CN1325319A - 燃料气蒸汽转化炉壁上的碳沉积的抑制 - Google Patents

燃料气蒸汽转化炉壁上的碳沉积的抑制 Download PDF

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CN1325319A
CN1325319A CN99813115A CN99813115A CN1325319A CN 1325319 A CN1325319 A CN 1325319A CN 99813115 A CN99813115 A CN 99813115A CN 99813115 A CN99813115 A CN 99813115A CN 1325319 A CN1325319 A CN 1325319A
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coating
reformer
fuel gas
alkaline earth
alumina
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CN1120214C (zh
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R·R·勒西厄尔
H·J·塞策
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Abstract

用于燃料电池动力装置的燃料气转化炉设备,包括燃料气通道(2),其中含有氧化铝微粒填充物(12),蒸汽流－烃燃料流混合物在此被加热。通道(2)的壁(4)具有防止壁(4)腐蚀的氧化铝涂层。该涂层(4)和填充物(12)被碱土金属氧化物层覆盖,该覆盖层抑制了壁(4)表面的碳积累,并防止通道(2)过早地堵塞。通过向转化炉通道表面施加碱土金属化合物的水基浆液,并将浆液干燥固化,在转化炉通道组元上形成碳积累限制层。涂敷的填充物料(14)可以将气流中剩余的任何游离碳转化成二氧化碳,或一氧化碳,从而进一步限制了设备中的碳沉积。

