CN106957674A - 重整烃的方法 - Google Patents
重整烃的方法 Download PDFInfo
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- CN106957674A CN106957674A CN201610973513.XA CN201610973513A CN106957674A CN 106957674 A CN106957674 A CN 106957674A CN 201610973513 A CN201610973513 A CN 201610973513A CN 106957674 A CN106957674 A CN 106957674A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
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- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B3/382—Multi-step processes
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- C01B3/386—Catalytic partial combustion
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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- C10G2/31—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen thermal, non catalytic conversion
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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Abstract
本发明涉及通过使用自热重整制造合成气的方法，其中来自下游费托合成的尾气被氢化并随后添加到该自热重整阶段。
Description
本申请是申请日2012年6月20日、申请号2012800325093、发明名称“重整烃的方法”的发明专利申请的分案申请。
技术领域
本发明涉及制造用于通过费托合成法制造烃的合成气的方法。本发明特别涉及通过使用自热重整制造合成气的方法，其中将来自下游工艺，特别是费托合成的尾气氢化并随后添加到自热重整中。在更一般的方面，本发明包括除去气体中的烯烃以减少与该气体接触的金属部件的金属尘化，特别是减少该气体流经的ATR、CPO或POx及其它下游设备中的金属尘化。
背景技术
制造用于费托合成的合成气通常通过使烃进料流过初级和次级重整阶段来获得。初级重整通常在管式蒸汽重整器或热交换重整器中进行，而次级重整通常在自热重整器中进行。当热交换重整器与随后的自热重整器结合时，来自自热重整器的热排放气体通常用作热交换重整器中的加热介质。已知的是再循环来自费托合成的尾气作为一部分用于在初级和次级重整阶段中制造合成气的烃进料。尾气可以在初级重整之前添加，或在进入次级重整（通常为自热重整）前添加到初级重整气体中。
来自费托合成的尾气含有氢、一氧化碳、二氧化碳以及链烷烃（如甲烷、乙烷、丙烷）与非最小烯烃（如丙烯）形式的轻质烃。该尾气还可以包括醇和其它链烷与烯烃性质的高级烃。已知的是，将此类尾气添加到合成气生产部分使得在重整过程中存在足够的二氧化碳以实现所需H2/CO摩尔比（通常大约2.0）。
本文中所用“尾气”是指未在所述阶段中重新使用的来自费托合成阶段的废气。
尾气的氢化在本领域是已知的。例如，在GB 632386中，将来自费托合成的尾气氢化以提高该气体的低的发热值，这类低发热值尤其是由于二氧化碳、一氧化碳和氢的存在所导致的。
WO-A-0142175公开了一种方法，其中将尾气氢化以饱和任何不饱和烃，并随后在单独的蒸汽重整器中重整。氢化用于降低在随后的蒸汽重整器的高温处理中的结焦倾向，因为当尾气中存在不饱和烃时，在所述重整器中的结焦倾向更大。所得重整尾气随后还可以送入自热重整器。因此，在氢化阶段和自热重整器之间使用蒸汽重整器。
