40％重量的原飘尘，使飘尘通过风力分级器得到约0.1％至约65％重量的、平均粒径为约0.1至约5微米的细粒部分。优选地此方法包括使得到的细粒部分通过磁选器的步骤，从而除去细粒部分中约0.1至99％重量的氧化亚铁。
优选地，本方法进一步包括用如表面活性剂、偶联剂、润滑剂或除酸剂等的表面改性剂处理或覆盖填料的步骤。优选地，表面改性剂选自于硅烷、硬脂酸盐、铝酸盐、钛酸盐和锆酸盐。优选的硅烷是乙烯胺基甲氧基硅氧烷。优选的硬脂酸盐是硬脂酸钙。优选的钛酸盐是钛酸胺。优选地，以约0.1至5％重量的干覆盖重量使用表面改性剂。
所得的填料可用于许多填料或填充剂应用中，也可用于组合物中。这些填料的具体用途包括聚丙烯的热塑性混合，低密度和高密度聚乙烯的模塑和挤出及不饱和聚酯和聚苯乙烯的热固性整体模塑、混合和增强注射模塑。填料也可用于刚性或柔性聚氯乙烯的热成型混合。
也提供了一种由飘尘制造改善了的火山灰产品的方法，其包括如下步骤：供给一些碳含量不超过0.1至40％重量的原飘尘，使飘尘通过风力分级器得到约35至95％重量的粗粒部分。优选地，此方法进一步包括使粗粒部分通过100目筛的步骤。所得的火山灰产品在28天内具有至少3000psi的压缩强度，且当用于水泥制造和替换应用时能提供均匀的水合。
虽然这里以单独的方法描述了制备矿物填料和火山灰产品的方法，但应该理解矿物填料和火山灰产品可由飘尘以同种方法制造。这种方法包括如下步骤：供给一些碳含量不超过0.1至40％重量的原飘尘；使飘尘通过风力分级器得到约35至95％重量的粗粒部分和约5至65％重量的细粒部分。然后优选地使得到的细粒部分通过磁选器获得矿物填料，优选地使粗粒部分通过100目筛获得火山灰产品。
因此，本发明的特征是提供一种由飘尘制造矿物填料和火山灰产品的方法。本发明的其它特征和优点可由如下描述、附图和所附的权利要求书明显看出。
为使本发明更易于理解，现给出附图以供参考，其中图1是流程图，说明了本发明的制造填料和火山灰产品的方法。
本发明的方法具有优于现有技术的几个优点，这在于它利用了不需要润温和干燥飘尘的干法加工的方法，这样需要更少的步骤，且更经济。本方法适用于C级和F级飘尘，其典型粒径分布为约0至150微米，且平均粒径为约10至15微米。另外，本发明的方法使用最小碳含量的飘尘，这改善了所得填料和火山灰产品的性能。
现在参考图1，说明本发明的方法。如图所示，将碳含量不超过约0.1至40％重量的、更优选地不超过约0.1至4％重量的原飘尘10输入进料斗12，然后通过风力分级器14，它将飘尘分离为平均粒径为约0.1至约5微米的细粒部分和平均粒径为约6至20微米的粗粒部分。本发明中优选使用的风力分级器是由ABB Raymond购得的RaymondHigh Performance Jet-StreamTM分级器。也可使用Raymond机械吹离器。
优选地将由风力分级器得到的飘尘的粗粒部分转移入料斗16，然后优选地使其通过100目筛20，筛目能除去飘尘中含有的、损害飘尘质量和粘固性能的硅石或碳的筛上料颗粒。所得火山灰的典型的化学组成是约0.1至60％重量的氧化铝，约0.5至50％重量的氧化钙，约0.5至50％重量的氧化硅，约0.5至10％重量的氧化镁，约0.1至5％重量的二氧化钛，约0.1至10％重量的铁和约0.1至10％重量的三氧化硫。微量的其它化合物也可能存在。
优选地使由风力分级器得到的细粒部分通过磁选器18，以除去细粒部分中约0.1至99％重量的氧化亚铁或磁铁。适用的磁选器包括由0SNA Equipment Inc.购买的Permro1lMagnetic Separator和由Ereiz Magnets Inc.购买的Carpco and Ereiz Magnetic Units。优选的分选器包括由Bunting Magnetics Co.购得的NHI(钕-铁-硼〕磁铁和由Walker Magnetics购得的磁选器。
