CN102559270A - 用于制造尾气费托设备的方法和装置 - Google Patents

用于制造尾气费托设备的方法和装置 Download PDF

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CN102559270A
CN102559270A CN2011103560073A CN201110356007A CN102559270A CN 102559270 A CN102559270 A CN 102559270A CN 2011103560073 A CN2011103560073 A CN 2011103560073A CN 201110356007 A CN201110356007 A CN 201110356007A CN 102559270 A CN102559270 A CN 102559270A
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gas
order
hydrogen
flow
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CN102559270B (zh
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P·S·华莱士
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Air Products and Chemicals Inc
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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

本发明涉及用于制造尾气费托设备的方法和装置。一种煤-液(CTL)转化系统包括：煤气化器，其构造成用以使煤燃料流部分地氧化以生成合成气体(合成气)流；费托(FT)反应器(226)，其构造成用以接收合成气流并生成尾气流；在FT反应器(226)的下游成流动连通地联接并构造成用以接收尾气流的吸收器(232)，该吸收器还构造成用以生成包含二氧化碳、C2烃和更高沸点气体成分(C3+)的第一流(226)和包含C1、一氧化碳、氢气和氮气的第二流(268)；以及包括选择性隔膜的第一隔膜分离器(236)，该选择性隔膜构造成用以分离来自吸收器的第二流而生成氢气渗透流以及包含甲烷和氢气的燃气轮机燃料气体的非渗透流。

Description

用于制造尾气费托设备的方法和装置
技术领域
本发明的领域主要涉及具有动力联产的煤-液转化设备，且更具体而言，涉及使用来自费托煤-液转化设备的副产品甲烷和净化气体的动力联产方法和系统。
背景技术
至少一些已知的基于费托(FT)的煤-液转化设备产生甲烷(C1)、乙烷和乙烯(C2)作为副产品，该副产品经净化作为尾气流。除C1和C2烃以外，尾气还包含大量未经反应的合成气和二氧化碳(CO2)。FT设备一般在商业上用于气液转化(GTL)并构造成用以将尾气再循环回到气化器，或燃烧尾气以用于生产蒸汽和发电。对于GTL而言这在经济上具有吸引力，因为C1和C2是流向气化器以及蒸汽和发电设施的新鲜给料。
但是，对于煤-液转化设备，C1在热值($/BTU)方面可为煤的10-20倍还多。因此，将C1再循环到供煤气化器并不经济。如果不能获得管路基础设施来将C1输送到更有价值的使用地点，则希望优先将C1转化为电力。尾气的较低热值和CO2含量的变化使要求热值(沃泊指数)相对恒定的燃料的燃气轮机发电变得复杂。
煤气化产生合成气，该合成气比来自GTL设备的合成气含有显著更多的氮气。额外的氮气需要更多来自FT合成环路的净化合成气以防止氮气蓄积。煤气化还产生显著更多的废热和HP(高压)蒸汽，从而降低燃料气体需求。
