CN107416770A - 制造合成气的方法 - Google Patents
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 86
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 23
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 97
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002918 waste heat Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 sulphur compound Chemical class 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
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Abstract
本发明涉及用于制造烃类(23)的方法，其中第一进料子料流(3)和第二进料子料流(4)由含烃进料料流(1)获得，其中第一进料子料流(3)借助部分氧化或自热重整(R)转化为第一合成气料流(8)，第二进料子料流(4)借助蒸汽重整(D)转化为第二合成气料流(10)，并随后与第一合成气料流(8)合并以提供第三合成气料流(5)，其至少第一部分(11)通过费托合成(F)转化为包含不同链长度的烃类的粗产物料流(16)，由此在尾气(17)中分离轻质烃类，以便回收它们并在部分氧化或自热重整(R)中使用它们，其特征在于不饱和烃类(21)与尾气(17)的至少一部分(19)分离，以变获得基本不含不饱和烃类的料流(20)作为部分氧化或自热重整(R)的进料。
Description
本发明涉及制造烃类的方法，其中第一进料子料流和第二进料子料流由含烃进料料流获得，其中第一进料子料流借助部分氧化或自热重整转化为第一合成气料流，第二进料子料流借助蒸汽重整转化为第二合成气料流，并随后与第一合成气料流合并以提供第三合成气料流，其至少第一部分通过费托合成转化为包含不同链长度的烃类的粗产物料流，在尾气中从其分离轻质烃类，以便回收它们并在部分氧化或自热重整中使用它们。
这种类型的方法从WO2006/117499A1中已知。通过部分氧化(POX)或自热重整(ATR)与蒸汽重整的平行连接，有利地能够结合所用工艺的长处，由此可以以相对简单和廉价的方式在宽范围的值中并根据费托合成的需要建立合成气中氢气对一氧化碳的比。同时，与个别工艺相比明显提高了合成气制造的效率。此外，在POX或ATR中使用尾气中存在的烃类有助于该工艺的高产率。
费托合成通常提供尤其包含合成油(称为“合成粗产物”)、具有四个或更少碳原子的轻质烃类、具有五个或更多(优选最多60个)碳原子的重质烃类以及未转化的合成气的粗产物料流。通常，尾气在冷阱中与粗产物料流分离，并包含饱和和不饱和的轻质烃类、以及含氧物(oxygenates)和未转化的合成气。
第一进料子料流，在用冷却工艺料流预热前，与回收的尾气混合，引入该POX或ATR反应器，并在放热工艺中与供应到该反应器的具有工业级纯度和亚化学计量量的氧反应。
尾气的回收将用于POX或ATR的原料的最大可能预热温度限制在不饱和烃类不会分解及在导管和反应器中造成烟炱沉积的温度。然而为了能够实现转化该原料所需的温度，必须提供提高量的氧气，这显著削弱了该工艺的经济可行性。
针对这一背景，由本发明解决的问题是提供初始规定的类型的方法，该方法对所提及的问题进行了改进。
根据本发明，通过从至少一部分尾气中分离不饱和烃类，以便获得基本不含不饱和烃类的料流作为用于部分氧化或自热重整的进料，由此解决了所述问题。
为了除去不饱和烃类，如本领域对此类目的已知的那样，适当地使用低温分离法。
优选地，基本不含不饱和烃类并由费托合成的尾气获得的料流与第一进料子料流一起或独立于第一进料子料流预热，并进料至POX或ATR。由于基本不存在不饱和烃类，直至与现有技术相比明显更高的温度均可实现该预热，而不具有任何形成烟炱沉积的风险，这使得能够以明显更少量的氧气进行POX或ATR。优选地，当其进料至POX反应器时，基本不含不饱和烃类的料流被预热至最高450℃的温度。如果将其进料至ATR反应器，预热甚至可能达到最高600℃的温度，因为所用料流抑制了分解过程。