除去氧化亚铁后，优选地用表面改性剂如除酸剂、表面活性剂、偶联剂或润滑剂处理填料，以便与聚合物更好地填充和偶联而引起很小或没有粘度的变化。这些表面改性剂旨在增强填料与聚合物或其它使用填料的介质之间的粘合。合适的表面改性剂或覆盖剂包括硅烷、硬脂酸盐、铝酸盐、钛酸盐和锆酸盐。优选的表面改性剂是硅烷和硬脂酸盐，可以水溶液、固体或预水解的形式使用它们。
优选的硅烷是乙烯胺基甲氧基硅氧烷，它是购自Dow Coming的硅烷在甲醇溶剂中的40％固溶体。优选地利用常规的喷涂设备将硅烷以水溶液的形式覆盖在填料颗粒上。优选的硬脂酸盐是购自WitcoCorportation的固体形式的规整的硬脂酸钙。可以通过几种方法使用硬脂酸盐。例如，将填料和硬脂酸钙溶解在水中然后烘干。或者，当粉碎填料时将硬脂酸钙用作表面处理。优选的方法是当使填料流过捏和碾磨混合器或桨式碾磨混合器时，将硬脂酸钙喷涂至填料上。
在与聚合物或其它介质混合之前或混合过程中可将表面改性剂使用于填料。然后袋装或以其它形式包装处理过的填料运送给用户。在油漆和纸应用中也可与水混合(浆化的)罐装运送。
填料的典型的化学组成包括约5至60％重量的氧化铝，约0.5至60％重量的氧化钙，约5至30％重量的氧化硅，约0.5至15％重量的氧化镁和约0.1至10％重量的二氧化钛。更优选地，该化学组成包括25至45％重量的氧化铝，约30至40％重量的氧化钙，约15至25％重量的氧化硅，约0.5至10％重量的氧化镁和约0.1至5％重量的二氧化钛。
填料由球形颗粒组成，这使应用时有更大的物料通过量和更好的混合。填料也易于覆盖和着色，且分散均匀。根据ASTM D281填料有约22/100的吸油量，根据ASTM 4611有0.24的比热。填料在水中的pH值为约6至8(ASTM 4972)，在高达约1000至2500°F的温度具有热稳定性，其比重为约2.5至3.1，莫氏硬度为约3至5.5。
为使本发明更易于理解，提供如下的实施例以供参考，这些实施例旨在说明本发明，并不限制其范围。实施例1
提供四种飘尘样品A，B，C和D。表1列举了所用样品A，B和C的主要成分(重量比)。每种样品的碳含量在0.37至0.40％的范围内，因此正如所示的具有很低的L01。然后根据本发明的方法通过不同程度(每分钟的转数)的风力分级器将样品A，B和C分离。样品D保持未处理的原飘尘形式。然后以1∶4的比率将样品A，B和C分别加入卜特兰水泥中制成实验批量的混合物。将四种混合物在4-4 3/4之间维持混凝土滑移。
下面表1说明了所用样品A，B和C的主要成分(重量比)。
                           表1
组分 样品A(重量％) 样品B(重量％) 样品C(重量％)
湿度     0.04     0.04     0.05
 LO1     0.17     0.19     0.24
 SiO2     42.13     45.86     42.02
 Al2O3     17.37     17.07     17.52
 Fe2O3     5.79     5.74     5.59
 SO3     0.99     0.80     0.95
CaO 23.23 21.01 23.28
 MgO     4.55     4.09     4.70
 Na2O     1.45     1.29     1.41
 K2O     0.36     0.34     0.37
P2O5 0.94 0.90 0.97
 TiO2     1.45     1.42     1.44
 SrO     0.32     0.30     0.32
 BaO     0.63     0.61     0.64
表2说明了3、7、14和28天后样品的压缩强度(psi)。
                                  表2
天数 样品A除去1-2微米(～12微米) 样品B除去2-3微米(～15微米) 样品C除去3-5微米(～20微米) 样品D原料～12微米
3天#1 1968 1356 1343 1560
#2 1895 1456 1433 1618