无气化器再循环、净化合成气增加以及燃料气体需求降低的组合导致燃料气体不平衡。
发明内容
在一个实施例中，一种用于煤-液(CTL)转化的系统包括构造成用以使煤燃料流部分地氧化以生成合成气体(合成气)流的煤气化器、构造成用以接收合成气流并生成尾气流的费托(FT)反应器，以及在FT反应器的下游成流动连通地联接并构造成用以接收尾气流的吸收器(absorber)。该吸收器还构造成用以生成包含二氧化碳、C2烃和更高沸点气体成分(C3+)的第一流以及包含C1、一氧化碳、氢气和氮气的第二流。该系统还包括第一隔膜分离器，该第一隔膜分离器包括构造成用以分离来自吸收器的第二流而生成氢气渗透流以及包含甲烷和氢气的燃气轮机燃料气体的非渗透流的选择性隔膜。
在另一实施例中，一种处理费托(FT)反应器的尾气的方法包括使用FT反应器生成尾气流、从尾气流吸收二氧化碳、C2烃和C3-C7烃而生成至少包含C1烃、一氧化碳、氢气和氮气的稀尾气流以及吸收剂流。该方法还包括净化稀尾气以生成包含甲烷、氮气和氢气的净化气流以及残余气流，分离净化气流而生成氢气渗透流以及包括甲烷、氢气和氮气的燃气轮机燃料气体的非渗透流，以及将非渗透流导送到构造成用以使用非渗透流生成电流的发电系统。
在又一实施例中，一种费托尾气处理系统包括构造成用以生成尾气流的费托(FT)反应器和与FT反应器成流动连通地联接并构造成用以接收尾气流的吸收器。该吸收器还构造成用以将尾气分离成至少包含C1烃、一氧化碳、氢气和氮气的稀尾气流以及包含二氧化碳、C2烃和C3-C7烃的吸收剂流。该系统还包括构造成用以生成包含甲烷和氢气的净化气流以及残余气流的稀尾气净化装置(purge)以及隔膜分离器，该隔膜分离器包括构造成用以分离净化气流而生成氢气渗透流以及包含甲烷和氢气的燃气轮机燃料气体的非渗透流的选择性隔膜。
附图说明
图1至图2示出本文所述的方法和系统的示例性实施例。
图1是根据本发明的示例性实施例的气化系统的示意图；以及
图2是根据本发明的另一示例性实施例的气化系统的示意图。
零件清单
100气化系统
110燃气轮机发电机
114燃气轮机
118发电机
120转子
130蒸汽轮机发电机
132蒸汽轮机
134发电机
136第二转子
140蒸汽发生系统
142热回收蒸汽发生器(HRSG)
144热传递装置
146管道
146经加热锅炉给水管道
148排气管道
150蒸汽管道
152烟气管道
208气化反应器
210管道
211浆化单元
212供煤管道
213供水管道
214煤浆管道
218热合成气管道
220经转换合成气管道
221水气转换反应器
223管道
224酸性气体去除(AGR)子系统
226费托(FT)反应器
228乙二醇干燥器
230管道
232吸收器
234管道
236隔膜分离器
238管道
240变压吸附(PSA)单元
242加氢裂化器FT提质单元
244管道
246管道
248管道
250CO2汽提塔
254管道
256FT产品精炼子系统
260管道
262管道
264第二选择性隔膜分离器
266流
268流
具体实施方式
以下详细描述举例但非限制性地说明本发明的实施例。可以预期的是，本发明总体适用于处理来自工业、商业和民用用途的费托反应器的尾气的分析和方法实施例。
如本文所用，以单数列出并冠以用词“一”或“一个”的元件或步骤应理解为不排除多个元件或步骤，除非明确指明这种排除。此外，本发明对“一个实施例”的谈及并非意图将其解释为排除也结合了所列出的特征的其它实施例的存在。
如本文所用，用语“选择性”当用于谈及隔膜时描述了隔膜容许该隔膜暴露于其的混合物的一种成分相对于混合物的其它成分穿过该隔膜转移的倾向。因此，CO2选择性隔膜是相对于混合物的其它成分例如H2S和H2的转移而言优先容许CO2穿过隔膜转移的隔膜。
