CN102239004A - 同时进行的暖气体脱硫作用和co轮换反应来改进合成气净化 - Google Patents

同时进行的暖气体脱硫作用和co轮换反应来改进合成气净化 Download PDF

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CN102239004A
CN102239004A CN200980148576XA CN200980148576A CN102239004A CN 102239004 A CN102239004 A CN 102239004A CN 200980148576X A CN200980148576X A CN 200980148576XA CN 200980148576 A CN200980148576 A CN 200980148576A CN 102239004 A CN102239004 A CN 102239004A
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sulphur
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M·瑟班
L·M·金
A·巴塔查里亚
K·M·旺当布舍
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Universal Oil Products Co
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Abstract

本发明包括了用于同时进行气体料流的脱硫和水煤气轮换反应的方法和材料，其包括将气体料流与镍铝酸盐催化剂进行接触。镍铝酸盐催化剂优选选自由如下组成的组，Ni2xAl2O2x+3，Ni(2-y)Ni0 yAl2O(5-y)，Ni(4-y)Ni0 yAl2O(7-y)，Ni(6-y)Ni0 yAl2O(9-y)和它们的中间体，其中x≥0.5并且0.01≤y≤2。优选地，x为1到3。更优选地，含镍化合物还包括Ni2xAl2O2x+3-zSz，其中0≤z≤2x。

Description

同时进行的暖气体脱硫作用和CO轮换反应来改进合成气净化
发明背景
本发明涉及用于从气体料流中进行硫化合物的脱除以及用于水煤气轮换反应的所使用材料和方法。更具体地说，本发明涉及利用含镍铝酸盐催化剂在450℃时提供脱硫作用和水煤气轮换反应的同时进行。
该气体料流可源于含碳原料的任何部分氧化或气化工艺过程。该气体料流可以是源自IGCC(Integrated Gasification Combined Cycle，集成气化联合循环)煤气化工厂的燃料气体，其可以是来自流体催化裂化单元(fluidcatalytic cracking unit，FCC)的烟道气(flue gas)，其可以是来自天然气的蒸汽重整(steam reforming)、特定气化反应或者来自煤的气化的合成气(synthesis gas，syngas)。合成气一般指主要包含一氧化碳和氢气的气体混合物，但是其也可能含有二氧化碳和少量的甲烷和氮气。
合成气作为各种大型化学工艺过程中的原料被使用，或者潜在地是有用的，例如：甲醇的生产，通过Fischer-Tropsch工艺过程的汽油沸程烃的生产，和氨的生产。
用于合成气生产的方法为大家所熟知，一般包括蒸汽重整，自热重整(auto-thermal reforming)，轻质烃类的非催化的部分氧化，和任意烃类的非催化的部分氧化。在这些方法中，一般用蒸汽重整来生产合成气，以转化为氨或者甲醇。在此类方法中，烃分子被分解来生产富氢气体料流。