Description

燃料气蒸汽转化炉壁上的碳沉积的抑制
                      技术领域
本发明涉及一种燃料气蒸汽转化炉(reformer)设备及其制备方法。更具体地说，本发明涉及一种燃料气蒸汽转化炉设备，其中转化炉气体通道用防碳氧化铝和碱土金属氧化物复合涂料涂浆涂布(washcoat)。
                      背景技术
燃料电池动力装置包括燃料气蒸汽转化炉，其可将燃料气，例如天然气或重质烃催化转化成氢和二氧化碳的主成分。所述的转化包括将燃料气和蒸汽的混合物通过催化床，所述的催化床根据被转化的燃料的不同加热至不同的转化温度。通常使用的催化剂是沉积在氧化铝颗粒上的镍催化剂。最常用于向燃料电池动力装置提供富氢气流的转化炉有三种类型。另外，通过使用部分氧化反应装置，烃燃料可以被转化成富氢气流。这就是管状热蒸汽转化炉、自热转化炉和催化壁转化炉。典型的管状热蒸汽转化炉由多条反应管组成，这些反应管位于保暖隔热的壳体内。在壳体内通过燃烧过量的燃料气加热反应管，并使炉气流过反应管。转化温度是在约1250°F至约1600°F范围内。单独的反应管一般包括被环状进气通道包围的中央排气通道。进气通道用催化的氧化铝颗粒填充，且燃料气-蒸汽歧管可将燃料气-蒸汽混合物传送至每个进气管的底部，于是燃料气-蒸汽混合物流过催化剂床。然后所产生的主要是氢和二氧化碳气的热混合气流过每个管的中央排气通道，以利于加热各环状催化剂床的内部；且由此从转化炉出来后可以进一步加工和利用。
典型的自热转化炉可以是单床或多床的管状组件。当由于待加工的燃料较难以重整，需要采用较高的操作温度时，重整常常采用自热转化炉。在自热转化炉中，通过向燃料和蒸汽混合物中加入空气，反应气体通过在反应床中燃烧过量的燃料而被加热，以便使剩余的燃料-蒸汽混合物的温度升高到燃料加工反应所需要的温度。一般来说，自热转化炉的炉壁温度是在约1400°F至约1800°F的范围内。这种管状转化炉公开于美国专利US4,098,587中。
现有技术转化炉的第三种类型已采用了催化壁通道，例如公开于美国专利US5733347中的催化壁通道。这些转化炉由具有内插波纹板的夹层平板构成，内插的波纹板构成转化炉气体通道和相邻的交流换热器-热交换器通道。各转化炉通道板部件直接与燃烧器通道板部件相邻，使得相邻的转化炉和燃烧器通道共享一个共有的壁。
除了上述的转化炉装置以外，部分氧化反应装置也可以用来产生富氢燃料流。该装置一般是一个送入烃燃料、蒸汽和氧化剂源的腔室，所述的氧化源通常是空气，这样使得该混合物自发部分氧化形成富氢混合物。例如，这样的装置公开于PCT申请WO9808771中。
前述现有技术的各转化炉结构，易于在转化炉设备的内部组件表面发生碳积累和沉积。碳积累最终会阻塞转化炉的气体通道，缩短转化炉的使用寿命，因而缩短装备有转化炉的燃料电池动力装置的使用寿命。显然，需要生产出一种转化炉设备组元(component)，并掌握其制备方法，由该组元得到的转化炉设备能防止碳积结在转化炉的表面。
                    本发明的公开
本发明涉及一种复合涂料及其制备方法，该复合涂料用于燃料电池蒸汽转化炉设备，涂有该复合涂料的转化炉组元上的碳沉积减少或消失。该复合涂料包括底层的氧化铝组分和最外层的抑制碳形成的金属氧化物组分。该转化炉设备具有涂有氧化铝组分的内钢壁，而且氧化铝组分拥有一层覆盖其上形成的非晶形或多晶的金属氧化物层。在转化炉设备中的某些通道也可以有金属氧化物颗粒床，它促使蒸汽-燃料混合物中的碳转化成一氧化碳，接着转化成二氧化碳。
用于抑制碳沉积的涂料的优选金属氧化物有碱土金属氧化物，例如CaO或MgO；碱土金属氧化物混合物，例如(CaO)X(MgO)Y，其中“X”和“Y”是0至约1之间的数；用碱金属氧化物取代的碱土金属氧化物，例如NaXCa(1-X)O，其中“X”是0至约0.2之间的数；稀土氧化物，例如La2O3或CeO2；用其它稀土元素取代的稀土氧化物，例如GdXCe(1-X)O2，其中“X”是0至约0.2之间的数；用碱土金属氧化物取代的稀土氧化物，例如(CaO)X·La2O3；和/或源自周期表Ⅷ族的过渡金属元素的金属氧化物，例如(NiO)X·La2O3，其中“X”是0至约1.0之间的数。
典型的组成如下：
                    表1
化合物              实例        测试值      数值范围碱土金属氧化物     (CaO)X·(MgO)Y   纯     X和Y是0.0至约
                                           1.0之间的数取代的碱土金属氧    NaXCa(1-X)O     0.08    X是0.0至约0.2之
化物                                         间的数稀土氧化物          CeO2或La2O3    纯用稀土元素取代的    GdXCe(1-X)O2           X是0.0至约0.2之稀土氧化物                                       间的数用碱土取代的稀土    (CaO)X·La2O3  0.2    X是0.0至约1.0之
氧化物                                       间的数周期表Ⅷ族过渡      (NiO)X·La2O3  0.15   X是0.0至约1.0之金属取代的稀土氧                                 间的数
化物
金属氧化物涂料将以非晶形或多晶涂料形成，该非晶形或多晶涂料得自金属的硝酸盐、乙酸盐或柠檬酸盐水溶液，且金属氢氧化物悬浮其中以形成浆液。该氢氧化物可以以金属氢氧化物的形式添加，或通过向溶液中添加少于化学计算量的碱，例如NaOH或NH4OH来形成，从而可以形成浆液或溶液中具有一定百分比可溶性盐的溶胶-凝胶混合物。可以向浆液中添加少量的表面活性剂，以有助于氢氧化物的分散，并且通过浆液可以提高所述转化炉表面的湿润。
为了形成氧化钙涂料，Ca(OH)2固体与浓Ca(NO3)2·5H2O溶液混合形成浆液。为了形成镧-镍氧化物涂料，制造具有所需阳离子定额的乙酸镍和硝酸镧溶液。通过添加氢氧化铵，以氢氧化物形式共沉淀一部分镍和镧来制备浆液。通常，所述的沉淀物最初以溶胶-凝胶形式产生，经静置熟化为浆液。在溶胶-凝胶状态或浆液状态下，可以把悬浮体涂布到转化炉表面。然后热处理涂料将所述涂料转化成多晶或非晶形的形式。当采用适当比例的硝酸盐和氢氧化物时，得到的非晶形涂层，在干燥时不会使底层的氧化铝层成碎片或剥落。通过利用上述的抑制碳涂料，显著减少或消除了碳从被加工燃料中沉积到转化炉通道壁上。
某些通道也可以拥有金属氧化物微粒组元，这些组元可将燃料-蒸汽流中的碳转化为碳的氧化物。该金属氧化物微粒料可以是颗粒的形式，一般是球形、环形或圆柱形，它们涂有氧化钙或任意上述的化合物。该碳的转化反应如下：
                
