CN1688676A - 氢气和高级烃的生产 - Google Patents

氢气和高级烃的生产 Download PDF

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CN1688676A
CN1688676A CNA038239019A CN03823901A CN1688676A CN 1688676 A CN1688676 A CN 1688676A CN A038239019 A CNA038239019 A CN A038239019A CN 03823901 A CN03823901 A CN 03823901A CN 1688676 A CN1688676 A CN 1688676A
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hydrogen
partial oxidation
kolbel
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丹尼斯·L.·雅各布松
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Abstract

含碳原料在部分氧化反应器中与氧气和水反应，生产出氢气和一氧化碳的混合物。氢气作为第一产物被取出，剩下的一氧化碳和水蒸气在双官能催化剂下生产出高级烃和二氧化碳。双官能催化剂提供了水气转移和Fischer－Tropsch功能。

Description

氢气和高级烃的生产
技术领域
本发明涉及从含碳原料的部分氧化中生产和回收氢气，以及用来自部分氧化反应器中的一氧化碳和水蒸气在含有铁基催化剂的淤浆反应器中生产出高级烃和二氧化碳的反应。
燃料电池作为大规模地生产电力的无污染的方法的出现以及减少汽油和柴油燃料中硫和芳香成分的需要增加了对氢气的需求。生产氢气的常规方法是天然气的水蒸气重整。与氢气一起形成的一氧化碳可以与水蒸气反应生产附加的氢气和一氧化碳(水煤气转移反应)。其它的原料如煤、石油焦和来自石油精炼操作的重油，当与水或水蒸气和氧气反应的时候生产出氢气、一氧化碳和二氧化碳的混合物。水煤气转移反应可以被用来从一氧化碳中生产更多的氢气。因此，为了使前面所提到的的方法中氢气的产量最大化，使用水煤气转移反应，原料中的碳被包含于二氧化碳中，该二氧化碳可以被分离、作为产物被出售或者被排放到大气中。对大气中的二氧化碳对全球变暖存在潜在影响的忧虑产生了使二氧化碳的产量和排放最小化的需求。本发明通过用Kolbel-Engelhardt(K-E)反应器代替水煤气转移反应器来生产有用的烃产物，降低了所生产的二氧化碳的量。
Kolbel-Engelhardt反应使用水蒸气代替氢气与一氧化碳在双官能催化剂下反应，主要地生产具有至少5个碳原子的烃和二氧化碳。该K-E反应最好在三相泡罩塔反应器中进行，该反应器中含有悬浮于蜡中的铁基粉末催化剂。该技术是前面所提到的一氧化碳在转移反应器中与水反应生产氢气和二氧化碳的常规技术的改进。(参见″ASingle IGCC Design for Variable CO2 Capture″，Luke F.O′Keefe等，Fifth European Gasification Conference，April 2002)。本领域的技术人员可以理解到，常规技术中所有的碳都被转移到二氧化碳中，而在目前的情况下，有一部分碳被转移到K-E反应器中所生产的烃中。
背景技术
在美国专利No.2,257,293中，H.Dreyfus教导了一种使用包括两个区的反应器制备烃的方法。第一区被用来进行水煤气转移反应以生产氢气和二氧化碳，第二区被用来在氢气和一氧化碳之间进行Fischer-Tropsch反应。在美国专利No.2,497,964中，Sumerford教导了一种将水蒸气加到流化床Fischer-Tropsch反应器以使碳的形成最小化的方法。在美国专利No.2,579,663中，Gilbert和Montgomery教导了一种使水蒸气和一氧化碳反应生产标准液态烃的方法。在美国专利No.2,786,863中，Kolbel和Engelhardt教导了一种使用水蒸气、一氧化碳和甲醇的混合物生产含氧化合物的方法。