EP-A-1860063公开了一种方法，在该方法中，首先将来自费托合成的废气（其中在该废气中存在烯烃）氢化，并随后通过重整过程转化为氢。因制氢单元中所用催化剂的碳沉积或结焦并且其在催化剂和重整器反应管上形成热点而将烯烃氢化。由此，将烯烃除去以避免在具有重整器管的蒸汽重整器（如燃烧式重整器）中的结焦。
发明内容
我们现在已经发现，将尾气添加到自热重整器（ATR）或催化部分氧化反应器（CPO）或非催化部分氧化反应器（POx）中——其是合意的以调节合成气中的H2/CO比——具有促进金属尘化腐蚀（特别是在ATR或CPO的燃烧器部件中）的严重缺陷，但是通过在将尾气直接添加到ATR中之前将尾气氢化，可以显著减少此类金属尘化。令申请人惊喜的是，经氢化法除去尾气中的特别为烯烃提供了显著降低尾气的侵蚀性并因此减少或消除ATR、或CPO或POx中的金属尘化的关键优点。同时保持了使用尾气调节H2/CO比的益处。
通过本发明提供的简单、经济和极佳的解决方案减少或消除设备（例如ATR、CPO或POx）中的金属尘化直接转化为减少或消除了工厂中昂贵的停机时间，并由此降低了维护成本。金属尘化已经另外通过使用在金属尘化条件下形成保护性表面的抗性合金组合物或金属涂层和/或通过在金属尘化侵蚀性较低的条件下运行该重整器（但是这另一方面削弱了该过程）来缓和。然而，当暴露于来自费托合成的尾气时，即使使用昂贵和以其它方式有效抵抗金属尘化的合金如Inconel 690也不能抵抗金属尘化的侵袭。
金属尘化是当含有一氧化碳的气体与高于大约ca. 400℃、特别是400-800℃的金属接触时会遇到的一类金属腐蚀。金属尘化令金属崩解为粉尘并广泛描述于文献中。
金属尘化是非常复杂的腐蚀过程，还没有被完全了解。但是，其通常由以下反应表示：
CO + H2 → C + H2O （1）
形成的碳有可能通过包括碳化物形成和/或碳在金属材料中的溶解的机理导致结构材料的腐蚀。
经放热反应2CO → C + CO2（布杜阿尔反应）和CO + H2 → C + H2O（CO还原）生成碳是金属尘化（MD）腐蚀的先驱。该放热反应在低温下有利。但是，温度越高，反应速率越高。结果，对给定气体的MD潜势（potential）在中等温度范围内，通常在大约400-800℃范围内将最高。
但是，必须理解，金属尘化和结焦是两种不同的现象。金属尘化是指金属部件的灾难性腐蚀，而结焦与催化剂相关联。结焦更具体指碳生成，因为生成了在蒸汽重整催化剂（通常为镍-基催化剂）的镍表面或载体材料上沉积和分解的碳质元素，此类碳生成而不利地影响蒸汽重整器（如管式重整器）的催化剂。这也会导致在含有催化剂的管中的热点的加剧。因此，对于本领域技术人员而言，金属尘化和结焦是两种不同的现象：尽管早已知晓烯烃的存在导致催化剂床中的积炭，还没有人注意或预料到烯烃也会导致诸如金属尘化的不同现象。
因此，在本发明的第一方面我们提供在自热重整器（ATR）、催化部分氧化反应器（CPO）或部分氧化反应器（POx）的至少燃烧器部件中具有降低的金属尘化潜势（potential）的由烃原料制造合成气的方法，包括：使所述烃原料通过ATR、CPO或POx，并从ATR、CPO或POx中取热排放合成气的流（stream of hot effluent synthesis gas），使来自费托合成阶段的尾气通过氢化阶段以制造氢化的尾气，并将氢化的尾气直接添加到所述ATR、CPO或POx中。
将尾气氢化获得了保护ATR、CPO或POx免受金属尘化的气体，特别是对于燃烧器金属部件位于反应器入口处并由此位于催化剂床上游的ATR与CPO，因为预料不到的是不存在烯烃使得该气体在金属尘化腐蚀方面具有较低的侵蚀性（aggressive）。
因此，以极佳和简单的方式提供了对长期存在的ATR、CPO或POx中金属部件（特别是ATR的燃烧器部件）的金属尘化问题的解决方案，在将来自费托合成的尾气并入该方法时会遇到该问题。
本文中所用术语“在自热重整器（ATR）、催化部分氧化反应器（CPO）或部分氧化反应器（POx）的至少燃烧器部件中降低的金属尘化潜势”指的是在与进料至其中（ATR、CPO、POx）的工艺气体接触的在反应器中的任何金属部件中降低金属尘化潜势，所述金属部件包括燃烧器金属部件，特别是对于ATR或POx而言。本领域技术人员要理解的是，ATR和POx意味着在反应器顶部使用燃烧器。ATR和CPO使用在燃烧区下方的催化剂床。CPO意味着并非总是需要使用燃烧器而是代之以混合器的催化反应器或催化气化器。此外，在POx（气化器）中不使用催化剂。
术语ATR包括次级重整器。