在本发明的一种配置中，仅从一部分尾气中除去不饱和烃类，其余作为原料再循环至费托合成和/或用作燃料。
从尾气中分离的不饱和烃类，其主要是具有2或3个碳原子的那些，可以被废弃。但是，明智的是在本发明的方法中将它们用于欠烧(underfiring)，或为了贷方(for acredit)被释放作为用于物理或热利用的产品。
优选将该进料料流(其是例如天然气)或两种进料子料流脱硫，脱硫在本发明的情况下指的是将相关料流中的硫和/或至少一种硫化合物(优选几种或全部硫化合物)减少至低于预定值的含量，尤其低于10ppm，优选低于1ppm。适当地，使用氢气(例如通过加氢脱硫)进行该脱硫，该氢气例如由一部分合成气料流获得和/或由从费托合成的粗产物料流中分离的尾气获得。
在本发明的一个实施方案中，额外预期的是，该进料料流在分成两个进料子料流之前将穿过吸附器单元，尤其吸附该进料料流中的一种或多种硫化合物并从进料料流中除去。去除的化合物是例如H2S、CS2、COS和/或HCN。此外，并未排除相应地处理两个进料子料流的每一个而不是在专用吸附器单元中处理进料料流的可能性。
作为不同的制造方法的结果，通过POX或ATR获得的第一合成气料流具有不同于通过蒸汽重整制得的第二合成气料流的组成，由此能够通过改变体积流速的比来影响合并所述两种料流获得的第三合成气料流中的氢气对一氧化碳的比。为此目的，例如，可以在闭环控制下将该进料料流分成两个进料子料流，以便将合成气中氢气对一氧化碳的比调节至给定值。或者或此外，还有可能通过在闭环控制下分流一个或多个子料流，在将第一和第二合成气混合以获得第三合成气料流之前改变该第一和第二合成气的体积流速。
优选地，将第三合成气料流中的所述氢气对一氧化碳的比调节到1.5至2.5的值。
还可以预计，在本发明的一个实施方案中，第一和第二合成气料流和/或由所述两种料流形成的第三合成气料流用水冷却，在这种情况下，形成的水蒸气尤其用于发电。适当地，该水蒸气在用于第二进料子料流的蒸汽重整的反应器的废热系统中过热，随后膨胀以便在连接到发电机的蒸汽轮机中做功。
在本发明的进一步的实施方案中，设想该第三合成气料流将分成第一合成气子料流和第二合成气子料流，并且第一合成气子料流将用作费托合成中的进料，第二合成气子料流将被经受水煤气变换反应，其中存在于第二合成气子料流中的一氧化碳与水反应以获得氢气和二氧化碳，使得第二合成气子料流中的一氧化碳含量降低，氢气含量同时提高。
优选地，该第二合成气子料流在水煤气变换反应后被经受变压吸附，其中存在于变换的合成气子料流中的二氧化碳，以及甲烷和水，在第一压力下吸附在吸附器中，并产生含氢料流，该含氢料流穿过该吸附器，具有98.0体积％至99.9体积％的氢含量。通过用含氢吹扫气流吹扫其以解吸吸附的二氧化碳和其它吸附物质(例如甲烷和水)并从吸附器中将其去除，满载的吸附器在低于第一压力的第二压力下再生。满载的吹扫气体料流随后优选用作燃料，以便例如提供用于第二进料子料流的蒸汽重整的热。
在本发明的进一步的实施方案中，氧气从空气中分离(例如在低温空气分馏装置中)并用作部分氧化中的氧化剂。优选地，具有至少95体积％的氧含量的纯氧用作氧化剂。
还可以预计，来自通过变压吸附获自第三合成气料流的变换部分的含氢料流的氢气将用于氢化在尾气去除后残留的粗产物料流部分的重质烃类。以这种方式处理的粗产物料流随后直接作为含烃产物料流释放，或分成包含不同长度的烃类的许多馏分，其随后作为含烃产物料流继续前行。或者或此外，氢气可用于该进料料流或一种或两种进料子料流的脱硫。
下面将参照图1中示意性显示的工作实例详细描述本发明。
图1显示了本发明的方法的优选配置。
进料料流1(其是例如天然气)被引导穿过用于脱硫的吸附器单元A，以便去除存在的硫化合物和氰化氢至低于1ppm的含量。随后，脱硫的进料料流2分成两个进料子料流3和4，有可能单独调节这些子料流各自的体积流速，以便更特别地设定第三合成气料流5中的氢气对一氧化碳的比(参见下文)。
第一进料子料流3与料流20混合，所述料流主要由饱和烃类和一氧化碳、二氧化碳和氢气组成，并与其一起在预热器单元H中预热，随后将两个料流引入反应器R中作为进料料流6并与氧化剂7反应，以提供第一合成气料流8。如果反应器R是POX反应器，预热可以在最高450℃的温度下进行，当反应器R是ATR反应器时，600℃也甚至是可能的。所用氧化剂7优选是工业级纯度的氧气，其例如通过低温空气分馏获得。该氧气还可以以其它方式获得，例如在膜法中或通过变压吸附获得。