Kolbel和Ralek，在″The Fischer-Tropsch Synthesis in the Liquidphase″，catalyst.Rev.-Sci.Eng.，21(2)，258(1980)中报道了，在淤浆反应器中，使用粉末状铁基Fischer-Tropsch催化剂，在水和一氧化碳之间生产烃的反应。该反应被称为Kolbel-Engelhardt(K-E)反应。
Louis de Vries(美国专利No.5,714,657)描述了一种包括继天然气的部分氧化(POX)后，在氢气和二氧化碳(逆水气转移)之间反应生成水和一氧化碳的方法。水和一氧化碳在K-E反应器中反应生成标准液态烃。来自于K-E反应器中的氢气和二氧化碳，通过POX反应器被循环回到逆水煤气转移反应器中来生产附加的一氧化碳和水。在美国专利No.6,416,568中，Wallace等教导了一种使用隔膜回收和净化从合成气体中分离出来的高压氢气流的方法。不能透过隔膜的含有一氧化碳的气体被用来作为燃气轮机/发电机组的燃料来生产电能。
发明内容
氢气、液态烃和二氧化碳是从诸如天然气、煤、石油焦或炼油厂炉底等原料中生产出来的。原料与氧气和水(和/或水蒸气)在部分氧化反应器(POX)中反应，生产出氢气和一氧化碳的混合物。由Texaco，Shell，Lurgi和其它公司所开发的部分氧化技术适合应用于本发明。例如，W.G.Schlinger等的美国专利No.3,544,291和GernotStaudinger的美国专利No.4,022,591中所描述的POX反应器可以被使用。氧气基本上与从空气分离设备获得的一样是纯的或者与在空气中一样用氮气和氩气稀释的。空气分离可以使用低温的或者压力回转吸收体系进行，这两种体系在商业上都是可行的。离开POX设备的热气体主要是氢气、一氧化碳、二氧化碳和水，它们通过冷淬或者在废热锅炉中冷却。典型地，如果原料是天然气或其它具有很少或没有灰的原料，可以使用废热锅炉。硫的化合物和二氧化碳通过使用冷却的甲醇、热的碳酸钾或胺体系的常规技术被除去。使用隔膜或其它的分离方式，如压力回转吸收，将第一产物氢气从剩余的二氧化碳和一氧化碳中分离出来。一氧化碳与水蒸气通过双官能催化剂反应，生产液态烃和二氧化碳(Kolbel-Engelhardt反应)。由于用于FT反应的氢气来自于水煤气转移反应，因此双官能的催化剂必须对水煤气转移反应和Fischer-Tropsch(FT)反应都具有活性。
为了获得最好的结果，催化剂粒子的直径应该优选位于1至150μ之间。按照Benham等的美国专利No.5,504,118制备的催化剂适合于本申请，并且在此引入作为参考。作为选择，根据美国专利No.5,504,118制备的催化剂可以通过添加键合剂来强化。
K-E反应器可以在介于450-550°F，更优选在460-520°F，最优选在480-500°F的温度范围内操作。K-E反应器可以在介于150-500psia，更优选在200-400psia，最优选在300-375psia的压力范围内操作。K-E反应器可以以每克催化剂每小时2-10标准升(normal liter)〔NL〕范围内的混合水蒸气和CO的容量速度操作，更优选，每克催化剂每小时2.5-7.5NL水蒸气和CO，最优选，每克催化剂每小时3.0-5.0NL水蒸气和CO。送到K-E反应器的气体的表观速度应该位于2-20cm/s的范围内，更优选为5-15cm/s，最优选为8-12cm/s。表观速度被定义为：在反应器的入口处的气体的温度和压力下，送到K-E反应器的混合气体在空的反应器中将具有的速度。水蒸气和一氧化碳的流量体积比应该位于0.5-2，更优选位于0.75-1.5，最优选位于0.9-1.1。
为了保持K-E反应器中的淤浆面保持恒定不变，以及使反应器中的催化剂藏量保持不变，必须使用催化剂/蜡分离装置。Benham等的已共同转让的美国专利No.6,068,760中所描述的催化剂/蜡分离装置适合应用于本发明，并在此引入作为参考。
部分氧化反应，可以被表示为：
(1)
其中z是原料中H∶C的比率。
也发生水煤气转移反应：
(2)
当用x代表与原料中每摩尔碳反应的水(或水蒸气)的摩尔数时，然后，方程式1和2可以结合起来给出：
