CN1774391A - 制备氢气和氢气与一氧化碳混合物的方法 - Google Patents

制备氢气和氢气与一氧化碳混合物的方法 Download PDF

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CN1774391A
CN1774391A CNA2004800100803A CN200480010080A CN1774391A CN 1774391 A CN1774391 A CN 1774391A CN A2004800100803 A CNA2004800100803 A CN A2004800100803A CN 200480010080 A CN200480010080 A CN 200480010080A CN 1774391 A CN1774391 A CN 1774391A
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hydrogen
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steam
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T·H·泰欧
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Shell Internationale Research Maatschappij BV
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Abstract

一种由碳质原料制备氢气和含氢气与一氧化碳的气体混合物的方法，该方法进行下述步骤：(a)制备温度高于700℃的氢气和一氧化碳的混合物(51)，(b)在对流蒸汽重整区(44)中催化蒸汽重整碳质原料，作为单独产品得到氢气与CO摩尔比大于2的蒸汽重整产品和冷却的步骤(a)的流出物，其中通过在蒸汽重整反应区和步骤(a)的流出物之间对流换热为蒸汽重整反应提供所需的热量，和(c)从蒸汽重整产品中分离氢气。

Description

制备氢气和氢气与一氧化碳混合物的方法
技术领域
本发明涉及制备氢气和氢气与一氧化碳混合物的方法。
背景技术
EP-A-168892描述了一种吸热蒸汽重整反应，该反应在位于至少一个管内的固定床中进行，通过使部分氧化反应的至少部分热产品气沿管运行而使管内温度保持为800-950℃。根据该公开的专利文献，部分氧化反应和吸热生产合成气的组合可以提高合成气的产率，提高H2/CO的比，降低每得到一立方米合成气产品使用的氧气量，降低用于生产含CO和H2的气体混合物的设备的投资费用(与部分氧化相比)。
DE-A-3345088描述了进行蒸汽重整反应的反应器和方法。该公开专利文献描述了由天然气原料开始进行蒸汽重整反应的反应器。该反应器由管板组成，多个充填有合适催化剂的管从管板伸入反应器。通过使天然气部分氧化反应的热流出物从反应器管外部通入反应器，以此提供反应需要的热。这种蒸汽重整反应器也称为所谓的对流蒸汽重整(CSR)反应器。
US-A-6224789公开了一种方法，其中自热蒸汽重整步骤和对流蒸汽重整步骤相组合生产合成气。
WO-A-8801983公开了一种对流蒸汽重整反应器，其中用于加热反应器管的热气体通过在所述反应器的下部燃烧加热气体得到。
上述工艺中得到的合成气可以用作费-托工艺的原料。在一般的费-托工艺中，进行加氢处理步骤，使费-托合成链烷类产品转化为有价值的产品如洗涤剂原料、溶剂、石脑油、煤油、瓦斯油、润滑基础油和具有不同冷凝点的蜡。一般的加氢处理步骤是加氢、加氢异构化、加氢裂解和催化脱蜡。这些步骤需要氢气。本发明的目的是提供同时同时制备氢气和合成气的有效方法。
发明内容
一种由碳质原料制备氢气和含氢气与一氧化碳的气体混合物的方法，该方法进行下述步骤：
(a)制备温度高于700℃的氢气和一氧化碳的混合物，
(b)在对流蒸汽重整区中催化蒸汽重整碳质原料，作为单独产品得到氢气与CO摩尔比大于2的蒸汽重整产品和冷却的步骤(a)的流出物，其中通过在蒸汽重整反应区和步骤(a)的流出物之间对流换热为蒸汽重整反应提供所需的热量，和