由于该尾气含有一氧化碳、二氧化碳、氢、包括烯烃的各种烃和多种如上所述的其它组分，根据下列反应C3H6 + H2 ↔ C3H8通过氢化降低烯烃浓度，由此转化该气体。对丙烯氢化给出该反应，其它烯烃的氢化根据类似反应进行。
适于将烯烃选择性氢化为饱和烃的催化剂优选基于铜，例如Cu/ZnO催化剂，或者铜与贵金属例如铂或钯的组合。铜-基催化剂，如Cu/ZnO催化剂在将烯烃选择性催化成链烷烃中是特别活性的，并较少生成或不生成甲醇或在它们的结构中具有两个或多个碳原子的高级醇。
在上面和下面的实施方案中，氢化优选在冷却的反应器中进行，特别是在100-150℃的温度下或更高，例如185℃。这能够高度转化烯烃如C3H6和C4H8，同时避免显著生成甲醇或高级醇和其它副产物。或者，氢化在绝热反应器中进行，其中入口温度优选为70-120℃，更优选80-100℃，出口温度为120-210℃，优选140-190℃，更优选150-185℃。
氢化步骤中的压力为20-70巴，优选20-50巴，更优选20-40巴。
在本发明的一个实施方案中，所述烃原料是已经通过至少一个绝热预重整阶段的气体。
绝热预重整优选在含有重整催化剂的固定床反应器中进行，由此将所有高级烃转化为碳氧化物、氢和甲烷的混合物。该吸热过程伴随着放热甲烷化与变换反应的平衡。除去高级烃允许随后的蒸汽重整采用更高的预热温度。
在本发明的另一实施方案中，所述烃原料是已经通过至少一个蒸汽重整阶段的气体。该蒸汽重整阶段可以例如是管式重整（蒸汽甲烷重整，SMR）或热交换重整（对流重整）。
在又一实施方案中，本发明还包括一种方法，其中所述烃原料是来自于以下过程的气体混合物：将原始烃进料气体分为两股流，使第一流通过至少一个蒸汽重整阶段以形成初级重整气体，使用第二流作为所述蒸汽重整阶段的旁路流，并随后将所述初级重整气体与该旁路流合并以形成所述烃原料。
根据该实施方案，蒸汽重整与ATR、CPO或POx串联布置。
在一个单独的实施方案中，还提供了其中蒸汽重整与ATR、CPO或POx并联排列的布置。因此，该方法包括将原始烃进料气体分为两股流，由此使形成的流之一成为所述烃原料，并使另一流通过至少一个蒸汽重整阶段以形成重整气体。
在与上面或下面的任一实施方案结合的另一实施方案中，提供了一种方法，其中蒸汽重整阶段是热交换重整，并且其中来自ATR、或CPO、或POx阶段的热排放合成气的至少一部分用作所述热交换重整中的加热介质。
因此，一个优选实施方案是一种方法，其中热交换重整器布置在上游并与ATR或CPO（优选ATR）串联。该原始烃进料（例如脱硫天然气）与蒸汽混合，并将所得混合物引导到热交换重整器的催化剂一侧。在该热交换重整器中，随后根据下列反应蒸汽重整该气体：CH4 + H2O ↔ CO + 3H2和CO + H2O ↔ CO2 + H2。离开热交换重整器的气体接近上述反应的化学平衡。通常，出口温度为600-850℃，或优选675-775℃。将离开该热交换重整器的初级重整气体送入ATR或CPO中。在该反应器（ATR或CPO）中还加入氧，在某些情况下还加入少量蒸汽。通过在反应器中结合蒸汽重整和部分氧化来生成合成气。离开反应器的气体不含氧，并且上述反应通常接近化学平衡。来自例如自热重整器的热排放气体的温度为950至1100℃，通常为1000至1075℃。
离开该反应器的热排放气体包含一氧化碳、氢、二氧化碳、蒸汽、残余甲烷和各种其它组分，包括氮和氩。将该合成气送入该热交换重整器的非催化一侧，在那里该合成气通过向热交换重整器的催化一侧经间接热交换供应热来冷却。来自热交换器这一侧的出口温度通常为500-800℃。
接下来，在另一优选实施方案中，热交换重整器与ATR、CPO或POx，优选ATR并联布置，并且来自该ATR、CPO或POx的热排放合成气用于提供用于热交换反应器中吸热重整反应的热。
在并联布置中，在所述热排放合成气已经将热传递至热交换重整之前、之中或之后将所述热排放合成气与所述重整气体混合。优选地，在所述热排放合成气已经将热传递至热交换重整之前将所述热排放合成气与所述重整气体混合。
在与上面或下面的任一实施方案结合的又一实施方案中，该方法还包括将包含蒸汽的流添加到所述热排放合成气、所述重整气体、或热排放合成气与重整气体的混合流中。
因此，无论热交换重整器与ATR、CPO或POx串联还是并联布置，将蒸汽引入来自ATR、CPO或POx的传递热至热交换重整器的气体中。这能够减少热交换重整器的金属部件，特别是壳程的金属尘化，尤其是当热交换重整器与ATR、CPO或POx串联布置时。包含蒸汽的流优选含有超过90体积%、更优选超过95体积%且最优选超过99体积%的蒸汽（气相H2O）。优选地，热排放合成气的温度为950至1050℃，更优选1025℃，而添加的蒸汽优选在55 barg下在271℃下，由此获得900至990℃的混合流（即与包含蒸汽的流结合的热排放合成气）温度。