(3)
所想得到的从气化器中排出的H2∶CO的比率规定了与原料反应的水(或水蒸气)的量。例如，如果r代表所想得到的H2∶CO的比率，那么：
(4)x＝(r-z/2))/(1+r)
从气化器排出的水的摩尔数由水煤气转移反应2的平衡常数确定。如果K代表平衡常数，那么，每摩尔气化的碳从气化器中排出的水的摩尔数是：
(5)NH2O＝[(x+z/2)x]/[K(1-x)]
Kolbel-Engelhardt反应需要水煤气转移反应(上面的方程式2)为Fischer-Tropsch反应提供H2：
(6)
结合方程式2和6，得出：
(7)
其中，u是H2O∶CO的使用比，在没有H2供给K-E反应器也没有净H2产出的情况下，其值为1/3。
附图说明
图1是联合生产氢气、烃和二氧化碳的工艺图。
在详细地解释本发明所公开的技术方案之前，应该理解，本发明不是将它的应用限制到所讨论的特定的设备中，因为本发明可以有其它的技术方案。此外，在这里所使用的术语是为了描述的目的，而不是为了限制。
具体实施方式
图1中显示了该方法的方块图。参照图1，送到分离设备1的空气生产出两种流——纯度为大约95％的氧气和基本上由氮气和氩气组成的流。作为选择，压缩空气可以不经过分离而被使用。预先加热的氧气或空气、水(和/或水蒸气)和原料如石油焦、煤或重油被送到部分氧化反应器2中，生产出〔主要地〕由氢气、一氧化碳、二氧化碳、水蒸汽、甲烷、灰和硫化合物组成的流。灰分在分离器3中被脱去，该气体通过直接的水淬或者通过废热锅炉4被冷却。这些气体在交换器5中被进一步冷却，冷凝水在分离器6中被除去。二氧化碳和硫化合物在酸性气体去除设备7中被除去，而氢气在氢气去除设备8中被除去。在氢气脱出之后所剩的气体主要是一氧化碳，其与水蒸气一起被送到K-E反应器9中。K-E反应的产物在产品回收设备10中被分离。来自产品回收设备10的尾气包含大百分比的二氧化碳，该二氧化碳可以在任选的CO2去除设备11中被除去。然后，剩余的尾气可以被用于联合循环发电厂12中的燃气轮机的燃料，或者用于其它需要燃料的工厂。从设备7和11中分离的二氧化碳可以作为产品被出售或者根据详情被隔离。
注解：计算是通过使用由Rentech(本发明的受让人)的工作人员开发的特有的自用计算机程序而进行的，以确定使用图1中的工艺可以获得的氢气和液态烃的量。
实施例1
将1千吨石油焦和水混合，形成按重量计含有62％的固体的浆料。该浆料和1002吨纯度为95％的氧气一起被送到部分氧化反应器中。在2445°F和400psia的压力下，离开反应器的气体具有下列的组成：
H2                  28.7MMSCF
CO                  45.9
CO2                 8.7
CH4                 0.2
H2O                10.1
N2+Ar             1.7
H2S                1.3
在除去H2S和H2O后，90％的H2(25.8MMSCF)被作为产品取出。在400psia下，剩余的气体和22.9MMSCF的饱和蒸汽一起，被送到以325psia和500°F工作的K-E反应器中。来自K-E反应器的产品由1728Bbl的C5+烃和39.0MMSCF的CO2组成。在这种情况下，原料中69.9％的碳被转移到所捕获的CO2中，23.0％的碳被转移到C5+烃。
在使用转移反应器代替K-E反应器的常规技术中，将生产69.9MMSCF的H2和51.0MMSCF的CO2。在这种情况下，将有91.3％的碳被转移到所捕获的CO2中。
实施例2
将1千吨匹兹堡No.8煤(Pittsburgh No.8 coal)和水混合，形成按重量计含有64％的固体的浆料。该浆料和878吨纯度为95％的氧气一起被送到部分氧化反应器中。在2387°F和400psia的压力下，离开反应器的气体具有下列的组成：
H2                  28.8 MMSCF
CO                  36.6
CO2                 9.2
CH4                 0.04
H2O                13.5
