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CN101802146A - 由气化得到的含硫合成气制造富甲烷气体混合物的方法 - Google Patents

由气化得到的含硫合成气制造富甲烷气体混合物的方法 Download PDF

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CN101802146A
CN101802146A CN200880106240.2A CN200880106240A CN101802146A CN 101802146 A CN101802146 A CN 101802146A CN 200880106240 A CN200880106240 A CN 200880106240A CN 101802146 A CN101802146 A CN 101802146A
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S·比奥拉茨
T·J·希尔德豪尔
M·西曼
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Scherrer Paul Institut
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Abstract

本发明公开了一种将粗气体转化成富甲烷和/或富氢气体的方法，步骤包括：a)提供源自煤和/或生物质气化过程的粗气体，从而使所述粗气体中除甲烷和氢成分之外还包含一氧化碳、二氧化碳、烷烃、烯烃、炔烃、焦油，特别是粗苯和萘，COS、硫化氢和有机硫化合物，特别是噻吩；由此氢与一氧化碳的比例在0.3-4的范围内；b)使此粗气体与设置为流化床反应器的催化剂在200℃以上的温度和大于等于1巴的压力下接触，以将所述粗气体转化成第一产物气体，从而同时将有机硫组分转化成硫化氢、重整焦油、发生水/气转换反应和由所述氢/一氧化碳成分产生甲烷；c)使所述第一产物气体进入硫吸附过程以产生第二产物气体，由此将硫化氢和COS含量从100-1000ppm降低到1000ppb或更低；d)任选地使所述第二产物气体进入二氧化碳脱除过程以产生至少几乎不含二氧化碳的第三产物气体；e)使所述第三产物气体进入第二甲烷化过程以产生甲烷含量在5体积％以上的第四产物气体；f)任选地使所述第四产物气体进入二氧化碳脱除过程以产生至少几乎不含二氧化碳的第五产物气体；g)使所述第五产物气体进入氢分离过程以将富氢气体与剩余的被称作代用天然气的富甲烷气体分离。