在与上面或下面的任一实施方案结合的再一实施方案中，在拆分所述原始烃进料之前进行至少一个绝热预重整阶段。因此，在将原始烃进料气体分成串联或并联布置的单独流之前，进行原始烃进料（通常包含甲烷和高级烃）的绝热预重整。
在与上面或下面的任一实施方案结合的另一实施方案中，该方法还包括在ATR、CPO或POx中进行重整之前将氢化尾气与烃原料混合；或者，以单独流形式将氢化尾气添加到ATR、CPO或POx中。
与上述串联布置的操作相关，还提供了一种方法，包括在ATR、CPO或POx中进行重整之前将氢化尾气与所述旁路流混合；或者，将氢化尾气与所述的初级重整气体混合。
在与上面或下面的任一实施方案结合的又一实施方案中，该方法进一步包括经费托合成将该合成气转化为液态烃，特别是柴油。
在第二方面，本发明包括使用来自费托合成阶段的氢化尾气作为减少自热重整器（ATR）、催化部分氧化反应器（CPO）或部分氧化反应器（Pox）中金属尘化的手段。
因此，根据该方面，本发明包括使用已知物质（氢化的尾气）以获得减少ATR、CPO或POx中金属尘化的令人惊讶的技术效果。由此避免昂贵的替代方法，如提供在金属尘化条件下形成保护性表面的抗性合金组合物或金属涂层。
将来自费托合成的尾气氢化，由此将烯烃（链烯烃）转化为链烷，并由此预料不到地与其中直接添加尾气而不氢化的情况相比在至少反应器的燃烧器部件中减少金属尘化。由于使用尾气对调节合成气中的H2/CO比是合意的，现在可以无需冒金属尘化问题所致的昂贵的停工期和在ATR、CPO或POx中的维护成本的风险了。
该氢化尾气优选含有少于1摩尔%的烯烃，更优选少于1摩尔%，最优选低于0.5摩尔%，如少于0.2摩尔%，或少于0.1摩尔%。
如附图中所示，将氢化尾气直接添加到ATR、CPO或POx中。术语“直接”是指没有任何改变氢化尾气的化学组成的中间过程，例如在所述氢化阶段与所述ATR、CPO或POx之间没有蒸汽重整器。
在更广泛的方面，本发明还包括减少设备中金属尘化的方法，所述设备含有废气，所述方法包括从所述废气中除去烯烃。特别地，通过其氢化除去烯烃。该方法特别可用于减少ATR、CPO或POx和废气通过其中的其它下游设备中的金属尘化。本发明包括通过除去通过该ATR、CPO或POx的废气中的烯烃含量减少ATR、CPO或POx 和其它下游设备中的金属尘化的方法。
优选地，所述去除烯烃含量的步骤是氢化阶段。
本文中所用术语“其它下游设备”是指位于ATR、CPO或POx下游并用于在生产蒸汽时冷却该合成气的废热锅炉和/或蒸汽过热器。
本文中所用术语“除去烯烃含量”是指将气体中的烯烃含量降低至少于0.2摩尔%，优选少于0.1摩尔%。
本文中所用术语“废气”是指含有烃和烯烃的任何气体，该气体必须在ATR、CPO或POx中重整以生成包含氢和一氧化碳的合成气。该废气优选是来自费托合成的尾气或来自用于生产汽油的下游工艺的尾气，如其中由包含甲醇和二甲醚的含氧化合物制造汽油的方法，例如通过美国专利US 4520216和US 4481305中公开的所谓TIGAS法。
本发明还包括不含烯烃的气体作为减少与该气体直接接触的设备的金属部件金属尘化的手段的用途。与该气体直接接触的设备优选是ATR、CPO或POx。优选地，该气体是废气；即来自工业过程，如上文定义的汽油合成的废气。
本文中所用并依据上文的术语“不含烯烃的气体”是指具有少于0.2摩尔%，优选少于0.1摩尔%的烯烃的气体。
本文中所用术语“与气体直接接触”是指将不含烯烃的气体直接添加至该设备或添加至单独的烃原料中，而不是首先通过重整的中间阶段，如蒸汽重整。
发明特征：
通过对应于所附权利要求的下列特征公开本发明。
1．在自热重整器（ATR）、催化部分氧化反应器（CPO）或部分氧化反应器（POx）的至少燃烧器部件中具有降低的金属尘化潜势的由烃原料制造合成气的方法，包括：使所述烃原料通过ATR、CPO或POx，并从ATR、CPO或POx中取出热排放合成气的流，使来自费托合成阶段的尾气通过氢化阶段以制造氢化尾气，并将该氢化尾气直接添加至所述ATR、CPO或POx中。
2．如特征1所述的方法，其中所述烃原料是已经通过至少一个绝热预重整阶段的气体。