(c)从蒸汽重整产品中分离氢气。
申请人发现：本发明的方法可以制备可用在费-托工艺中的合成气，还可以同时制备可用在下游加氢处理单元中的氢气。
附图说明
图1示出部分氧化反应器和对流蒸汽重整反应器的组合。
图2示出涉及图1的装置、费-托合成及其部分下游单元操作的集成方法。
具体实施方式
可以用能够生产具有为步骤(b)中的对流蒸汽重整区提供所需热量的所需热容的氢气和一氧化碳混合物的任何方法实施步骤(a)。
可以用公知的传统蒸汽重整装置实施步骤(a)，其中烃原料通过充填有蒸汽重整催化剂的管，并且其中所需热量由反应器管外部的燃烧器提供。这种蒸汽重整工艺步骤的例子例如公开在WO-A-9315999和EP-A-171786中。原料优选是含甲烷的原料如天然气。
步骤(a)的优选实施方案是公知的自热重整(ATR)工艺。ATR的原料可以是含烃原料如天然气。优选地，步骤(b)中制备的部分蒸汽重整产品用作步骤(a)的原料，其中用ATR中的含氧气体将其部分氧化。这种ATR步骤可以在由耐热衬里、可能还有水冷套的容器组成的传统类型的ATR反应器中进行，所述原料供给合适的燃烧器喷嘴。得到的火焰反应的产品在这种ATR反应器下部的催化剂床中存在的镍二段重整催化剂上趋于平衡。
步骤(a)的另一个优选实施方案是碳质原料和氧气的非催化部分氧化(POX)。在步骤(a)中进行部分氧化或ATR的优点是步骤(a)和部分步骤(b)的组合合成气产品的H2/CO摩尔比是1.5-3，优选1.9-2.3，使合成气产品适用于下面讨论的各种领域。
部分氧化和步骤(b)中的碳质原料优选是气态烃，合适的是甲烷。在本发明的上下文中，甲烷原料包括天然气、伴生气或C1-4烃的混合物。合适的烃主要包括，即大于90v/v％、特别是大于94v/v％的C1-4烃，特别是包括至少60v/v％的甲烷，优选至少75％，更优选90％的甲烷。优选使用天然气或伴生气。在步骤(b)和任选的步骤(a)中，在用所述气体作为原料之前优选脱除原料中所有的硫。
用于步骤(a)和步骤(b)的部分氧化或传统蒸汽重整工艺的原料优选是上述气态原料。在该优选实施方案中，步骤(a)和(b)的全部气态原料的10-90wt％，优选20-50wt％供给步骤(b)。
在步骤(a)中，可以根据公知的原理如Oil and Gas Journal，1971年9月6日，第85-90页中所述Shell Gasification Process进行部分氧化。描述部分氧化工艺例子的公开文献有EP-A-291111、WO-A-9722547、WO-A-9639354和WO-A-9603345。在这些工艺中，优选在没有催化剂的情况下使原料与含氧气体在部分氧化条件下接触。
含氧气体可以是空气(含有约21％的氧气)，优选富氧空气，合适的是最高含有100％氧气的空气，优选含有至少60vol％的氧气，更优选含有至少80vol％的氧气，更优选含有至少98vol％的氧气。可以用深冷技术生产富氧空气，但是优选用膜基法生产，例如WO-A-9306041中描述的方法。
在POX工艺步骤中原料与步骤(a)中的含氧气体的接触优选在置于反应器内的燃烧器中进行。为了调节步骤(a)中部分氧化反应得到的气态产品中的H2/CO比，可以在原料中加入二氧化碳和/或蒸汽。以气态产品的量计，至多15vol％，优选至多8vol％，更优选至多4vol％的二氧化碳或蒸汽加入原料。作为合适的蒸汽源，可以使用任选的下游烃合成中生产的水。
步骤(a)中部分氧化反应的气态产品的温度优选是1100-1500℃，H2/CO摩尔比是1.5-2.6，优选1.6-2.2。
可以用公知的蒸汽重整工艺实施步骤(b)，其中蒸汽和气态烃原料在CSR反应器中与合适的重整催化剂接触。对流蒸汽反应区优选包括配有一个或多个装有重整催化剂的管的管式反应器。这种反应器的各种设计都是已知的，都适用于本发明。这些反应器的例子描述在WO-A-0137982、EP-A-983964或WO-A-8801983中。