图1是根据本发明的示例性实施例的气化系统100的示意图。在示例性实施例中，气化系统100是包括燃气轮机发电机110的整体气化联合循环(IGCC)发电设备。燃气轮机114经由第一转子120以可旋转的方式联接到第一发电机118上。燃气轮机114与至少一个燃料源和至少一个空气源(两者都在下文更详细地描述)成流动连通地联接并构造成用以接收分别来自燃料源和空气源的燃料和空气。燃气轮机114构造成用以混合空气和燃料、产生热燃烧气体(未示出)并将气体内的热能转化为旋转能。旋转能经由转子120传输到发电机118，其中发电机118构造成用以促进将旋转能转化为电能(未示出)以便输送到包括但不限于电网(未示出)的至少一个负载。
IGCC设备100还包括蒸汽轮机发电机130。在示例性实施例中，蒸汽轮机发电机130包括经由第二转子136可旋转地联接到第二发电机134上的蒸汽轮机132。
IGCC设备100还包括蒸汽发生系统140。在示例性实施例中，系统140包括经由至少一个经加热锅炉给水管道146而与至少一个热传递装置144成流动连通地联接的至少一个热回收蒸汽发生器(HRSG)142。HRSG 142构造成用以经由管道146接收来自装置144的锅炉给水(未示出)以便促进将锅炉给水加热成蒸汽。HRSG 142还构造成用以经由排气管道148接收来自涡轮机114的排气，以进一步促进将锅炉给水加热成蒸汽。HRSG 142经由蒸汽管道150而与涡轮机132成流动连通地联接。过剩的气体和蒸汽经由烟气管道152从HRSG142排放到大气。
管道150构造成用以将蒸汽从HRSG 142导送到涡轮机132。涡轮机132构造成用以接收来自HRSG 142的蒸汽并将蒸汽中的热能转换为旋转能。旋转能经由转子136传输到发电机134，其中发电机134构造成用以促进将旋转能转化为电能(未示出)，以便输送到包括但不限于电网的至少一个负载。蒸汽经冷凝并经由冷凝物管道(未示出)作为锅炉给水返回。
气化系统100包括经管道210而与氧化剂(例如但不限于空气)流成流动连通地联接的气化反应器208。系统100还包括煤研磨和/或浆化单元211。单元211分别经由供煤管道212和供水管道213而与煤源和水源(均未示出)成流动连通地联接。在一个实施例中，单元211构造成用以混合煤和水以形成经由煤浆管道214导送到气化反应器208的煤浆流(未示出)。尽管图中将煤浆显示为供给燃料，但也可使用包含干燥含碳材料的任何含碳材料作为用于气化系统100的燃料。
气化反应器208构造成用以分别经由管道214和210接收煤浆流和氧化剂流。气化反应器208还构造成用以促进产生热的原质合成气体(合成气)流(未示出)。原质合成气包含括一氧化碳(CO)、氢气(H2)、二氧化碳(CO2)、硫化羰(COS)和硫化氢(H2S)。CO2、COS和H2S通常统称为酸性气体，或原质合成气的酸性气体成分。
在示例性实施例中，气化反应器208经由热合成气管道218而与水气转换反应器221成流动连通地联接。在另一实施例中，热传递装置144成流动连通地联接在气化反应器208与水气转换反应器221之间。装置144构造成用以接收热的原质合成气流并经由管道146将至少一部分热量传递到HRSG 142。随后，装置144产生经管道218导送到水气转换反应器221的经冷却的原质合成气流(未示出)。在示例性实施例中，热合成气直接导送到水气转换反应器221。水气转换反应器221构造成用以例如利用下式将一氧化碳和水转化为二氧化碳和氢气：
CO+H2O→CO2+H2    (1)
在示例性实施例中，系统100还包括经由经转换合成气管道220而与水气转换反应器221直接成流动连通地联接的酸性气体去除(AGR)子系统224。在各种实施例中，冷却装置成串行流动连通地联接在水气转换反应器221与AGR子系统224之间，该AGR子系统224构造成用以经由经转换合成气管道220接收冷却的经转换的合成气流。酸性气体去除子系统224还构造成用以促进如下文进一步所述那样从原质合成气流去除酸性气体成分(未示出)的至少一部分。这种酸性气体成分包括但不限于CO2、COS和H2S。酸性气体去除子系统224还构造成用以促进将酸性气体成分的至少一部分分离成包括但不限于CO2、COS和H2S的成分。此外，酸性气体去除子系统224经由管道223而与费托反应器226成流动连通地联接。