3．如特征1或2所述的方法，其中所述烃原料是已经通过至少一个蒸汽重整阶段的气体。
4．如特征1至3任一项所述的方法，其中所述烃原料是来自以下过程的气体混合物：将原始烃进料气体分成两股流，使第一流通过至少一个蒸汽重整阶段以形成初级重整气体，使用第二流作为所述蒸汽重整阶段的旁路流，并随后将所述初级重整气体与该旁路流合并以形成所述烃原料。
5．如特征1至3任一项所述的方法，包括将原始烃进料气体分成两股流，由此使该流之一成为所述烃原料，并使另一流通过至少一个蒸汽重整阶段以形成重整气体。
6．如特征3-5任一项所述的方法，其中该蒸汽重整阶段是热交换重整，其中来自ATR、CPO或POx的热排放合成气的至少一部分用作所述热交换重整中的加热介质。
7．如特征5或6所述的方法，其中在所述热排放合成气将热传递至热交换重整之前、之中或之后将所述热排放合成气与所述重整气体混合。
8．如特征6或7所述的方法，包括将包含蒸汽的流添加至所述热排放合成气、所述重整气体、或热排放合成气与重整气体的混合流中。
9．如特征4至8任一项所述的方法，其中在拆分所述原始烃进料之前进行至少一个绝热预重整阶段。
10．如特征1至9任一项所述的方法，包括在ATR、CPO或POx中进行重整之前将氢化尾气与烃原料混合。
11．如特征1至9任一项所述的方法，包括以单独流形式将该氢化尾气添加至ATR、CPO或POx中。
12．如特征4、8和9任一项所述的方法，包括在ATR、CPO或POx中进行重整之前将氢化尾气与所述旁路流混合。
13．如特征4、6、8和9任一项所述的方法，包括将该氢化尾气与所述初级重整气体混合。
14．如特征1至13任一项所述的方法，进一步包括经费托合成将该合成气转化为液体烃。
15．减少设备中金属尘化的方法，所述设备含有废气，所述方法包括从所述废气中除去烯烃。
16．如特征15所述的方法，其中通过其氢化除去烯烃。
17．如特征15-16任一项所述的方法，其中该设备是ATR、CPO或POx。
18．不含烯烃的气体用于减少与所述气体直接接触的设备金属部件的金属尘化的用途。
19．如特征18所述的用途，其中与该气体直接接触的设备是ATR、CPO或POx。
20．如特征18-19任一项所述的用途，其中该气体是来自费托合成的尾气。
21．如特征18-20任一项所述的用途，其中不含烯烃的气体通过将所述烯烃氢化成链烷来获得。
附图说明
参照附图进一步描述本发明。图1显示了使用包括预重整器的单独的自热重整器时本发明的示意图。图2显示了串联的热交换重整与自热重整，并将氢化尾气添加至初级重整气体中。图3显示了具有初级重整阶段旁路的方法，将氢化尾气添加到旁路流中、或初级重整气体与旁路流的混合流中。
附图详述
附图1显示了使用单独的自热重整器制造用于费托合成的合成气的实施方案的一般示意图。将清洁的（不含硫和其它对重整催化剂的毒物）烃进料气体100，如天然气或其它含烃气体源与工艺蒸汽110混合，任选部分经饱和器/加湿器。将该混合物预热并在预重整器300中绝热预重整以便将任何高级烃转化为H2、CO、CO2和CH4。将所得烃原料混合物120与氧气130、保护蒸汽140和氢化尾气150一起进料到自热重整器400中。从该自热重整器400中提取合成气热排放物160，并进一步处理以生成进料到下游费托段500中的合成气。制造液体烃170，在进入自热重整器400之前使废气再循环流180通过氢化阶段600。也就是说，将氢化尾气从氢化器直接添加到自热重整器400中。
在图2中，将原始烃进料气体与蒸汽10的混合物送至热交换重整器25，在那里该混合物被催化蒸汽重整，并随后作为流30离开该热交换重整器。将初级重整气体流30与来自费托段150的氢化尾气65混合，形成ATR进料流70。将混合流70进料至自热重整器75，并还提供氧化剂80和保护蒸汽（未显示）。该初级重整气体部分燃烧，并在自热重整器75中在重整催化剂上趋向平衡。使来自自热重整器的热排放合成气110通过热交换重整器25。通过与在热交换重整器25中在催化剂上经受重整的气体热交换来冷却该合成气。由此冷却的合成气作为流120离开该热交换重整器，并进一步处理以形成进料至下游费托段150的合成气。将液体烃产品140与尾气再循环流60一起取出。在与初级重整气体30合并前，使该尾气再循环流60通过氢化器160以形成氢化尾气流65。也就是说，氢化尾气由该氢化器直接添加到该自热重整器400中。