应用于对流蒸汽重整区的催化剂和工艺条件可以是蒸汽重整领域的普通技术人员熟知的那些催化剂和工艺条件。合适的催化剂包括任选负载在载体如氧化铝上的镍。气态原料的空速优选是700-1000L(S.T.P.)/L催化剂/hr，其中S.T.P.表示15℃的标准温度和1bar(绝对)的标准压力。蒸汽与碳(烃和CO)的摩尔比优选是0-2.5，更优选低于1，最优选0.5-0.9。如果在步骤(b)中使用这样低的蒸汽与碳的比，则催化剂优选包括VIII族金属。催化剂更优选包括(a)氧化物载体材料和(b)包括约0.1-7.0wt％的至少一种选自Pt、Ni、Pd和Co的金属的涂层，金属优选是铂；所述载体材料包括：
(i)至少80wt％的在涂布所述涂层前已经在最高约670℃的温度下煅烧的ZrO2；(ii)0.5-10mol％的至少一种选自Y、La、Al、Ca、Ce和Si的氧化物，优选La2O3。这种催化剂的例子例如描述在EP-A-695279中的催化剂。原料优选还包括一定量的CO2，其中CO2与碳(烃和CO)的摩尔比优选是0.5-2。步骤(b)的产品气的温度优选是600-1000℃，H2/CO摩尔比是0.5-2.5。
步骤(a)的含氢气和一氧化碳的气体的温度在步骤(b)中优选从1000-1500℃的温度降至300-750℃的温度。在步骤(b)中，对流蒸汽重整区中反应器管的金属壁表面温度优选保持低于1100℃。
一氧化碳和氢气的混合物(蒸汽重整产品)可以单独用于制备氢气，也可以部分与步骤(a)中得到的产品气组合，供给步骤(a)的部分氧化反应器，或者在如上所述在步骤(a)中使用ATR情况下用作原料。合适地，步骤(b)中得到的蒸汽重整产品的10vol％以上用于步骤(c)中。
在优选的实施方案中，在步骤(a)是POX工艺步骤的情况下，步骤(b)中得到的部分蒸汽重整产品供给步骤(a)。本发明还涉及下面的方法实施方案，其中使用对流蒸汽反应器，其具有分开的用于蒸汽反应器产品和冷却的步骤(a)的流出物的出口。将步骤(b)的部分蒸汽重整产品与步骤(a)的原料混合，或者更优选将其直接加入步骤(a)的部分氧化反应器中，此时的优点是可能仍然存在于蒸汽重整产品中的任何甲烷或高级气态烃随后可以进一步转化为氢气和一氧化碳。当针对蒸汽与碳的比小于1、特别是0.5-0.9的原料进行蒸汽重整步骤(b)时，这一点特别有利。在步骤(b)原料中的蒸汽与碳的比较小时操作该工艺是有利的，因为得到的合成气产品中还含有少量蒸汽，并且还可以使用较小的反应器设备。在蒸汽与碳的比很小情况下操作步骤(b)的缺点是蒸汽重整产品中存在更多未转化的甲烷。通过将部分蒸汽重整产品引导到步骤(a)可以克服这一缺点。将组合的混合物用在步骤(b)中，为实施步骤(b)提供所需的反应热。
上述实施方案示于图1。图1示出对流蒸汽重整反应器(44)。为了清楚起见，图1中没有示出反应器(44)的内构件。图1中还示出配有燃烧器(52)的部分氧化反应器(51)。碳质原料(50)和含氧气体(50′)供给燃烧器(52)。图1还示出步骤(b)的产品气(55)供给反应器(51)的上半部分。
蒸汽重整产品(55)优选靠近燃烧器(52)(即在反应器(51)的上半部分)供给，以最大获益于能使可能存在于产品(55)中的甲烷转化的反应器(51)区域内存在的800-1050℃的高温。相对于步骤(b)的原料(43)中以烃存在的碳，蒸汽重整产品(55)中的甲烷含量可以是5-30mol％碳。当在较低的温度和/或上述较低的蒸汽与碳的比下操作步骤(b)时，可以得到较高的甲烷含量。步骤(b)中的低温适宜为700-800℃，这是针对离开反应器(44)的蒸汽重整产品(55)测量的。由于反应器(44)内构件中使用的材料强度的原因，需要低温。
目的是操作步骤(b)使反应器(44)内构件温度保持在可接受水平的另一个实施方案是一方面使其具有用于蒸汽重整产品(55)的较高出口温度，另一方面降低(56)的温度。这可以通过将虚线(55′)所示的蒸汽重整产品与部分氧化反应的气态产品在远离燃烧器(52)的位置处混合来实现，使得当混合这两个物流时，蒸汽重整产品(55′)中存在的甲烷不会大量转化。优选在反应器(51)的下部进行混合。由于温度为1100-1500℃的部分氧化反应产品与温度低得多的蒸汽重整产品(55)混合，所以温度会比部分氧化反应产品的温度下降250-500℃。