N2+Ar             1.4
H2S                0.8
在除去H2S和H2O后，90％的H2(25.9MMSCF)被作为产品取出。在400psia下，剩下的气体和18.3MMSCF的饱和蒸汽一起，被送到以325psia和500°F工作的K-E反应器中。来自K-E反应器的产品由1380Bbl的C5+烃和31.8MMSCF的CO2组成。在这种情况下，原料中67.9％的碳被转移到所捕获的CO2中，21.9％的碳被转移到C5+烃中。
在使用转移反应器代替K-E反应器的常规技术中，将生产出61.5MMSCF的H2和42.9MMSCF的CO2。在这种情况下，将有91.5％的碳被转移到所捕获的CO2中。
实施例3
将1千吨来自炼油厂的H-油(H-oil)和988吨纯度为95％的氧气及257吨水蒸汽一起送到部分氧化反应器中。在2400°F和450psia的压力下，离开反应器的气体具有下列成分
H2                  37.4MMSCF
CO                  49.2
CO2                 2.2
CH4                 0.7
H2O                4.0
N2+Ar             1.5
H2S                1.3
在除去H2S和H2O后，90％的H2(33.7MMSCF)被作为产品取出。在400psia下，剩下的气体和24.6MMSCF的饱和蒸汽一起，被送到以375psia和500°F工作的K-E反应器中。来自K-E反应器的产品由1854 Bbl的C5+烃和33.0MMSCF的CO2组成。在这种情况下，原料中62.1％的碳被转移到所捕获的CO2中，25.9％的碳被转移到C5+烃中。
在使用转移反应器代替K-E反应器的常规技术中，将生产出81.4MMSCF的H2和47.9MMSCF的CO2。在这种情况下，将有90.1％的碳被转移到回收的CO2中。
实施例4
将1千吨来自精炼厂的石油焦和729吨水混合形成淤浆并将其和5746吨空气一起送到部分氧化反应器中。在2445°F，400psia的压力下离开反应器的气体具有下列的成分
H2                 22.8MMSCF
CO                 36.5
CO2                18.3
CH4                0.01
H2O                   21.2
N2+Ar                119.8
H2S                   1.3
在除去H2S和H2O后，90％的H2(20.5MMSCF)被作为产品取出。在400psia下，剩下的气体和18.2MMSCF的饱和蒸汽一起，被送到以300psia和500°F工作的K-E反应器中。来自K-E反应器的产品由1375Bbl的C5+烃和39.8MMSCF的CO2组成。在这种情况下，原料中71.2％的碳被转移到所捕获的CO2中，18.3％的碳被转移到C5+烃。
在使用转移反应器代替K-E反应器的常规技术中，将生产出55.7MMSCF的H2和51.3MMSCF的CO2。在这种情况下，将有91.7％的碳被转移到回收的CO2中。
实施例5
将3000万标准立方英尺的甲烷和731吨的98％纯氧一起送到部分氧化反应器中。在2100°F和400psia的压力下，离开反应器的气体具有下列组成：
H2                    53.4MMSCF
CO                    28.0
CO2                   1.0
CH4                   1.1
H2O                  4.5
N2+Ar               0.1
在除去H2O后，90％的H2(48.1MMSCF)被作为产品取出。在400psia下，剩下的气体和14.0MMSCF的饱和蒸汽一起，被送到以375psia和500°F工作的K-E反应器中。来自K-E反应器的产品由1054Bbl的C5+烃和19.5MMSCF的CO2组成。在这种情况下，原料中65.0％的碳被转移到所捕获的CO2中，26.2％的碳被转移到C5+烃中。