在图3中，将原始烃进料气体（10）的混合物分成两股流20和40。将第一流20进料至热交换重整器25中，在那里该第一流20被催化蒸汽重整并随后作为初级重整气体30离开该热交换重整器。第二流40在热交换器45中预热，并绕开该热交换重整器。该初级重整气体30与预热的第二流50混合。将氢化尾气65添加到该混合流中或添加到预热的第二流50中，由此形成ATR进料流70。将该ATR进料流进料至自热重整器75，并还向其中提供氧化剂80和保护蒸汽（未显示）。该ATR进料流部分燃烧，并在自热重整器75中在重整催化剂上趋向平衡。使热排放合成气110通过热交换重整器25。通过与在热交换重整器25中在催化剂上经受重整的气体热交换来冷却该混合物流。由此冷却的合成气作为流120离开该热交换重整器，并进一步处理以生成进料至下游费托段150中的合成气。将液体烃产品140与尾气再循环流60一起取出。使该尾气再循环流60通过氢化器160以形成氢化尾气流65，其随后与初级重整气体30或旁路流50合并。挥着，该氢化尾气65还可以添加到初级重整流30中。也就是说，氢化尾气由该氢化器直接添加到该自热重整器400中。
实施例
在相同的试验装备中进行两次试验：
将800毫米长的Inconel 690样品放置在反应器中。将该反应器放置在具有三个加热区的炉中。Inconel 690样品的温度随着在炉中的位置而改变。样品温度为200至640℃。作为试验1，将样品暴露于具有表1中给出的组成的气体连续流。流速为100 Nl/h。压力为29barg。该条件保持626小时。在试验后使用立体显微镜和扫描电子显微镜检查该样品。该样品受到金属尘化腐蚀的侵袭。
类似于第一试验进行第二试验，除了在表1中给出了所用气体组成，作为试验2，并且条件保持672小时。试验后检查样品显示该样品没有受到金属尘化腐蚀的侵袭。
表1 气体组成（摩尔%）
| 组分 | 试验1 | 试验2 |
| 氢 | 12.1 | 12.1 |
| 水 | 22.6 | 22.6 |
| 一氧化碳 | 6.9 | 6.9 |
| 二氧化碳 | 7.8 | 7.8 |
| 乙烯 | 0.14 | 0 |
| 乙烷 | 0 | 0.14 |
| 甲烷 | 49.8 | 49.8 |
| 丙烷 | 0.45 | 0.45 |
| 1-丁烯 | 0.21 | 0 |
| 丁烷 | 0 | 0.21 |
两个试验中的两种气体组成相同，除了试验1中的气体含有烯烃（链烯），而试验2中的气体含有相应的链烷。在试验1中发生金属尘化侵蚀，但是在试验2中没有发生，其具有更长的持续时间。
存在链烯使得该气体对于金属尘化侵蚀具有更强的侵蚀性。由此，与其中使用尾气而未氢化的情况相比，使用氢化的尾气减少或消除了金属尘化。
Claims (16)
1.由烃原料制造液态烃的方法，包括：
a. 使所述烃原料通过ATR、CPO或POx，并从ATR、CPO或POx中取出热排放合成气流，
b. 经费托合成将该合成气转化为液体烃，
c. 使来自该费托合成阶段的尾气通过氢化阶段以制造含有少于1摩尔%烯烃的氢化尾气，和
d. 将该氢化尾气直接添加至所述ATR、CPO或POx中；
e. 任选地回收制造的该液态烃。
2.如权利要求1所述的方法，其中所述烃原料是已经通过至少一个绝热预重整阶段的气体。
3.如权利要求1或2所述的方法，其中所述烃原料是已经通过至少一个蒸汽重整阶段的气体。
4.如权利要求1至3任一项所述的方法，其中所述烃原料是来自以下过程的气体混合物：将原始烃进料气体分成两股流，使第一流通过至少一个蒸汽重整阶段以形成初级重整气体，使用第二流作为所述蒸汽重整阶段的旁路流，并随后将所述初级重整气体与该旁路流合并以形成所述烃原料。
5.如权利要求1至3任一项所述的方法，包括将原始烃进料气体分成两股流，由此使该流之一成为所述烃原料，并使另一流通过至少一个蒸汽重整阶段以形成重整气体。
6.如权利要求3-5任一项所述的方法，其中该蒸汽重整阶段是热交换重整，其中来自ATR、CPO或POx的热排放合成气的至少一部分用作所述热交换重整中的加热介质。
7.如权利要求5或6所述的方法，其中在所述热排放合成气将热传递至热交换重整之前、之中或之后将所述热排放合成气与所述重整气体混合。
8.如权利要求6或7所述的方法，包括将包含蒸汽的流添加至所述热排放合成气、所述重整气体、或热排放合成气与重整气体的混合流中。
9.如权利要求4至8任一项所述的方法，其中在拆分所述原始烃进料之前进行至少一个绝热预重整阶段。
10.如权利要求1至9任一项所述的方法，包括在ATR、CPO或POx中进行重整之前将氢化尾气与烃原料混合。
11.如权利要求1至9任一项所述的方法，包括以单独流形式将该氢化尾气添加至ATR、CPO或POx中。
