CN1643173A - 防金属尘化的合金 - Google Patents

防金属尘化的合金 Download PDF

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CN1643173A
CN1643173A CNA038061333A CN03806133A CN1643173A CN 1643173 A CN1643173 A CN 1643173A CN A038061333 A CNA038061333 A CN A038061333A CN 03806133 A CN03806133 A CN 03806133A CN 1643173 A CN1643173 A CN 1643173A
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manganese
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CN1300358C (zh
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特里克·A·拉马纳雷阿南
金昌旻
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ExxonMobil Technology and Engineering Co
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Abstract

本发明包括一种防金属尘化的组合物物质，及一种防止暴露于碳过饱和环境下金属表面上金属尘化的方法。

Description

防金属尘化的合金
技术领域
本发明涉及一种控制暴露于碳过饱和环境下反应器材料的尘化腐蚀的方法，还涉及一种物质的组合物。
背景技术
在许多的烃转化工艺中，例如，CH4转化为合成气，会遇到具有高的碳活性和相对低氧活性的环境。在这样的工艺中使用的高温反应器材料和热交换器材料，由于被称为金属尘化的非常强烈形式的腐蚀，在使用中性能劣化。
在400～900℃的温度，及在具有相对低氧分压(约10-10～约10-20大气压)的碳过饱和(碳活性＞1)环境中，Fe、Ni和Co基合金经历非常有害形式的高温腐蚀的金属尘化。这种形式的腐蚀特征在于本体金属崩解为金属粉末。尽管可以得到许多工业化的合金，可设计为在低氧分压环境下形成保护性的Cr2O3或Al2O3膜，在碳活性远超过其均一程度的情况下，这些氧化物的成核和生长速度通常不总足够的快以阻挡碳的侵入环境中。
文献中现有的控制金属尘化腐蚀的方法包括使用表面涂层和气态的抑制剂，特别是H2S。由于涂层组分内部扩散进入合金基质中而使涂层降解。因此，尽管涂层是一种短期保护可行的方法，但它们通常对于长期的二十年或更长使用寿命而言是不可取的。H2S抑制存在两个缺点。一是H2S往往易于使大多数烃转化工艺中使用的催化剂中毒。而且，H2S必须从出口物流中移出，这大幅增加了工艺的成本。
在本领域中需要的是一种合金组合物，该组合物可在低氧分压(约10-10～约10-20大气压)和碳过饱和(碳活性＞1)环境中耐金属尘化腐蚀。
发明内容
本发明包括一种防金属尘化的组合物物质，包括(a)当合金表面暴露于碳过饱和环境下时可在其表面上形成保护性氧化物涂层的合金，(b)所述的氧化物涂层在所述的合金表面上含有至少两个层，当所述的合金暴露于具有低氧分压的金属尘化环境下时可形成保护性氧化物涂层。外层，也指第一层(该层与碳过饱和接触或离合金最远)由热力学稳定的氧化物构成，其可迅速覆盖合金表面并阻挡碳进入合金。第一层是热力学稳定的氧化锰，其形成的速度比过饱和环境中碳能够透入合金表面的速度更快。因此，氧化锰也称为快速形成层。在氧化锰层之下，第二层(本发明指所述的第二氧化层)或者在形成所述氧化锰层同时或之后形成。第二层的保护性氧化物涂层是氧化物膜，其在氧化锰层下面形成并粘结到氧化锰层上，其组成取决于形成其的合金组成。因此，本发明包括一种防金属尘化的组合物，包括(a)合金和(b)在所述合金上的保护性氧化物涂层，其中所述的保护性氧化物涂层包括至少两个氧化物层，其中第一氧化物层是氧化锰层，其中所述的合金包括成合金金属和基底金属，所述的成合金金属含有铬和锰的混合物，所述的基底金属含有铁、镍和钴，其中所述合金中存在的所述锰的浓度至少为约10wt％的Mn，在所述合金中存在的所述铬的浓度至少为约25wt％的Cr，及其中铬和锰的结合量≥40wt％，及其中所述的第一氧化物层是距离所述合金表面最远的层。
在碳过饱和环境下使用合金的过程中可原位形成保护性氧化物涂层，或在合金使用之前将合金置于碳过饱和环境下进行制备。本发明的优点在于在碳过饱和环境下使用合金的过程中，如果保护性氧化物涂层发生破裂，会在裂缝处形成保护性涂层以修复氧化物层，因此可保护合金在使用时被金属尘化。
本发明也包括防止暴露于碳过饱和环境中金属表面的金属尘化的方法，包括构造防金属尘化合金组合物的所述的金属表面，或用防金属尘化的合金组合物涂布所述的金属表面，所述的合金组合物包括含有成合金金属和基底金属的金属合金，所述的成合金金属包括铬和锰的混合物，所述的基底金属含有铁、镍和钴，其中所述合金中存在的所述锰的浓度至少为约10wt％的Mn，在所述合金中存在的所述铬的浓度至少为约25wt％的Cr，及其中铬和锰的结合量≥40wt％，及其中所述的第一氧化物层是距离所述合金表面最远的层。
金属表面可由合金构成，或涂布有合金，在碳过饱和环境中单元操作期间可原位形成上述的保护性氧化物膜。
因此本发明还包括一种保护性氧化物涂层，其包括至少两个氧化物层，其中所述的第一层是氧化锰层，所述的第一层是在所述合金上距离所述合金最远的层。