无论碳源和气化过程，生成的燃料气必须在燃气轮机中燃烧之前或者用于化学合成，例如甲醇，氨，脲生产，或者Fischer-Tropsch合成法之前，进行实质上的净化。热燃料气的净化避免了由于与使用化学或者物理溶剂的湿法洗涤技术有关的冷却和后续的再加热的显热(sensible heat)损失。理想地，燃料气体的净化在燃料气体分配系统可以设计的最高温度时进行。这将大大改进整体的加工效率，然而，在所述热燃料气体净化系统可以市购之前，仍有需要克服的重要障碍。仅有热微粒去除系统，即，烛形过滤器(candle filter)或烧结金属过滤器，已经在商业上在长期应用场合成功应用，在200℃到250℃下在位于荷兰的Nuon的Shell煤气化工厂，以及在370℃到430℃下在Wabash River工厂的E-气煤/焦炭气化系统中。全部大型暖脱硫作用示范单元均已失败，主要是由于不合适的硫清除剂材料。
暖气体脱硫演示单元(
Figure BDA0000066176340000021
Pine Air-Blown IGCC和Tampa ElectricPolk Power station)都使用了Zn-基S-清除剂材料。Pine Air-Blown和Hot Gas Cleanup IGCC，其使用了KRW鼓风增压的流化床煤气化系统，其使用含有0.5-0.9％硫的Southern Utah烟煤(设计煤炭)和含有2-3％硫的东部烟煤(计划试验)。目的是演示引入热气体净化(HGCU)的鼓风增压的流化床IGCC技术；来评价低Btu气体燃气轮机；以及在足够确定商业前景的尺度上来评估长期可靠性、可获得性，可维护性，和环境特性。在42个月的演示操作中，没有达到稳态运行，并且Zn-基S-清除剂材料失效，因为其无法在夹带床反应器中物理保持。在538℃反应中，通过挥发，Zn消失了。第二个大型热气体脱硫作用演示单元位于Tampa Electric Polk发电厂，其预计通过GE Environmental Services Inc.开发的热气体净化系统来清洁10％的燃料气体。热气体脱硫单元是Zn氧化物基吸附剂的断续移动的床，其在482℃下操作。演示再次失败了，因为很高的磨损损失(其使得使用了特殊吸附剂的操作成本效率很差)，并且还因为由于Zn硫酸盐的形成和Zn的挥发而导致的严重的反应性损失。(参见：ThePineIGCC Project，U.S.DOE andPine Power Project Reports，1996年12月；2001年1月(DE-FC-21-92MC29309)。The Tampa Electric IGCCProject，U.S.DOE和Tampa Electric Reports，1996年8月；2000年7月；2002年8月(DE-FC-21-91MC27363))。
公开了含Zn的硫吸收剂的使用的一些专利，包括Phillips Petroleum拥有的数个专利：US5,045,522；US5,130,288；US5,281,445；US5,306,685；和US6,479,429。还有RTI(Research Triangle Institute)的数个专利：US5,254,516；US2004/0170549A1；和US7,067,093。没有从气体料流脱除硫化合物和水煤气轮换反应同时进行的在先公开。
对于目前热气净化系统的发展状况，在同样的高温条件下，无法除去除了硫化合物和固体颗粒之外的全部其它污染物。甚至，由于迫切的CO2法规，所有集成气化联合循环(IGCC)气化器将必须安装至少一个CO轮换反应器，由此需要将燃料气体冷却到适合进行水煤气轮换催化反应的温度。考虑到这些CO2法规，在气化工业中，倾向于通过利用直接水骤冷气化器(direct water quench)。骤冷模式设计显著地降低了合成气冷却的资金成本，同时热集成保持了良好的总体热效率。骤冷模式对于水煤气轮换反应是有利的，因为原料合成气通过一部分骤冷水的蒸发产生的蒸汽而变得饱和。优选通过直接水骤冷的夹带流动淤浆进料气化，并通常使用GEEnergy的方案，并近来，Shell，Lurgi和Siemens也提供了水骤冷冷却法。除了有效地冷却原料合成气并回收部分显热之外，在骤冷步骤中进行了有意义的污染物去除。在水骤冷步骤中，将固体颗粒，碱金属，非挥发性金属，氯化物，大部分羰基金属和一部分氨均被全部除去。在水骤冷步骤之后留在原料合成气中的污染物包括50-100ppmv氨，1到4ppmv羰基Fe和Ni，50-100ppmv HCN，Hg，As，和含硫的气体，即，H2S和COS。在合成气在燃气轮机中燃烧或者用于化学合成之前，所有这些污染物均要除去。
