CN1296323C - 以Cr2O3为基的耐火复合材料 - Google Patents

以Cr2O3为基的耐火复合材料 Download PDF

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CN1296323C
CN1296323C CNB2004100239837A CN200410023983A CN1296323C CN 1296323 C CN1296323 C CN 1296323C CN B2004100239837 A CNB2004100239837 A CN B2004100239837A CN 200410023983 A CN200410023983 A CN 200410023983A CN 1296323 C CN1296323 C CN 1296323C
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powder
particle diameter
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cr2o3
composite
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CN1690016A (zh
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朱德先
施飞
陈人品
张宏达
张亚栋
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Abstract

本发明公开了一种以Cr2O3为基的耐火复合材料。这种复合材料是在电熔Cr2O3合成料基体中，引入适量Y2O3和活性烧结Al2O3，活性工业Cr2O3，经成型和高温烧成制得。Y2O3和Al2O3在该材料中起着活化主成分Cr2O3晶格作用，从而降低材料的烧成温度，提高成品率，降低生产成本。与此同时，Y2O3与熔渣具有良好的相容性，可改善其抗渣蚀性和抗渗透性，也可避免现有材料中ZrO2与熔渣反应导致的体膨效应，引起材料的过早损毁，Y2O3也不含放射性物质对人体健康的损害作用。