附图简述
图1描述了对于合金组成为20.1Fe-39.4Ni-10.0Mn-30.5Cr，在50CO-50H2、650℃下金属尘化160小时后的两个层化的保护性氧化物膜的扫描电镜显微照片。
图2是描述了组成为20Fe-45Ni-35Cr的防渗碳合金(35/45)，在50CO-50H2中650℃下金属尘化160小时后的蚀损斑形貌的扫描电子显微照片。
发明的详细描述
本发明描述的其上形成保护膜的合金包括含有Cr和Mn组合物的合金。本发明的Cr和Mn是指成合金元素。除了成合金元素，合金还含有基底元素。基底元素形成大部分的合金，因此其存在的总量大于约44％。因此除了Cr和Mn以外，其他的金属，本发明是指基底金属可存在于合金中，包括Fe、Ni、Co及其混合物。另外，成合金元素例如Si和Al也可存在于合金中。优选使用Fe-Ni-Mn-Cr合金。
本发明形成合金的基底元素选自Fe、Ni和Co及三者的混合物。基底金属可以任何的组合形式存在，或仅仅是使用单一的基底金属形成合金。
表1、在各种不同的Fe-Ni-Mn-Cr合金的Linde B加工表面上，在50CO-50H2气体混合物中550℃和650℃下进行160小时的腐蚀后的碳沉积引起的质量增加(一种金属尘化腐蚀的测量方法)。
    合金组成(wt％)   (Mn+Cr)的量(wt％)   550℃的质量增加(mg/cm2)   650℃的质量增加(mg/cm2)
30.4Fe∶30.4Ni∶14.7Mn∶24.5Cr   39.2   118.0～122.0   90.0～95.0
20Fe∶40.5Ni∶14.9Mn∶24.6Cr   39.5   65.0～67.0   28.0～32.0
20.1Fe∶39.4Ni∶10.0Mn∶30.5Cr   40.5   21.0～24.0   无碳
30.0Fe∶29.5Ni∶10.2Mn∶30.3Cr   40.5   17.0～19.0   无碳
19.7Fe∶32.9Ni∶14.4Mn∶33.0Cr   47.4   0.7～0.9   无碳
14.8Fe∶39.3Ni∶14.9Mn∶31.0Cr   45.9   0.5～0.9   无碳
45.0Fe∶29.5Mn∶25.5Cr   55.0   0.2～0.5   无碳
24.9Fe∶19.6Ni∶28.9Mn∶26.6Cr   55.5   0.7～1.2   无碳
59.8Ni∶14.0Mn∶26.2Cr   40.2   1.2～1.7   无碳
7Fe∶77Ni∶16Cr(In600)*   120.0～130.0   60.0～65.0
20Fe∶45Ni∶35Cr(35/45)**   230.0～250.0   140.0～160.0
*Inconel 600合金(N06600)
**35/45防渗碳合金(KHR-45A)
本发明的合金可用于构造暴露于金属尘化环境中的设备表面，或易于金属尘化的现有表面可用所述合金通过本领域的普通技术人员的惯用技术手段进行涂布。例如，可使用热喷涂、等离子体沉积、化学气相沉积和喷涂的技术。因此，精炼厂的设备可由上述的合金构造，或用上述的合金进行涂布，在设备使用期间形成保护性氧化物膜或在使用之前形成保护性氧化物膜。
当作为现有表面的涂层时，这样的涂层厚度为约10～约200μm，优选为约50～约100μm。
由本发明得到的作为涂层的表面包括在使用期间任意时间任何与碳过饱和环境接触的设备或反应器系统，包括反应器、热交换器、管道等。
通过将合金置于例如50CO∶50H2混合物的金属尘化环境中，从而在合金的表面上形成本发明所述的合金表面的保护性涂层或膜。因此，在合金暴露于金属尘化环境的反应条件下在合金使用中或之前形成保护涂层。优选的温度为约350℃～约1050℃，优选为约550℃～约1050℃。典型的接触时间为约1小时～约200小时，优选为约1小时～约100小时。
以下的实施例是举例说明的，而不是对本发明的限制。
实施例
通过电弧熔化制备含有不同Fe、Ni、Mn和Cr浓度的合金。电弧熔化的合金被轧成厚度约1/16英寸的薄片。片材在惰性氩气氛下1100℃下退火处理过夜，冷却炉到室温。从片材中切割0.5英寸×0.25英寸的长方形样品。样品表面被抛光到磨粒为600的光洁度或Linde B光洁度(0.05μm的氧化铝粉末)，并用丙酮清洗。在金属尘化实验中使用的所有熔体的样品用附加于扫描电子显微镜的能量色散X-光谱进行分析。得到的化学分析结果列于表1中。将样品暴露于50CO-50H2的气态环境中160小时。这是一种特别强烈的气态混合物，其中大多数的高温合金都会经历金属尘化。几个备选的商业合金也置于同样的条件下处理。
接触后详细的合金电子显微照片表明在Fe-Ni-Mn-Cr体系中特定的合金组成可防金属尘化腐蚀。两层的保护性氧化物膜由MnO外层和MnCr2O4内层组成。图1中显示的是组成为20.1Fe∶39.4Ni∶10.0Mn∶30.5Cr的合金，在650℃下置于碳过饱和金属尘化环境中(50CO-50H2)160小时后的两层保护膜的扫描电子显微图象。在样品的表面发现没有通常伴随金属尘化腐蚀的碳沉积。图2显示的防渗碳商业合金组合物受到了广泛的金属尘化侵袭。图2的电子显微图象显示出在50CO-50H2、650℃下金属尘化160小时后，在腐蚀区域金属尘化特征的蚀损斑形貌。在图2中也同时观察到伴随这样的侵袭不可避免的碳沉积。
表1显示出在550℃和650℃下Fe-Ni-Mn-Cr合金的防金属尘化性。由于金属尘化通常伴随有碳沉积，因此碳沉积引起的质量增加可作为金属尘化腐蚀的度量。分别测量了在550℃和650℃下50CO-50H2气体混合物中腐蚀160小时后，不同Fe-Ni-Mn-Cr合金Linde B光洁度表面上的质量增加。