Description

由气化得到的含硫合成气制造富甲烷气体混合物的方法
本发明涉及将煤或生物质转化成至少几乎不含硫的代用天然气的方法。此外，本发明还涉及由气化得到的含硫合成气制造富甲烷气体混合物的方法。
特别是，本发明涉及一种由生物质、煤或石脑油连续制造合成天然气(SNG)的方法。更具体地，本发明涉及由这些较便宜的含硫碳氢材料制造清洁气态加热燃料。
背景技术
由生物质制造SNG是从″不清洁/难燃烧″的燃料向清洁燃烧的公知商品的转化。用户可以自由地将SNG用于发电、加热或移动。另外一大有利方面是已有的基础设施如管道和压缩天然气(NG)汽车。将甲烷化的产物气体加入此网络必须脱除CO2并压缩到5-70巴以符合一般天然气的标准。
生物质向SNG的转化是一个复杂的过程，其可被大致构造为四个主要单元：气化、粗气体净化、燃料合成和气体净化。固体的进料被热转化成粗气体，并随后被脱除掉颗粒、焦油和硫。在燃料合成中，所述粗气体被转化成粗SNG(CH4/CO2混合物)，所述粗SNG在注入天然气网之前被脱除掉CO2和任选地脱除掉H2(气体净化)。
根据气化的温度，在进料中存在硫会导致形成H2S、COS或有机硫物质。低温(LT)气化会促使形成诸如噻吩、硫醇和硫醚之类的有机硫物质，而高温(HT)气化会导致只形成H2S和COS。
HT和LT气化的典型粗气体组成如表1所示。
  表1
  低温气化(600-1000℃)   高温气化(1000-2000℃)
  H2S、CO、CO2、H2O   H2S、CO、CO2、H2O
  CH4   几ppm
  烷烃、烯烃、炔烃(特别是乙烯)   无
  焦油(萘、...)   无
  H2S、COS   H2S、COS
  有机S物质(硫醇、硫醚、噻吩   无
  HCN、NH3   HCN、NH3
  表1
  有机N物质(例如吡啶)   无
对于SNG的合成，LT气化是有利的(更高的总体冷气效率)，因为粗气体中已经含有相当数量的CH4。这种粗气体的缺陷是高含量的有毒组分，如烯烃、炔烃、H2S、COS、有机S物质、HCN、NH3、有机N物质。
因此，为保护在燃料合成中施加的催化剂，需要进行有效的气体净化。图1a显示了制造用于诸如费托合成或甲醇、DME和SNG生产等应用的合成气体的现有技术的例子。
使用了低温洗涤器来除去焦油、有机S物质和有机N物质。H2S、COS被吸附在可用于此目的的吸附剂(活性炭、氧化锌或其它金属氧化物)上。一般，在气体净化之后是水-气转换反应器、CO2分离和多个甲烷化单元。为将气体的卡值提高到气网的质量限度，脱除了CO2和H2。单元4-9的顺序可以不同。
此工艺方案的缺陷在于，操作单元数量多以及所述单元的不同温度水平(特别是冷却到洗涤器温度)。为避免工艺中的这类温度梯度，通常使用来自HT气化的粗气体，这种方法的一个例子如图1b所示(US3928000、EP0120590)。不同的气体组成使得能够实现抗S水-气转换(WGS)和抗S甲烷化，并减少操作单元的数量。然而，由于SNG组成会导致更高的能量损失，所以所述粗气体组成对于SNG合成来说是较为不利的。首先，在气化单元中为产生纯H2、CO、CO2混合物所需的能量较高；其次，由于甲烷化反应的放热焓，在合成中纯H2、CO、CO2混合物会导致更高的热损耗。
发明描述
通过本发明的方法，可以避免图1a所示方法的不合适的温度水平次序和操作单元数量，以及图1b所示方法的能量损失。可以由含10-95mol％的甲烷的含硫进料生产富甲烷流。
低温气化之后的第一个步骤是一个特征在于能同时进行加氢脱硫/脱氮、甲烷化、WGS、焦油重整和裂化以及烯烃和炔烃的加氢/重整的多功能处理单元。COS和由有机硫物质通过水解产生的H2S通过吸附在常见的吸附材料如ZnO、CuO上而被除去。可在第二甲烷化步骤之前或之后除去CO2。为了调节卡值，分离过量的H2并可将其再循环到单元2。
加氢脱硫单元(HDS)是石化工业中进料脱硫或天然气在蒸汽转化之前脱硫的常见工艺步骤。为这些单元施加的催化剂既会催化甲烷化反应又会催化水气转换反应，这是不期望的，因为这些放热反应会导致反应器的热散逸。然而，在本发明的方法中，甲烷化和WGS反应是期望的。
为控制由于放热反应而导致的升温，可以应用配备有散热装置的流化床反应器。催化剂的流态化为从碳沉积物中内部再生催化剂提供了额外的可能性，其中所述碳沉积物是由诸如LT气化装置发生炉气体中的乙烯或焦油导致的。这样一种内部再生可用于流化床甲烷化并可通过分段加入再循环的H2和/或流化床上部的蒸汽得到强化。
此外，可通过添加水蒸汽、再循环的H2以及适当选择温度和压力来使离开所述单元的粗气体流适合第二甲烷化单元的要求，从而使处理单元的总数量减到最少。
同时进行加氢脱硫/脱氮、甲烷化、WGS、焦油重整和裂化以及烯烃和炔烃的加氢/重整的多功能处理单元。COS和由有机硫物质通过水解产生的H2S通过吸附在常见的吸附材料如ZnO、CuO上而被除去。可在第二甲烷化步骤之前或之后除去CO2。为了调节卡值，分离过量的H2并可将其再循环到单元2。
加氢脱硫单元(HDS)是石化工业中进料脱硫或天然气在蒸汽转化之前脱硫的常见工艺步骤。为这些单元施加的催化剂既会催化甲烷化反应又会催化水气转换反应，这是不期望的，因为这些放热反应会导致反应器的热散逸。然而，在本发明的方法中，甲烷化和WGS反应是期望的。
为控制由于放热反应而导致的升温，可以应用配备有散热装置的流化床反应器。催化剂的流态化为从碳沉积物中内部再生催化剂提供了额外的可能性，其中所述碳沉积物是由诸如LT气化装置发生炉气体中的乙烯或焦油导致的。这样一种内部再生可用于流化床甲烷化并可通过分段加入再循环的H2和/或流化床上部的蒸汽得到强化。
此外，可通过添加水蒸汽、再循环的H2以及适当选择温度和压力来使离开所述单元的粗气体流适合第二甲烷化单元的要求，从而使处理单元的总数量减到最少。