因此，本发明的目的是提供一种改进的用于转化炉设备的抑制碳沉积的涂料，和含有该改进涂料的转化炉设备。
本发明的另一个目的是提供一种在燃料电池燃料气转化炉设备中，在燃料气-蒸汽流导管壁上形成防剥落和成碎片的，防止碳沉积的涂层方法。
                      附图简述
借助于下述对本发明优选实施方案的详细描述，并参照附图，本发明的这些和其它目的及优点对本领域技术人员来说是显而易见的，其中：
图1是根据本发明形成的燃料气转化炉通道的局部截面图；和
图2是图1的通道侧壁的局部放大截面图，显示出涂料沉积在通道壁的内部。
                实现本发明的具体方式
现在参照附图，图1显示出部分燃料加工设备通道的局部截面图，统一用数字2表示，其在根据本发明已采用的一般燃料电池动力装置中形成燃料-蒸汽混合物转化炉设备组元的一部分。转化炉通道2的壁4优选由渗铝钢或者含铝合金钢构成。如图2中所示，转化炉通道壁4的内表面6有氧化铝涂层8，该氧化铝涂层8防止钢的腐蚀。通过常规的铝化(aluminizing)方法，如ASTMB875中所述的方法，并且增加热处理步骤形成铝化涂层8，该热处理是在约1825°F下保温约2-12小时。铝化与随后的热处理步骤结合，在钢上形成连续粘附的多孔氧化铝涂层。这样的表面是理想的表面，在其上堆积着抑制碳沉积的碱土金属氧化物料层。
多孔氧化铝涂层8的所选择部分被氧化钙、氧化镁、镧-镍氧化物复合物、诸如钠取代的氧化钙之类的碱金属取代的碱土金属氧化物等的非晶形层10覆盖和渗透。在转化炉的操作过程中，层10可阻止或防止碳从燃料-蒸汽流中直接沉积到通道2的加热壁上。
一定长度的通道2需要升高气体的温度至转化炉的进口温度，该通道用微粒填充床12填充，所述的微粒填充床12由金属氧化物颗粒14构成，该金属氧化物颗粒14有：涂覆在氧化铝基质上的氧化钙；涂覆在氧化铝基质上的氧化钙/氧化铁复合物；或如上所述的其它化合物。
下面描述在流动通道2中形成所需的碳抑制层的方法。硝酸钙易溶于水，而氢氧化钙不溶于水。硝酸钙单独形成蜡状的吸湿固体。氢氧化钙单独形成白色结晶粉末。在一个最佳方式中，本发明可以采用一定浓度的氢氧化钙比硝酸钙操作，在该浓度下，当加热时，氢氧化钙在硝酸钙水溶液中的浆液形成胶体并固化。
向硝酸钙溶液中添加氢氧化钙粉末形成浆液。将该浆液涂到要被涂布的管表面上。随着温度升高，氢氧化钙溶解度升高，同时溶液损失水分并因此被浓缩。硝酸钙和氢氧化钙一起形成固体，形成所需的非晶形或多晶涂层。
前述工序的详细实例如下。约500g的Ca(NO3)2·4H2O(硝酸钙四水合物)与约330g的蒸馏水在一个1L的广口塑料瓶中混合。将约0.3g的浓HNO3添加到上述混合物中。该溶液被冷却，并混合直至四水合物溶解于水和酸中。将约66g的Ca(OH)2加入水-酸-四水合物溶液中，并摇动所得到的混合物，由此该混合物形成胶体，接着，在室温下静置约1至2小时后变成流体。将约1.3至约1.4g的表面活性剂“TRITON-100”添加进流体混合物中，并在使用前充分摇动。用Liquinox®洗涤剂清洗待涂覆的转化炉管，然后用水润湿。清洗后的管子用烧杯刷擦洗。该清洗并擦洗后的管子用(约30°至约40℃的)水冲洗。在240°F温度下干燥该均匀润湿的管子，并冷却至室温。然后使用湿润的漆刷，将浆液涂漆到待涂覆的表面，以使浆液的起泡量尽可能地少。施加一薄层涂料，并用干的漆刷去除过量的液体。接着将已涂布的部分在烘箱中加热至110℃的温度，以确保涂层达到前述温度。将干燥的已涂布的部分贮藏在相对湿度小于60％的气氛中。
在浆液中如果硝酸盐对氢氧化物的比值太高，则得到蜡状涂层。硝酸盐对氢氧化物的比值是20∶1时，产生蜡状涂层。如果前述比值太低，则得到粉状涂层。硝酸盐对氢氧化物的比值是16∶1时，产生粉状涂层。硝酸盐对氢氧化物的比值是18∶1时，产生光亮的非晶形涂层，该涂层在触觉上是固体，当加热至分解温度时，即大于约1380°F时，它不会剥落。
在不脱离本发明构思的情况下，可以对本发明所公开的实施方案作许多改进和变化，除了权利要求所要求保护的范围以外，这些实施方案并不意味着对本发明的限制。