本发明公开了一类在250℃-550℃能够同时完全除去源自气化过程的燃料气体中的硫(除去H2S和COS)以及将CO轮换成为CO2的材料。该CO2料流可通过加入附加的脱硫(sweet)CO轮换单元来进一步轮换，所述轮换单元位于集成脱硫作用和CO轮换单元的下游。因此，该氢的制造得到了最大化并且清洁，浓缩CO2料流能够使用物理溶剂工艺，例如UOP的Selexol处理工艺，或者备选地使用高温CO2吸收剂来进行捕捉。该集成脱硫作用和CO轮换概念代表了下一代的合成气处理方法。目前，可再生的溶剂型脱酸性气方法在IGCC和化学合成应用场合，例如，UOP的Selexol处理工艺(US2,649,166和US3,363,133)或Linde Engineering的Rectisol处理工艺(US2,863.5277)中得到使用。不幸地，这些方法需要将燃料气体冷却到低温，然后随后再加热它到足够下游使用的温度。与溶剂洗涤型净化过程有关的这个问题可以通过使用了本发明公开的概念来得到解决。本发明涉及利用含镍的铝酸盐催化剂在450℃时提供脱硫作用和水煤气轮换反应的同时进行。该CO2料流可通过加入附加的脱硫CO轮换单元来进行进一步浓缩(完全的CO轮换)，所述轮换单元位于集成单元的下游。因此，该氢的制造得到了最大化并得到了清洁，浓缩的CO2料流能够使用物理溶剂工艺，或者备选地使用高温CO2吸收剂来进行捕捉。与该概念相关地，存在几个主要的优点：通过连续从气体料流中除去H2S，COS水解平衡被完全地转移向右，该CO2料流通过水煤气轮换反应得到浓缩，并且设备成本可能得到大大的减低。
发明概述
本发明包括了一种气体料流的同时脱硫和气体轮换的方法，其包括将气体料流与镍铝酸盐催化剂进行接触。该镍铝酸盐催化剂优选选自如下组成的组，Ni2xAl2O2x+3、Ni(2-y)Ni0 yAl2O(5-y)、Ni(4-y)Ni0 yAl2O(7-y)、Ni(6-y)Ni0 yAl2O(9-y)和它们的中间体，其中x≤0.5并且0.01≤y≤2。优选地，x为1到3。更优选地，含镍化合物还包括Ni2xAl2O2x+3-zSz，其中0≤z≤2x。该含镍化合物与在气体料流中的超过10％的含硫化合物起反应。优选地，该含镍化合物与在气体料流中的超过50％的含硫化合物起反应。在气体料流内，至少10％的一氧化碳转化成二氧化碳。该含镍化合物在250℃到550℃时接触气体料流。优选地，温度为400℃到500℃，压力为10到80巴。GHSV(在STP)优选是高于500m3/m3/hr。蒸汽和CO的摩尔比率为从0.5∶1到4∶1，优选摩尔比率为从1.5∶1到3.5∶1。
该气体料流通过烃类、包括燃料气体和合成气的气化来进行生产。
本发明还包括该催化剂在燃料气体的处理中的应用，所述燃料气体包含一氧化碳，氢，二氧化碳，含硫化合物和各种杂质。
发明详述
我们在此公开了一类能够将燃料气体除硫(H2S和COS的完全脱除)并且同时将CO轮换到CO2的材料。该类材料由镍铝酸盐组成，其从作为起始原料的水滑石制备而来。该镍铝酸盐催化剂优选选自如下组成的组，Ni2xAl2O2x+3，Ni(2-y)Ni0 yAl2O(5-y)，Ni(4-y)Ni0 yAl2O(7-y)，Ni(6-y)Ni0 yAl2O(9-y)和它们的中间体，其中x≥0.5并且0.01≤y≤2。优选地，x为1到3。更优选地，含镍化合物还包括Ni2xAl2O2x+3zSz，其中0≤z≤2x。Ni铝酸盐材料(Ni 4.09:Al2O 7.09:2.4H2O)已显示了具有优异的硫吸收能力，即，在预穿透之前10重量％的S，并且同时实现了40-50％的CO到CO2的转化。该材料是可再生的。
另外，在此我们公开了一类在含硫气体料流中进行COS到H2S的完全水解和氢化所使用的材料和方法，从所述气体料流中进行所述H2S的完全脱除的所述材料和方法，以及将CO轮换成为CO2的所述材料和方法。该镍铝酸盐催化剂优选选自如下组成的组，Ni2xAl2O2x+3、Ni(2-y)Ni0 yAl2O(5-y)、Ni(4-y)Ni0 yAl2O(7-y)、Ni(6-y)Ni0 yAl2O(9-y)和它们的中间体，其中x≥0.5并且0.01≤y≤2。优选地，x为1到3。更优选地，含镍化合物还包括Ni2xAl2O2x+3zSz，其中0≤z≤2x。