Claims (4)

1.一种防金属尘化腐蚀的组合物，包括(a)合金和(b)在所述合金上的保护性氧化物涂层，其中所述的保护性氧化物涂层包括至少两个氧化物层，其中第一氧化物层是氧化锰层，其中所述的合金包括成合金金属和基底金属，所述的成合金金属含有铬和锰的混合物，所述的基底金属含有铁、镍和钴，其中所述合金中存在的所述锰的浓度至少为约10wt％的Mn，在所述合金中存在的所述铬的浓度至少为约25wt％的Cr，及其中铬和锰的结合量≥40wt％，及其中所述的第一氧化物层是距离所述合金表面最远的层。
2.一种防止暴露于碳过饱和环境中金属表面的金属尘化的方法，包括构造防金属尘化合金组合物的所述的金属表面，或用防金属尘化的合金组合物涂布所述的金属表面，所述的合金组合物包括含有成合金金属和基底金属的金属合金，所述的成合金金属包括铬和锰的混合物，所述的基底金属含有铁、镍和钴，其中所述合金中存在的所述锰的浓度至少为约10wt％的Mn，在所述合金中存在的所述铬的浓度至少为约25wt％的Cr，及其中铬和锰的结合量≥40wt％，及其中所述的第一氧化物层是距离所述合金表面最远的层。
3.如权利要求2的方法，其中将合金置于碳过饱和金属尘化环境下，在其表面上形成一种保护性氧化物涂层，其中所述的保护性氧化物涂层包括至少两个氧化物层，其中所述的第一氧化物层是氧化锰层，其中所述的第一氧化物层是距离所述合金表面最远的层。
4.如权利要求3的方法，其中所述的保护性氧化物涂层在碳过饱和金属尘化环境中，在使用所述合金过程中原位形成。
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