Description

以Cr2O3为基的耐火复合材料
所属技术领域
本发明属于一种耐火复合材料，主要涉及一种含Y2O3的以Cr2O3为基的耐火复合材料，主要用于以水煤浆或石油焦为原料的加压气化炉工作内衬。
背景技术
以水煤浆为原料的加压气化炉已在国内外得到广泛应用。水煤浆气化法是一种既经济又高效的先进气化工艺，随着气化工艺的发展，目前又成功开发了一种以石油焦为原料的气化法。它与水煤浆气化工艺相比，具有效率更高，有用工艺气体产率更大，且成本更低的优点，但其炉衬被蚀更严重，寿命更低。长期来，无论是水煤浆加压气化炉还是石油焦加压气化炉工作衬，一直使用以Cr2O3为基的耐火材料，早期使用的MgO-Cr2O3-ZrO2-SiO2材料，由于气化工艺的进步，炉衬侵损特别严重，寿命较低。因此，开发了一种Cr2O3-Al2O3-ZrO2材料，其Cr2O3含量较高，降低了衬里的侵损速度，明显提高其寿命，但长期使用发现，该材料中的ZrO2由于受熔渣中的富SiO2和富CaO作用，产生ZrO2-SiO2和ZrO2-CaO化合产物，上述产物尽管熔点较高。但其自身密度较ZrO2低，导致砖在使用过程中产生较大的体膨效应，从而使砖在使用过程的不同段带产生不同程度的裂纹，最终因受热应力和机械应力的作用，裂纹逐渐扩大，以片状或块状形式离开砖体进入熔渣中，加速了砖的损毁，这种材料(砖)用于以石油焦为原料的加压气化炉，其侵损情况较水煤浆气化炉更为严重。另一方面，Cr2O3-Al2O3-ZrO2材料中的ZrO2熔点高达2600℃，是这些组元中熔点最高的氧化物，它除了与Al2O3具有共熔关系外，与主成分Cr2O3无共熔点。因此，制品的烧成温度很高。从而可能导致成品率的降低，成本明显的增大。从另一角度考虑，ZrO2中含有一定量的放射性物质如HfO2(氧化铪)，ThO2(氧化钍)等，对人体健康产生一定的影响。
发明内容
为克服现有Cr2O3-Al2O3-ZrO2材料在使用过程存在着较易受蚀、体膨效应、烧成温度高、放射性物质对人体的损害等不足，本发明的主要目的是提供了一种含Y2O3的以Cr2O3为基的耐火复合材料，使其在水煤浆或石油焦气化条件下，更能抗熔渣的化学侵蚀，不产生体膨效应且无放射性物质，烧成温度较低。
本发明的次要目的是利用上述耐火复合材料，使其用于水煤浆或石油焦加压气化炉工作衬，且具有制造简单、生产成本低、性能良好、使用寿命长的特点。
本发明解决其技术问题所采用的技术方案是：以高致密度的电熔Cr2O3合成料为骨料，与含Y2O3的Cr2O3-Al2O3微粉组成的基质组合，引入结合剂制成的耐火复合材料。
本发明所述的耐火复合材料的组成(重量比)为：
电熔Cr2O3合成料，其中，
粒径为1～4mm                    40～50％
粒径为0～1mm                    15～25％
粒径＜66μm                     16～25％
混合活性粉                      10～19％
外加结合剂                      2.5～3.5％
上述组成中以粒径为1～4mm、粒径为0～1mm的电熔Cr2O3合成料作骨料；基质部分由粒径＜66μm的电熔Cr2O3合成细粉以及混合活性粉构成。
混合活性粉由活性工业Cr2O3粉、活性烧结Al2O3粉和Y2O3粉组成，其组成(重量比)为：活性烧结Al2O3粉3～7％，粒度小于5μm；活性工业Cr2O3粉4～8％，粒经小于44μm；Y2O3粉0.2～5％，粒径小于44μm。
本发明所述的耐火复合材料的优选组成(重量比)为：电熔Cr2O3合成料中：
粒径为1～4mm                        44-48％
粒径为0～1mm                        20～22％
粒径＜66μm                         20～22％
混合活性粉中：
活性工业Cr2O3粉                     5～7％
活性烧结Al2O3粉                     4～5％
Y2O3粉                   0.8～1.5％
所述的结合剂是磷酸或磷酸二氢铝或有结合作用的其它磷酸盐或硫酸盐，或是它们中二者按任何比例的组合。
由于本发明引入Y2O3对水煤浆或石油焦气化后的熔渣介质具有良好的抵抗沥滤浸析和化学侵蚀作用，也就是说，本发明引入的Y2O3对该熔渣介质具有良好的化学稳定性，或者说，它与熔渣介质具有良好的相容性。与此同时，Y2O3在高温烧成过程中可使材料主成分Cr2O3晶格扭曲变形，活化其晶格，显著促进该复合材料的烧结，也无与放射性物质共生，基质中的活性烧结Al2O3微粉与材料中的主成分Cr2O3在烧成过程形成连续固溶体，起活化Cr2O3晶格作用，也可明显降低该复合材料的烧成温度，但其量要控制在合适范围，最好控制在4～6％(重量比)，这样，既可保持其该复合材料具有良好的抗熔渣介质的化学侵蚀性，又能明显地起促烧作用。由此看来，该耐火复合材料中引入的Y2O3和Al2O3微粉对其烧结性具有双重的促进作用，其烧结温度明显降低，较现有技术生产的Cr2O3-Al2O3-ZrO2产品降低80～100℃。
本发明提出的耐火复合材料采用磷酸或磷酸盐或硫酸盐作结合剂，其中，磷酸或磷酸盐两类结合剂对以Cr2O3为基的耐火材料来说，尤为合适，其原因在于磷酸或磷酸盐在制品烧成过程对氧的亲合力远较Cr2O3大，即使在弱氧化气氛中烧成，也不致将高密度Cr3+氧化成低密度Cr5+或Cr6+，可避免此氧化过程引起制品的体膨效应，从而导致其开裂。同时，此类结合剂在整个烧成过程，制品强度随着温度升高而增加，无强度下降区。由此看来，采用此类结合剂既有利富Cr2O3复合制品的烧结，也对其获得高强度起重要作用。
这种复合材料通过具有不同尺寸的颗粒骨料的合理分布，在其孔隙内由基质微粉的充填，可达到高的堆积密度，经成型机成型后的坯体密度可达4.2～4.3g/cm3。坯体经60℃～110℃烘干后，于1640～1670℃的弱还原气氛下烧成。
利用本发明耐火复合材料制成的用于水煤浆或石油焦加压的气化炉工作衬，可降低其气化炉衬侵损速率，提高使用寿命，也可降低制品的烧成温度，提高成品率，降低生产成本，同时，也免除放射性物质对人体的损害。
具体实施方案
实施例1：
本发明所述的耐火复合材料的组成(重量比)为：
电熔Cr2O3合成料：
粒径为1～4mm                        48％
粒径为0～1mm                        17％
粒径＜66μm                         24％
混合活性粉中：
活性烧结Al2O3粉4.5％，粒度小于5μm；
活性工业Cr2O3粉5％，粒经小于44μm；
Y2O3粉1.5％，粒径小于44μm。
将上述组成中的Cr2O3粉，活性烧结Al2O3粉和Y2O3粉按上述要求比例混合，用磷酸或磷酸二氢铝溶液作结合剂，其加入量(外加)为3％(重量比)。在成型机上加压成型，经80℃烘干后，于1650℃的弱还原气氛下烧成。
实施例2：
本发明所述的耐火复合材料的组成(重量比)为：
电熔Cr2O3合成料：
粒径为1～4mm                      49％
粒径为0～1mm                      16％
粒径＜66μm                       22％
混合活性粉中：
活性烧结Al2O3粉5％，粒径小于5μm；
活性工业Cr2O3粉7％，粒径小于44μm；
Y2O3粉1.0％，粒径小于44μm。
将上述组成中的Cr2O3粉，活性烧结Al2O3粉和Y2O3粉按上述要求比例混合，用磷酸或磷酸二氢铝溶液作结合剂，其加入量(外加)为3％(重量比)。在成型机上加压成型，经80℃烘干后，于1650℃的弱还原气氛下烧成。
本发明烧后制品的主成分Cr2O3含量可在85～95％(重量比)之间。其它物理性能经国家质量检测中心检测结果如下：
显气孔率：        14～16％
体积密度：        4.20～4.30g/cm3
常温耐压强度：    150～180Mpa