在使用转移反应器代替K-E反应器的常规技术中，将生产出76.8MMSCF的H2和27.0MMSCF的CO2。在这种情况下，将有90.0％的碳被转移到回收的CO2中。
虽然参照公开的技术方案对本发明进行了描述，然而可以对本发明进行多种修改和变化，其结果依然落于本发明的范围内。关于在这里所公开的具体技术方案并不意味着也并不应该推断为是对本发明的限制。

Claims (26)

1、一种从含碳原料中生产和回收氢气和烃的方法，其包括：
首先，在部分氧化反应器中使含碳原料与氧气(或空气)和水或水蒸汽反应；
从所述的部分氧化反应器排出的气体中回收氢气和一氧化碳；
使从部分氧化反应器中排出的一氧化碳与水蒸气在Kolbel-Engelhardt反应器中反应，生产烃和二氧化碳；并且
回收在Kolbel-Engelhardt反应器中生成的烃和二氧化碳。
2、权利要求1的方法，其中所述的含碳原料是煤。
3、权利要求2的方法，其中所述的煤以水淤浆被送到部分氧化反应器中。
4、权利要求1的方法，其中所述的含碳原料是石油焦。
5、权利要求4的方法，其中所述的石油焦以水淤浆被送到部分氧化反应器中。
6、权利要求1的方法，其中所述的含碳原料是来自炼油厂的残油。
7、权利要求6的方法，其中与来自炼油厂的残油一起加入的水在气化器操作压力下是饱和水蒸气。
8、权利要求1的方法，其中所述的含碳原料是天然气。
9、权利要求1的方法，其中从部分氧化反应器中排出的气体的H2∶CO的比率为约0.5-2.5。
10、权利要求1的方法，其中使用可选择性地渗透氢气的膜使回收的氢气由从部分氧化反应器排出的气体中分离。
11、权利要求1的方法，其中通过压力回转吸收使回收的氢气由从部分氧化反应器排出的气体中分离。
12、权利要求1的方法，其中Kolbel-Engelhardt反应器是三相淤浆泡罩塔反应器。
13、权利要求12的方法，其中Kolbel-Engelhardt反应器使用沉淀的铁催化剂。
14、权利要求13的方法，其中催化剂含有钾。
15、权利要求14的方法，其中钾和铁的重量比为约0.005-0.015，更优选为约0.0075-0.012，最优选为约0.008-0.010。
16、权利要求13的方法，其中催化剂含有铜。
17、权利要求16的方法，其中铜和铁的重量比为约0.005-0.020，更优选为约0.0075-0.015，最优选为约0.009-0.012。
18、权利要求13的方法，其中催化剂是经喷雾干燥的。
19、权利要求17的方法，其中所述催化剂的粒径为约1-150微米，优选约10-100微米，最优选约20-80微米。
20、权利要求13的方法，其中催化剂含有用于提高抗磨耗性的化合物。
21、权利要求12的方法，其中Kolbel-Engelhardt反应器的温度被保持在约450°F-550°F，优选约460°F-520°F，最优选约480°F-500°F。
22、权利要求12的方法，其中Kolbel-Engelhardt反应器的压力被保持在约150-500psig，优选约200-450psia，最优选约300-400psia。
23、权利要求12的方法，其中加入到Kolbel-Engelhardt反应器的水在该反应器的操作压力下是饱和水蒸气。
24、权利要求22的方法，其中Kolbel-Engelhardt反应器中饱和水蒸气和一氧化碳的摩尔比为约0.5-1.5，更优选为约0.75-1.2，最优选为约0.9-1.1。
25、权利要求12的方法，其中K-E反应器以每克催化剂每小时约2-10标准升的混合的蒸气和一氧化碳的空速进行操作，优选每克催化剂每小时约2.5-7.5标准升，最优选每克催化剂每小时约3.0-5.0标准升。
26、权利要求12的方法，其中加入到K-E反应器的气体的表观速度为约2-20cm/s，优选约5-15cm/s，最优选约8-12cm/s。
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CN102918136A (zh) * 2010-05-10 2013-02-06 液化石油公司 生产烃组合物的方法

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