实施例1
最终结构式Ni4.09Al2O7.09:2.4H2O的Ni铝酸盐材料，通过层状双氢氧化物(Layered Double Hydroxide，LDH)金属氧化物固溶体(Metal OxideSolid Solution，MOSS)路线来进行制备。在这一过程中，通过将328.0g的50％NaOH水溶液与1170.0g的去离子水进行混合，然后加入136.1g的NaCO3:H2O来制备透明溶液。将345.3g Ni(NO3)2:6H2O和217.7gAl(NO3)3:9H2O溶解到840.0g去离子水中来制备第二溶液。然后在搅拌下，将金属硝酸盐的水溶液在超过2小时的时间内逐滴加入到第一溶液中。将反应混合物加热至80℃，并保持在该温度下16到18小时，同时予以搅拌。然后通过真空过滤将固体分离出来，并用去离子水(26升)有力冲洗，在环境空气中干燥。在这时，X射线衍射证实了Ni-Al-O层状双氢氧化物材料的合成，其然后在450℃被锻烧(在流动空气中)6小时，接着在550℃煅烧4小时，来生成金属氧化物固溶体。得到的材料含有58.5重量％Ni，表面积为189m2/g，孔隙容积＝0.337cm3/g，
实施例2
使用实施例1中制备的Ni4.09Al2O7.09:2.4H2O材料，在大气压力，450℃，与模拟吹氧气化器的气体，其含有1.1％H2S+0.0763％COS+45％H2+46％CO+7.2％CO2+0.7％CH4，来完成硫化/CO轮换实验。蒸汽已经被一起进料，其蒸汽：CO的摩尔比率为3.5∶1。湿基GHSV是2100h-1。用2％O2的N2，在500℃，GHSV＝2100h-1的条件，进行氧化再生。在该最初第一阶段，在S穿透之前，硫吸收能力是10重量％S，CO至CO2和CH4的转化率为95％。Ni铝酸盐产生了10％CH4，其表示有60％平衡量甲烷的生成。在H2气氛中，样品已被加热到反应温度，使得存在于Ni铝酸盐材料中的一些Ni已经被还原为金属状态，由此产生了甲烷化反应的活性位点。在500℃氧化循环以后，当没有促进甲烷化反应的Ni0存在于镍铝酸盐材料中时，没有观察到CH4的形成。CO到CO2的转化率为50％。然而，在S穿透之前的硫吸收能力仍然是10重量％S。不希望有甲烷的形成，因为其对不被捕捉的碳量做出了贡献；然而，正如下文所显示的，在所有后续循环中，甲烷的生成量为0。
在第一循环中，随着Ni金属逐渐被硫化，甲烷形成量连续减少。在不希望受到任何理论束缚的情况下，我们相信存在于原料中的硫化合物抑制了甲烷化反应，因为它们吸收于H2将吸附的位点，即，Ni0，由此降低了加氢活性。硫毒化了Ni催化剂氢化碳原子的能力，其比毒化形成碳-碳键的能力更加严重。然而，因为原料中含有大量蒸汽，C-C键的形成也得到了抑制，使得含C化合物发生的唯一反应是水煤气轮换反应。该材料在500℃，2％O2的N2中，通过氧化再生进行再生。在氧化步骤仅仅检测到二氧化硫。
在第二循环中，在500℃氧化再生以后，材料完全恢复了硫吸收能力，但仅仅恢复42％的CO转化活性。在第二循环中，没有形成CH4。由于不存在Ni0，并且也可能由于在再生步骤之后剩余的0.5到1.5重量％残留硫导致的硫毒化效应，甲烷的形成被完全抑制。残留硫的存在通过KOH洗涤溶液的S-X射线荧光分析和XAFS分析来得到证实。正如之前指出的，硫强烈吸附在H2也要吸附的位点上，由此降低了催化剂的加氢活性。CH4的形成的完全抑制，但是在接着H2预处理步骤的氧化再生步骤之后的第二硫化循环中，相似的CO轮换为CO2的转化，指出了残留硫(来自之前硫化循环)可毒化用于甲烷化的位点的事实。人们可预想，H2处理将还原一些镍至Ni0，由此生成了用于甲烷化的活性位点。然而，该甲烷产率是零，同时CO轮换为CO2的转化率与没有所述预还原步骤的转化率相似。这表明，用于甲烷化的位点(Ni0)被硫所毒化，同时Ni氧化物(在氧化循环之后生成)位点对CO轮换和硫吸收仍然可得到。在第二循环中，在预穿透之前，硫吸收是10重量％硫。Ni材料的CO到CO2的轮换活性保持不变，CO到CO2的转化率为40-50％，甚至在材料被硫化之后。硫化镍已知是一个酸性(sour)CO轮换催化剂。