第二进料子料流4经受蒸汽重整D，为此其与水蒸气和/或二氧化碳9混合，并在700℃至950℃的温度和15巴至45巴的压力下，在合适的催化剂设置在其中的蒸汽重整器D的反应器管中转化为第二合成气料流10。
由于该生产方法，两个合成气料流8和10具有不同的氢气对一氧化碳的比，随后混合以获得具有1.5至2.5范围内的氢气/一氧化碳比的第三合成气料流5。
第三合成气料流5在冷却单元K中冷却和干燥后分成第一合成气子料流11和第二合成气子料流12，其体积流速的比为0.01至0.05。第一合成气子料流11作为进料被进料至费托合成F中，第二合成气子料流12经受水煤气变换反应W，其中存在的一氧化碳与水反应，以获得氢气和二氧化碳，由此获得具有提高的一氧化碳含量和降低的氢气含量的合成气子料流13。在水煤气变换中获得的合成气子料流随后施以已知的变压吸附D以获得富氢料流14和装载有去除的气体组分的吹扫气体料流15，该吹扫气体料流15随后充当燃料，并例如用于向蒸汽重整器D供热。
在费托合成F中，第一合成气子料流11转化为粗产物料流16，其包含具有四个或更少碳原子的轻质烃类、具有五个或更多碳原子的重质烃类，以及未转化的合成气。尾气17在冷阱S中与粗产物料流16分离，并尤其由未转化的合成气以及饱和和不饱和的轻质烃类组成。尾气17的第一部分18作为进料再循环到费托合成中，同时第二部分19送入去除单元T，在该单元中获得主要不含不饱和烃类的料流20和很大程度上由不饱和烃类组成的料流21。主要不含不饱和烃类的料流20随后与第一进料子料流3合并，而很大程度上由不饱和烃类组成的料流21可以例如作为产物释放。
在变压吸附D中制得的富氢料流14用在氢化反应器Z中，用于氢化去除尾气17后残留的粗产物料流22中的重质或不饱和烃类，并在该方法中转化为含烃产物料流23。
Claims (9)
1.用于制造烃类(23)的方法，其中第一进料子料流(3)和第二进料子料流(4)由含烃进料料流(1)获得，其中第一进料子料流(3)借助部分氧化或自热重整(R)转化为第一合成气料流(8)，第二进料子料流(4)借助蒸汽重整(D)转化为第二合成气料流(10)，并随后与第一合成气料流(8)合并以提供第三合成气料流(5)，其至少第一部分(11)通过费托合成(F)转化为包含不同链长度的烃类的粗产物料流(16)，由此在尾气(17)中分离轻质烃类，以便回收它们并在部分氧化或自热重整(R)中使用它们，其特征在于不饱和烃类(21)与尾气(17)的至少一部分(19)分离，以变获得基本不含不饱和烃类的料流(20)作为部分氧化或自热重整(R)的进料。
2.如权利要求1所述的方法，其特征在于与尾气(17)的至少一部分(19)分离的不饱和烃类(21)用于在所述方法中欠烧或为了贷方被释放作为用于物理或热利用的产品。
3.如权利要求1至2之一所述的方法，其特征在于设定第一进料子料流(3)和第二进料子料流(4)的体积流速比，以便设定第三合成气料流(5)中的氢气和一氧化碳的比。
4.如权利要求1至3任一项所述的方法，其特征在于通过在闭环控制下分流一个或多个子料流，在将第一合成气(8)和第二合成气(10)合并以获得第三合成气料流(5)之前，改变该第一合成气(8)和第二合成气(10)的体积流速比，以便设定所述第三合成气料流(5)中氢气和一氧化碳的比。
5.如权利要求3或4所述的方法，其特征在于将所述第三合成气料流(5)中氢气对一氧化碳的比设定为1.5至2.5范围内的值。
6.如权利要求1至5任一项所述的方法，其特征在于所述第三合成气料流(5)在冷却单元(K)中用水冷却以产生水蒸气，所述水蒸气随后用于产生电能，并且在蒸汽重整器(D)的废热系统中过热后，所述水蒸气在连接到发电机的蒸汽轮机中膨胀。
7.如权利要求1至6任一项所述的方法，其特征在于所述第三合成气料流(5)分成第一合成气子料流和第二合成气子料流(11，12)，第一合成气子料流(11)用作费托合成(F)的进料，而第二合成气子料流(12)经受水煤气变换反应(W)，以便降低第二合成气子料流(12)中的CO含量和提高氢气含量。
8.如权利要求7所述的方法，其特征在于在水煤气变换反应(W)后，所述第二合成气子料流(12)经受变压吸附(D)，以获得富氢料流(14)和装载有去除的气体组分的吹扫气体料流(15)。
9.如权利要求8所述的方法，其特征在于所述富氢料流(14)用于费托合成(F)中获得的重质烃类的氢化(Z)，和/或用于进料料流(1)或一种或两种进料子料流(3，4)的脱硫。
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