用于转化主要由一氧化碳(CO)和氢气(H2)组成的合成气的费托反应其特征在于以下综合反应：
(2n+1)H2+nCO→CnH(2n+2)+n H2O，其中            (2)
“n”表示正整数。
在FT反应器226中生成的尾气经管道230导送到乙二醇干燥器228，以去除微量的水。经干燥的气体导送到吸收器232，在其中使用冷冻的液化石油气(LPG)和石脑油来吸收大部分C2、大部分CO2和几乎全部更高沸点的气体成分(C3+)。
净化装置用来从稀尾气去除C1和H2并经管道234将剩余部分再循环到FT反应器226。净化气体经管道238传送到隔膜分离器236，在其中提取大部分(大约30-50％)的氢气。隔膜分离器236是包括用于将气流分离成富C1(甲烷)气流和富H2气流的隔膜的选择性隔膜分离器。
富H2气流(几乎无氮气)受压缩并且一部分氢气经管道244再循环到FT反应器226。其余氢气导送到变压吸附(PSA)单元240，该单元240产生用于加氢裂化器FT提质单元242的大致纯氢气。来自隔膜分离器236的非渗透流经管道246作为燃料气体导送到燃气轮机发电机110。PSA尾气流经管道248导送到HRSG 142以用于补充燃烧。
吸收器232和隔膜分离器236操作使得余量H2和CO2在燃料气流中保持相对恒定，从而在燃气轮机发电机110维持相对恒定的沃泊指数。
来自吸收器232的含有CO2、C2和C2+的液体导送到CO2汽提塔250，在其中从液体去除CO2和C2。从汽提塔250的底部去除LPG流。CO2/C2废气(offgas)经管道254作为再循环CO2流传送到气化反应器208。一部分CO2/C2废气可与燃料气体混合，以帮助控制恒定的沃泊指数。
FT产品精炼子系统256构造成用以进一步处理来自FT反应器226的输出液流。FT产品精炼使用蒸馏和/或分馏工艺来生成例如输送燃料流。
图2是根据本发明的另一示例性实施例的气化系统100的示意图。在示例性实施例中，在FT产品精炼子系统256中生成的H2流经管道260导送到隔膜分离器236。来自FT产品精炼子系统256的H2流趋于增加流向隔膜分离器236的给料中氢气的比例，从而使得捕获更多氢气以用于在系统100内部使用或外输。来自FT产品精炼子系统256的其它气体经管道262捕获并导送到吸收器232。第二选择性隔膜分离器264接收来自隔膜分离器236的大部分氢气流，该隔膜分离器236生成无污染物的氢气流266以用于内部使用和/或外输，以及导送到HRSG 142以用于补充燃烧和/或通气的残余气流268。如本文所用，无污染物的氢气定义为不包含其它有意保留的物质的较纯氢气。
本发明的实施例包括FT尾气处理系统，该FT尾气处理系统促进通过从C1和最少量的净化气体产生外输动力来消除燃料气体不平衡。这些实施例提供的优点在于，通过将电力作为副产品售卖和增加LPG产量(所有作为LPG捕获的C3+)而增加产品收入，通过增加FT尾气中的合成气再循环到FT反应器而不增加FT反应器内的惰性物质含量而降低气化投资成本，产生与FT提质单元(加氢裂化器)相容的较高纯度氢气流，以及尾气中的CO2和C2再循环到气化反应器208，这促进降低来自AGR 224的再循环CO2的需求。C2也再循环到气化反应器208。C2的较高热值允许以最低的附加氧气消耗使该材料气化并且最少的高值C1再循环到气化器。