对于降低的CO轮换活性的另一理由可以是，在MOSS材料中在硫化-氧化处理之后出现的物理变化。然而，在两个氧化循环之后，材料损失了50％的表面积(表1)，暗示一些MOSS结构也许已经瓦解。通过XRD看到的狭NiO峰，说明可能一些金属已经迁移，生成了更大的烧结金属氧化物晶粒。在450℃煅烧的新鲜MOSS材料与在550℃煅烧的新料具有一样的表面积，说明仅热处理不会破坏MOSS结构，但是硫化-氧化处理促进了一些表面积的损失和表面的粗糙化。
表1：暴露于不同温度和气氛下的
Ni铝酸盐的表面积，孔隙容积和孔隙直径
Figure BDA0000066176340000081
表2总结了Ni铝酸盐在脱硫和CO轮换方面的特性。根据如下公式来计算CO2和CH4的产率。
Y CO 2 = % CO 2 out - % CO 2 in % CO in
和
Y CH 4 = % CH 4 out - % CH 4 in % CO in + % CO 2 in
其中，XCO＝一氧化碳转化率(％)；YCO2＝二氧化碳的产率(％)；YCH4＝甲烷产率(％)；％(CO2，CO，CH4)in指的是在原料气中的CO2，CO或CH4体积％，％(CO2，CO，CH4)out指的是在排出气体中的CO2，CO或CH4体积％。
表2：Ni铝酸盐(Ni/Al＝2)在暖气体脱硫和CO轮换方面的性能
Figure BDA0000066176340000091
实施例3(对比实施例)
通过标准浸渍技术来制备负载Ni的氧化铝样品。制备含有溶解到30去离子水中的14.83g的Ni(NO3)3:6H2O的溶液。边温和搅拌，边往溶液中，加入10.7g的R-50/R51γ-氧化铝挤出物。继续在室温下搅拌20小时，在80℃强制通风空气烘箱中，间歇搅拌下，将溶液进行蒸发，得到干燥固体。所形成的干燥固体然后在流动空气下，以3℃/min的加热速率达到550℃，并保持6小时，来进行锻烧。得到的产品通过ICP进行测定，含有38.3％Al，21.1％Ni，其900℃时的LOI＝12.84％，导致最终产品结构式为Ni0.51Al2O3.51:1.0H2O。N2的BET表面积被测定为163m2/g，孔隙容积＝0.361cc/g。该成品通过X射线衍射分析，其含有NiO和γ-氧化铝。在γ-氧化铝上的NiO在实施例2描述的条件下进行测试。CO到CO2的转化率与Ni铝酸盐材料相似，然而，在S穿透之前的硫吸收能力仅仅是3.9重量％S。
表3：Ni负载在氧化铝上的催化剂在暖气体脱硫和CO轮换方面的性能

Claims (10)

1.一种用于从气体料流中除去硫的催化剂，所述催化剂包含一种含镍化合物。
2.权利要求1的催化剂，其中所述含镍化合物选自由如下组成的组：Ni2xAl2O2x+3、Ni(2-y)Ni0 yAl2O(5-y)、Ni(4-y)Ni0 yAl2O(7-y)、Ni(6-y)Ni0 yAl2O(9-y)和它们的中间体，其中x≥0.5并且0.01≤y≤2。
3.权利要求2的催化剂，其中1≤x≤3。
4.权利要求3的催化剂，其中含镍化合物进一步包含Ni2xAl2O2x+3-zSz，其中0≤z≤2x。
5.一种从气体料流中除去硫的方法，其包括将所述料流与权利要求1-4的催化剂进行接触。
6.权利要求5的方法，其中含镍化合物将所述硫从所述气体料流中除去的同时，所述含镍化合物同时也催化了水煤气轮换反应。
7.权利要求6的方法，其中所述气体料流包含一氧化碳、二氧化碳、氢气、和硫化合物。
8.权利要求6的方法，其中所述含镍化合物与所述气体料流中超过10％的硫化合物反应。
9.权利要求6的方法，其中所述含镍化合物在250℃到550℃的温度下接触所述气体料流。
10.权利要求6的方法，其中蒸汽和CO的摩尔比为0.5∶1到4∶1。
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