因为蒸汽重整产品(55′)的出口温度适当地高出上述实施方案的物流，所以蒸汽重整产品(55′)具有较低的甲烷含量，相对于步骤(b)的原料(43)中以烃存在的碳，甲烷含量适宜为1-10mol％碳，优选2-5mol％碳。
这种甲烷优选在优选的自热重整步骤(g)中转化，也称为反应器(51)下半部分中存在的催化后重整。后重整催化剂床(53)可以是任何公知的重整催化剂，如含镍催化剂或上述用于CSR反应器的任何催化剂。自热重整步骤(g)的流出物随后供给对流蒸汽重整反应器(44)的入口(38)，其中的气体为对流蒸汽重整区供热。从出口(42)得到最终的合成气产品(63)。
在步骤(g)中，温度下降值适宜为20-70℃，优选40-60℃。步骤(g)中得到的甲烷含量下降的物流(56)的温度优选是950-1100℃，更优选980-1050℃。步骤(g)中的甲烷转化率适宜为10-50wt％。
图1还示出H2/CO摩尔比较高的蒸汽重整产品(55)的一部分(60)如何从蒸汽重整产品(55)中分离。图2示出该物流(60)如何根据步骤(c)供给氢气回收单元(61)以得到适用于加氢处理单元(66)的氢气(62)。
蒸汽重整产品(60)中的H2/CO摩尔比大于2，优选大于3，一般不大于6。氢气回收单元(61)可以是公知的膜分离单元、变压吸附器(PSA)或之后是PSA的膜单元组合。
上述工序得到的合成气(63)可有利地用作费-托合成工艺、甲醇合成工艺、二甲醚合成工艺、醋酸合成工艺、氨合成工艺的原料，或者供给使用合成气混合物作为原料的其它工序如涉及羰基化和加氢甲酰化反应的工序。优选向步骤(a)和(b)中供应再循环气。这些再循环气例如在前面例举的使用本发明方法制备的合成气的工艺得到的。这些再循环气可以包括C1-5烃，优选C1-4烃，更优选C1-3烃。这些烃或其混合物在5-30℃(1bar)、特别是20℃(1bar)下是气态。还可以存在氧化化合物如甲醇、二甲醚、醋酸。
本发明特别涉及制备含氢气和一氧化碳的气体(合成气)的方法，其中还可以实施附加步骤(d)、(e)和(f)。在步骤(d)中，用费-托催化剂将合成气催化转化为包括烃的物流。在步骤(e)中，步骤(d)的包括烃的物流分离成烃产品和气态再循环物流。适宜的烃产品是具有5个或更多个碳原子、优选4个或更多个碳原子、更优选3个或更多个碳原子的那些产品。气态再循环物流可以包括合成工艺中生产的普通气态烃、氮气、未转化的甲烷和其它原料烃、未转化的一氧化碳、二氧化碳、氢气和水。
在步骤(e)中，再循环物流供给步骤(a)和/或(b)。再循环物流优选供给步骤(a)的燃烧器，或者直接供给部分氧化反应器的内部。
任选地，再循环物流供给步骤(a)之前，将再循环物流中存在的部分或全部二氧化碳从再循环物流中分离。部分二氧化碳适于供给步骤(a)。
步骤(d)和(e)可以用公知的费-托工艺如Sasol工艺和ShellMiddle Distillate工艺实施。合适的催化剂的例子基于铁和钴。一般的反应器结构包括浆液反应器和管式反应器。这些工艺和其它工艺例如详细描述在EP-A-776959、EP-A-668342、US-A-4943672、US-A-5059299、WO-A-9934917和WO-A-9920720中。
图2示出图1的结构与费-托合成工艺单元(64)及其下游加氢转化单元(66)的组合。除图1外，图2还示出合成气(63)如何供给费-托合成工艺单元(64)。在单元(64)中，气态再循环物流(54)从烃产品(65)中分离后再循环到部分氧化反应器(51)。
在加氢处理单元中，(65)中存在的烃产品一般包括较大比例的沸点高于370℃的化合物，用公知的加氢裂解和加氢异构化方法将这种烃产品转化为中间馏分如煤油和瓦斯油产品。任何剩余的残渣都可以通过催化脱蜡工艺(图中未示出)进一步转化为基础油，这些工艺也需要氢气。这些下游加氢处理单元的例子描述在如WO-A-0107538、WO-02070631、WO-02070629和WO-02070627以及这些公开专利所引用的文献中。
加氢处理单元(66)还可以是加氢单元，其中在氢气和合适的加氢催化剂存在下，费-托合成产品(65)中存在的氧化物和烯烃选择性转化为链烷烃，以得到主要包括正链烷烃的各种产品。这些产品的例子是沸程为石脑油至煤油的溶剂、碳原子数为109-19的直链洗涤剂原料和冷凝点为30-150℃的蜡。