12.如权利要求4、8和9任一项所述的方法，包括在ATR、CPO或POx中进行重整之前将氢化尾气与所述旁路流混合。
13.如权利要求4、6、8和9任一项所述的方法，包括将该氢化尾气与所述初级重整气体混合。
14.如权利要求1至13任一项所述的方法，其中步骤c)的该氢化尾气含有少于0.5摩尔%。
15.如权利要求1至13任一项所述的方法，其中步骤c)的该氢化尾气含有少于0.2摩尔%。
16.如权利要求1至13任一项所述的方法，其中步骤c)的该氢化尾气含有少于0.1摩尔%。
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA201100485 | 2011-06-29 | ||
| DKPA201100485 | 2011-06-29 | ||
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| CN201280032509.3A CN103748033B (zh) | 2011-06-29 | 2012-06-20 | 重整烃的方法 |
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| CN110944938A (zh) * | 2017-07-25 | 2020-03-31 | 托普索公司 | 用于制备合成气的方法 |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2838849C (en) * | 2011-06-29 | 2020-09-01 | Haldor Topsoe A/S | Process for reforming hydrocarbons comprising feeding a hydrogenated tail gas to the reforming stage |
| MX2015003867A (es) * | 2012-10-23 | 2015-07-17 | Haldor Topsøe As | Proceso para la preparacion de hidrocarburos. |
| GB201303723D0 (en) * | 2013-03-01 | 2013-04-17 | Johnson Matthey Plc | Process for treating gas mixtures |
| DE102016002728A1 (de) * | 2016-03-08 | 2017-09-14 | Linde Aktiengesellschaft | Verfahren zur Erzeugung von Synthesegas |
| KR102596324B1 (ko) * | 2017-07-25 | 2023-10-31 | 토프쉐 에이/에스 | 합성 가스의 제조 방법 |
| AU2018305876B2 (en) * | 2017-07-25 | 2023-12-14 | Haldor Topsøe A/S | Method for the preparation of synthesis gas |
| PL3658491T3 (pl) | 2017-07-25 | 2024-02-05 | Topsoe A/S | Sposób wytwarzania gazu do syntezy amoniaku |
| BR112020006088B1 (pt) * | 2017-09-29 | 2023-12-19 | Research Triangle Institute | Métodos e sistema de processamento de gás para produzir uma corrente de gás hidrogênio purificada |
| US10738247B2 (en) * | 2017-11-15 | 2020-08-11 | Gas Technology Institute | Processes and systems for reforming of methane and light hydrocarbons to liquid hydrocarbon fuels |
| CN109453544A (zh) * | 2019-01-04 | 2019-03-12 | 朗慕 | 高效自动液液萃取机 |