上述处理FT反应器的尾气的方法和系统的实施例提供了用于减少煤-液转化设备中的燃料气体不平衡的成本有效并可靠的手段。更具体而言，本文所述的方法和系统促进减少无气化器再循环的影响，增加了净化合成气，并降低了与燃料气体不平衡有关的燃料气体需求。另外，上述方法和系统促进通过电力的副产品售卖和使用基本上所有作为LPG捕获的C3+而增加LPG产量来增加产品收入，促进通过增加FT尾气中的合成气再循环到FT反应器而不增加FT单元中的惰性物质含量来降低煤气化投资成本，促进生产与FT提质单元相容的高纯度氢气流，以及促进尾气中的CO2和C2再循环到气化器，这减少了来自酸性气体去除单元的再循环CO2需求并且C2的较高热值允许以最低的额外氧气消耗来气化C2。因此，本文所述的方法和系统促进以节省成本和可靠的方式来消除燃料气体不平衡。
上文详细描述了用于消除煤-液转化设备中的燃料气体不平衡的示例性方法和系统。所述的装置并不限于本文所述的特定实施例，而相反，每个构件都可与本文所述的其它构件独立和分开地使用。各系统构件也可与其它系统构件相结合地使用。
此书面描述使用了包括最佳模式在内的实例来公开本发明，并且还使本领域的任何技术人员能够实施本发明，包括制造和利用任何装置或系统以及执行任何所结合的方法。本发明可取得专利的范围通过权利要求来限定，并且可包括本领域技术人员想到的其它实例。如果这些其它实例具有与权利要求的文字语言并无不同的结构元件，或者如果这些其它实例包括与权利要求的文字语言无实质性区别的同等结构元件，则认为这些其它实例包含在权利要求的范围之内。

Claims (7)

1.一种煤-液(CTL)转化系统，包括：
煤气化器，所述煤气化器构造成用以使煤燃料流部分地氧化以生成合成气体(合成气)流；
费托(FT)反应器(226)，所述费托反应器构造成用以接收所述合成气流并生成尾气流；
在所述费托反应器(226)的下游成流动连通地联接并构造成用以接收所述尾气流的吸收器(232)，所述吸收器还构造成用以生成包含二氧化碳、C2烃和更高沸点气体成分(C3+)的第一流(266)以及包含C1、一氧化碳、氢气和氮气的第二流(268)；以及
包括选择性隔膜的第一隔膜分离器(236)，所述选择性隔膜构造成用以分离来自所述吸收器的所述第二流而生成氢气渗透流以及包含甲烷和氢气的燃气轮机燃料气体的非渗透流。
2.根据权利要求1所述的转化系统，其特征在于，所述转化系统还包括所述第二流(268)的气体净化装置，所述气体净化装置构造成用以生成包含甲烷和氢气的净化气流以及残余气流。
3.根据权利要求1所述的转化系统，其特征在于，所述转化系统还包括与所述第一隔膜分离器(236)成流动连通地联接的第二隔膜分离器(264)，所述第二隔膜分离器构造成用以生成基本上无污染物的氢气流和残余气流。
4.一种费托尾气处理系统，包括：
构造成用以生成尾气流的费托(FT)反应器(226)；
与所述费托反应器成流动连通地联接并构造成用以接收所述尾气流的吸收器(232)，所述吸收器还构造成用以将所述尾气分离成至少包含C1烃、一氧化碳、氢气和氮气的稀尾气流以及包含二氧化碳、C2烃和C3-C7烃的吸收剂流；
构造成用以生成包含甲烷和氢气的净化气流以及残余气流的稀尾气净化装置；以及
包括选择性隔膜的隔膜分离器(236)，所述选择性隔膜构造成用以分离所述净化气流而生成氢气渗透流以及包含甲烷和氢气的燃气轮机燃料气体的非渗透流。
5.根据权利要求4所述的系统，其特征在于，所述系统还包括与生成的渗透流成流动连通地联接并构造成用以生成基本上无污染的氢气流的变压吸附(PSA)单元(240)。
6.根据权利要求4所述的系统，其特征在于，所述系统还包括构造成用以使煤燃料流部分地氧化以生成合成气体(合成气)流的煤气化器，所述费托反应器(226)构造成用以接收来自煤气化器的合成气流。
7.根据权利要求4所述的系统，其特征在于，所述系统包括在所述吸收器(232)与煤气化器之间成流动连通的CO2汽提塔(250)，所述汽提塔构造成用以生成CO2和C2流，以用于再循环到所述煤气化器的进口并生成液化石油气(LPG)流。
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