Claims (11)

1、一种由碳质原料制备氢气和含氢气与一氧化碳的气体混合物的方法，该方法进行下述步骤：
(a)制备温度高于700℃的氢气和一氧化碳的混合物，
(b)在对流蒸汽重整区中催化蒸汽重整碳质原料，作为单独产品得到氢气与CO摩尔比大于2的蒸汽重整产品和冷却的步骤(a)的流出物，其中通过在蒸汽重整反应区和步骤(a)的流出物之间对流换热为蒸汽重整反应提供所需的热量，和
(c)从蒸汽重整产品中分离氢气。
2、权利要求1的方法，其中蒸汽重整产品的H2/CO摩尔比是3-6。
3、权利要求1-2任一项的方法，其中氢气通过膜分离、变压吸附步骤、或之后是变压吸附步骤的膜分离进行分离。
4、权利要求1-3任一项的方法，其中步骤(b)中得到的部分蒸汽重整产品在步骤(a)中用作自热重整装置的原料，其中所述蒸汽重整产品被氧源部分氧化。
5、权利要求1-3任一项的方法，其中步骤(a)通过碳质原料和氧的非催化部分氧化进行。
6、权利要求5的方法，其中步骤(b)中得到的蒸汽重整产品和冷却的步骤(a)的流出物的剩余部分在向步骤(b)的蒸汽重整反应区供热后组合。
7、权利要求5的方法，其中蒸汽重整产品的剩余部分供给步骤(a)。
8、权利要求7的方法，其中蒸汽重整产品的剩余部分供给步骤(a)，使该物流与部分氧化的流出物混合，从而使部分氧化的流出物的温度下降250-500℃。
9、权利要求8的方法，其中温度下降的混合物在用于步骤(b)前进行催化后重整步骤，以提供进行蒸汽重整反应所需的热量。
10、权利要求1-9任一项的方法，其中对流蒸汽重整区包括配有一个或多个装有重整催化剂的管的管式反应器。
11、权利要求1-10任一项的方法，其中得到的一氧化碳和氢气的混合物用作费-托合成原料，并且步骤(c)中得到的氢气用于加氢转化工艺，在加氢转化工艺中费-托衍生的链烷烃原料转化为加氢、加氢异构化和/或催化脱蜡产品。
CNA2004800100803A 2003-04-15 2004-04-13 制备氢气和氢气与一氧化碳混合物的方法 Pending CN1774391A (zh)

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CNA2004800100822A Pending CN1774393A (zh) 2003-04-15 2004-04-13 进行蒸汽重整反应的反应器和制备合成气的方法

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EP1622828A1 (en) 2006-02-08
JP2006523596A (ja) 2006-10-19
WO2004092063A1 (en) 2004-10-28
CN1774393A (zh) 2006-05-17
JP2006523597A (ja) 2006-10-19
EP1622829A1 (en) 2006-02-08
WO2004092061A1 (en) 2004-10-28
US20080028680A1 (en) 2008-02-07
KR20050120719A (ko) 2005-12-22
EP1622827A1 (en) 2006-02-08
US7462209B2 (en) 2008-12-09
CN100381353C (zh) 2008-04-16
CN1774392A (zh) 2006-05-17
JP2006523598A (ja) 2006-10-19
JP2006523595A (ja) 2006-10-19
US20060191201A1 (en) 2006-08-31
WO2004092062A1 (en) 2004-10-28
US8986631B2 (en) 2015-03-24
US20070140954A1 (en) 2007-06-21
EP1613552A1 (en) 2006-01-11
US20090126272A1 (en) 2009-05-21
CN1832900A (zh) 2006-09-13
WO2004092060A1 (en) 2004-10-28
US20060260194A1 (en) 2006-11-23
US7550635B2 (en) 2009-06-23

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