| CN115298134A (zh) * | 2020-02-28 | 2022-11-04 | 托普索公司 | 制备合成气的方法 |
| AU2021379842A1 (en) | 2020-11-13 | 2023-06-29 | Technip Energies France | A process for producing a hydrogen-comprising product gas from a hydrocarbon |
| WO2024094818A1 (en) | 2022-11-04 | 2024-05-10 | Topsoe A/S | Conversion of unsaturated hydrocarbon containing off-gases for more efficient hydrocarbon production plant |
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- 2012-06-20 MX MX2013015028A patent/MX2013015028A/es not_active Application Discontinuation
- 2012-06-20 CN CN201280032509.3A patent/CN103748033B/zh active Active
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| CN1310828C (zh) * | 2002-09-26 | 2007-04-18 | 赫多特普索化工设备公司 | 生产合成气的方法 |
| WO2006056594A1 (en) * | 2004-11-26 | 2006-06-01 | Shell Internationale Research Maatschappij B.V. | Method for treatment of a gas |
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| CN110944938A (zh) * | 2017-07-25 | 2020-03-31 | 托普索公司 | 用于制备合成气的方法 |
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| MX2013015028A (es) | 2014-01-24 |
| EA025435B1 (ru) | 2016-12-30 |
| CA2838849C (en) | 2020-09-01 |
| BR112013033570A2 (pt) | 2017-12-19 |
| CA2838849A1 (en) | 2013-01-03 |
| KR101920775B1 (ko) | 2018-11-21 |
| US20160045861A1 (en) | 2016-02-18 |
| WO2013000782A3 (en) | 2013-04-04 |
| KR20140043923A (ko) | 2014-04-11 |
| EA030771B1 (ru) | 2018-09-28 |
| CN103748033A (zh) | 2014-04-23 |
| US20160046488A1 (en) | 2016-02-18 |
| CN106957674B (zh) | 2019-03-01 |
| EA201490176A1 (ru) | 2014-04-30 |
| WO2013000782A2 (en) | 2013-01-03 |
| AU2012278043A1 (en) | 2014-01-16 |
| AU2012278043B2 (en) | 2016-01-07 |
| US20170002281A1 (en) | 2017-01-05 |
| EA201691199A1 (ru) | 2016-10-31 |
| US9162886B2 (en) | 2015-10-20 |
| US20140135409A1 (en) | 2014-05-15 |
| CN103748033B (zh) | 2016-12-07 |
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