Claims (5)

1、一种以Cr2O3为基的耐火复合材料，其特征在于：制备所述复合材料的原料组成(重量比)为：
电熔Cr2O3合成料，其中：
粒径为1～4mm                     40～50％
粒径为0～1mm                     15～25％
粒＜66μm                        16～25％
混合活性粉                       10～19％
外加结合剂                       2.5～3.5％
其中，混合活性粉的组成(重量比)为：
粒径小于5μm的活性烧结Al2O3粉     3～7％；
粒径小于44μm的活性工业Cr2O3粉    4～8％；
粒径小于44μm的Y2O3粉             0.2～5％。
2、根据权利要求1所述的以Cr2O3为基的耐火复合材料，其特征在于：由粒径＜66μm电熔Cr2O3合成粉和混合活性粉组成基质部分。
3、根据权利要求1所述的以Cr2O3为基的耐火复合材料，其特征在于：所述的耐火复合材料的组成(重量比)为：
电熔Cr2O3合成料中：
粒径为1～4mm                     44～48％
粒径为0～1mm                     20～22％
粒径＜66μm                      20～22％
混合活性粉中：
活性工业Cr2O3粉                  5～7％
活性烧结Al2O3粉                  4～5％
Y2O3粉                           0.8～1.5％。
4、根据权利要求1所述的以Cr2O3为基的耐火复合材料，其特征在于：所述的结合剂是磷酸或磷酸二氢铝或有结合作用的其它磷酸盐或硫酸盐，或是它们中二者按任何比例的组合。
5、根据权利要求1所述的以Cr2O3为基的耐火复合材料，其特征在于：耐火复合材料在成型机上加压成型，经60°～110℃烘干后，于1640°～1670℃的弱还原气氛下烧成。
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