Claims (8)

1．一种烃燃料气蒸汽转化炉设备，包括一个或多个用于接收燃料气和蒸汽混合物的燃料气通道，所述的燃料气通道拥有防止所述燃料气通道内部腐蚀的氧化铝涂层，并且至少部分所述的氧化铝涂层被碱土金属氧化物涂料覆盖，所述的碱土金属氧化物涂料抑制所述燃料气通道的碳沉积。
2．根据权利要求1的转化炉设备，其中所述的气体通道包括外部的钢或钢合金部件。
3．根据权利要求1的转化炉设备，其中所述氧化铝涂层是多孔的。
4．根据权利要求3的转化炉设备，其中所述的金属氧化物涂料渗入所述的氧化铝涂层的孔中。
5．根据权利要求1的转化炉设备，其中所述的碱土金属金属氧化物是CaO、MgO、(CaO)x·(MgO)y，其中X和Y是0至约1.0。
6．一种形成防止碳沉积组元的方法，该组元被设计成用于烃燃料转化炉，所述的方法包括以下步骤：
a)提供一种具有氧化铝表面的组元；
b)提供一种碱土金属化合物和一种碱土金属氧化物的溶液；
c)用所述溶液涂布所述组元；和
d)加热所述的被涂布的组元，以在所述氧化铝表面，将所述的溶液转化成非晶形或多晶涂层。
7．根据权利要求6的方法，其中所述的氧化铝表面是多孔的，并且所述的溶液渗入所述的多孔氧化铝表面，以与后者牢固结合。
8．根据权利要求7的方法，其中所述的溶液是含碱土金属离子的可溶性盐溶液。
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AU2843000A (en) 2000-06-05
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AU2148600A (en) 2000-05-29
US6258330B1 (en) 2001-07-10
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CN1330570A (zh) 2002-01-09
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