 平均值   1930   1410   1390   1590
7天#1 2868 2274 2104 2859
#2 2513 2212 2170 2897
 平均值   2650   2240   2140   2870
 14天#1   3651   2561   2502   3848
#2 3506 2678 2694 3508
 平均值   3580   2620   3850   3680
28天#1 4294 3274 3451 4278
 #2   4126   3251   3329   4398
 平均值   4210   3260   3390   4340
所有飘尘都通过了所有混凝土混合物要求的在28天内必须保持的大于3000psj的要求。值得注意的是1微米粒径的筛上料(样品A)比原飘尘具有更高的3天后强度。
虽然已用一定具有代表性的实施方案和细节来说明本发明，但很明显对本领域技术人员来说，可在不偏离本发明范围内改变这里公开的方法和设备，这在所附权利要求书中作了限定。

Claims (13)

1、一种由飘尘制造矿物填料的方法，包括如下步骤：
供给一些的碳含量不超过0.1至40％的原飘尘；使所述的飘尘通过风力分级器得到0.1％至60％重量的、平均粒径为约0.1至约5微米的细粒部分；和用表面改性剂处理所述细粒部分，该表面改性剂选自于硅烷、硬脂酸盐、铝酸盐、钛酸盐和锆酸盐。
2、根据权利要求1所述的方法，进一步包括使所述的细粒部分通过磁选器以从所述细粒部分中除去氧化亚铁的步骤。
3、根据权利要求1所述的方法，其中所述的表面改性剂包含乙烯胺基甲氧基硅氧烷。
4、根据权利要求1所述的方法，其中所述的表面改性剂包含硬脂酸钙。
5、根据权利要求1所述的方法，其中所述的表面改性剂包含钛酸胺。
6、根据权利要求1所述的方法，其中所述的矿物填料含有5至60％重量的氧化铝，0.5至50％重量的氧化钙，5至30％重量的氧化硅，0.5至15％重量的氧化镁和0.1至10％重量的二氧化钛。
7、根据权利要求3所述的方法，其中以0.1至5％重量的干覆盖重量使用所述的表面改性剂。
8、根据权利要求1所述的方法，其中所述的原飘尘具有不超过0.1至4％重量的碳含量。
9、一种由飘尘制造火山灰产品的方法，包括如下步骤：
供给一些的碳含量不超过0.1至40％重量的原飘尘；使所述的飘尘通过风力分级器得到35％至95％重量的粗粒部分。
10、根据权利要求9所述的方法，进一步包括使所述的粗粒部分通过100目筛。
11、根据权利要求9所述的方法，其中所述的火山灰产品在28天内具有至少3000psi的压缩强度。
12、根据权利要求9所述的方法，其中所述的原飘尘具有不超过0.1至4％重量的碳含量。
13、一种由飘尘制造矿物填料和火山灰产品的方法，包括如下步骤：供给一些  碳含量不超过0.1至40％重量的飘尘；使所述飘尘通过风力分级器得到35至95％重量的粗粒部分和5至65％重量的细粒部分；使所述的细粒部分通过磁选器得到所述的矿物填料并用表面改性剂处理所述填料，该表面改性剂选自硅烷、硬脂酸盐、铝酸盐、钛酸盐和锆酸盐；使粗粒部分通过100目筛得到所述的火山灰产品。
CN00805198A 1999-02-17 2000-02-16 由飘尘制造矿物填料和火山灰产品的方法 Expired - Fee Related CN1117039C (zh)

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US09/251,515 1999-02-17
US09/357,046 1999-07-19
US09/357,046 US6242098B1 (en) 1999-02-17 1999-07-19 Method of making mineral filler and pozzolan product from fly ash

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