Claims (15)

1.由源自气化的合成气体混合物制造进一步应用于高温燃料电池或用于生产合成天然气(SNG)的富甲烷气体混合物的方法，其中所述源自气化的合成气体混合物中至少含有某些对常规甲烷化单元有害的化合物如有机硫或有机氮化合物、烷烃、烯烃、炔烃、芳烃如萘、甲苯、苯、酚等或其它非芳族烃，所述方法包括：a)至少一个可以进行甲烷化、水气转换反应和将大部分或部分上述有害化合物通过例如
-有机硫物质的加氢脱硫，
-有机氮物质的加氢脱硫，
-烷烃、烯烃、炔烃的加氢或重整，
-烃类的加氢、重整或裂化，
转化成不太有害的化合物的单元，其中该单元在200-900℃的温度、0.8-70巴的压力下工作且包含催化剂，所述催化剂含有金属例如钼、钴、钌、镍、钨或它们的硫化物作为活性相且负载在含例如铝、硅、钛、锆、铈、钆、锰、钒、镧、铬或它们的氧化物的材料上。
2.权利要求1的方法，其在具有粒径范围为20-2000μm的催化剂颗粒的流化床反应器中进行。
3.权利要求1和2的方法，其配备有用于控制温度的传热装置，优选地在是所述流化床反应器中。
4.权利要求1-3中任意一项的方法，其在所述反应器的顶部、底部和/或中间具有额外的氢进料(例如来自再循环流)，例如作为二次注入输入流化床。
5.权利要求1-4中任意一项的方法，其在所述反应器的顶部、底部和/或中间具有额外的水蒸气进料，例如作为二次注入输入流化床。
6.权利要求1-5中任意一项的方法，其具有额外的活性炭、ZnO或其它金属氧化物床以除去诸如H2S和/或COS之类的物质。
7.权利要求6的方法，其在所述活性炭、ZnO或其它金属氧化物床之前具有额外的水去除，以提高分离效率，例如通过膜。
8.权利要求1-7中任意一项的方法，其具有额外的二氧化碳去除。
9.权利要求1-8中任意一项的方法，其具有额外的水蒸气进料，继之以第二甲烷化步骤。
10.权利要求1-8中任意一项的方法，其具有额外的水蒸气进料，继之以在流化床反应器中进行的第二甲烷化步骤。
11.权利要求9或10的方法，其具有额外的二氧化碳去除。
12.权利要求1-11中任意一项的方法，其具有额外的水去除。
13.权利要求1-12中任意一项的方法，其具有额外的氢去除。
14.权利要求1-12中任意一项的方法，其具有额外的氢去除，且所述氢被用作再循环流输入所述第一甲烷化单元。
15.将粗气体转化成富甲烷和/或富氢气体的方法，包括下列步骤：a)提供源自煤和/或生物质气化过程的粗气体，从而使所述粗气体中除甲烷和氢成分之外还包含一氧化碳、二氧化碳、烷烃、烯烃、炔烃、焦油，特别是粗苯和萘，COS、硫化氢和有机硫化合物，特别是噻吩；由此氢与一氧化碳的比例在0.2-5的范围内；b)使此粗气体与设置为流化床反应器的催化剂在200℃以上的温度和大于等于1巴的压力下接触，以将所述粗气体转化成第一产物气体，从而同时将有机硫组分转化成硫化氢、重整焦油、发生水/气转换反应和由所述氢/一氧化碳成分产生甲烷；c)使所述第一产物气体进入硫吸附过程以产生第二产物气体，由此将硫化氢和COS含量从100-1000ppm降低到1000ppb或更低；d)任选地使所述第二产物气体进入二氧化碳脱除过程以产生至少几乎不含二氧化碳的第三产物气体；e)使所述第三产物气体进入第二甲烷化过程以产生甲烷含量在5体积％以上的第四产物气体；f)任选地使所述第四产物气体进入二氧化碳脱除过程以产生至少几乎不含二氧化碳的第五产物气体；g)使所述第五产物气体进入氢分离过程以将富氢气体与剩余的被称作代用天然气的富甲烷气体分离。
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