CN103562125A - 由合成气产生气体产品的方法 - Google Patents
由合成气产生气体产品的方法 Download PDFInfo
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- CN103562125A CN103562125A CN201280018128.XA CN201280018128A CN103562125A CN 103562125 A CN103562125 A CN 103562125A CN 201280018128 A CN201280018128 A CN 201280018128A CN 103562125 A CN103562125 A CN 103562125A
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- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000007789 gas Substances 0.000 claims abstract description 97
- 239000001257 hydrogen Substances 0.000 claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 66
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000000295 fuel oil Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000008246 gaseous mixture Substances 0.000 claims description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 21
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 20
- 235000011089 carbon dioxide Nutrition 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 9
- 239000010742 number 1 fuel oil Substances 0.000 claims description 7
- 238000002309 gasification Methods 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000009434 installation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000001131 transforming effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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Abstract
本发明涉及用于获得主要由氢组成的第一气体产品(13)和含有氢和一氧化碳的第二气体产品(12)的方法和设备，其中通过部分氧化(POX)由含有煤和／或重油的进料(3)产生的合成气(4)通过转化过程(S)、随后的干燥过程及去除酸性气体的过程(A)而反应生成富含氢的气体混合物(6)，该气体混合物被分离成为具有产品纯度的氢馏份(7)以及含有氢和一氧化碳的残余气体(8)。根据本发明，将所述含有氢和一氧化碳的残余气体(8)的至少一部分(10)用于获得含有氢和一氧化碳的第二气体产品(12)。
Description
技术领域
本发明涉及用于获得主要由氢组成的第一气体产品和含有氢和一氧化碳的第二气体产品的方法，其中通过部分氧化由含有煤和／或重油的进料产生的合成气通过转化、随后的干燥及去除酸性气体而反应生成富含氢的气体混合物，该气体混合物又被分离成为具有产品纯度的氢馏份以及含有氢和一氧化碳的残余气体。本发明进一步涉及实施该方法的设备。
背景技术
在工业规模上主要通过含碳进料的气化生产氢。一种在工业上广泛应用的气化方法是部分氧化(P0X)，通过部分氧化由烃类尤其是由更高沸点的烃类或煤产生所谓的“合成气”。在此，一般预热的进料与水蒸汽和氧化剂在反应室内在1300至1500℃的温度下以及高达100巴的压力下反应生成合成粗煤气，其大部分由氢、一氧化碳、二氧化碳和水组成。该反应所需的热量是通过进料中的烃类的不完全(部分)氧化产生的，为此将不足以使进料物质完全转化的量的氧引入反应室内。
为了提高氢的量，对合成气实施转化，其中一氧化碳和水在存在催化剂的情况下反应生成二氧化碳和氢。在转化后，将二氧化碳及其他酸性气体例如在甲醇洗涤装置中从转化的气体分离出，从而获得富含氢的气体混合物，然而该气体混合物不具有氢气产品所需的高于99体积％的纯度。因此，根据现有技术，将富含氢的气体混合物送入例如低温气体分离装置，在其中产生对于许多应用具有足够高的纯度的氢气产品以及氢含量低的残余气体。
除了氢气产品以外，经常还应当产生所谓的“合成煤气(Oxogas)”作为产品，该合成煤气是氢、一氧化碳以及可能存在的二氧化碳的具有确定组成的混合物。合成煤气的一个例子是甲醇合成气，其由氢(H2)、一氧化碳(CO)和二氧化碳(CO2)组成，其化学计量数S具有约为2的数值，该化学计量数由组分[H2]、[CO]和[CO2]的摩尔浓度根据S=([H2]-[CO2])／([CO]+[CO2])计算得出。
根据现有技术，一部分合成气在转化之前被分流以产生合成煤气，并在一个分离的处理过程中进行干燥及例如在物理洗气装置中从酸性气体分离出。如此获得的气体混合物的化学计量数S的数值通常小于合成煤气所需的数值。因此，为了调节S，从具有产品纯度的氢馏份分流出氢，并送至气体混合物中。若应当产生含有二氧化碳的合成煤气，则在酸性气体分离步骤中将二氧化碳不完全地从合成气去除。
用于对合成气的为了产生合成煤气而分流出的部分进行处理所需的装置涉及相当可观的投资成本，若与氢气产品的量相比所产生的合成煤气的量越少，则投资成本的大小越发挥决定性作用。若氢气产品的量比合成煤气的量多出超过四倍，则根据经验而言，实施该方法是不经济的。
发明内容
因此，本发明的目的是提出克服了现有技术的缺点的前述类型的方法和设备。
所提出的目的在方法方面根据本发明是通过将至少一部分含有氢和一氧化碳的残余气体用于获得含有氢和一氧化碳的第二气体产品而实现的。
残余气体通常含有所有成分，这些成分也存在于待分离的富含氢的气体混合物中，其由该气体混合物分离出；但是具有不同的组成。若该富含氢的气体混合物除了含有氢以外还含有一氧化碳和二氧化碳，则残余气体也含有这些物质，但是其中氢含量明显更低，而一氧化碳和二氧化碳的含量明显更高。该残余气体已经可以具有经济上可利用的合成煤气的组成，或者可以例如通过分离出二氧化碳和／或混入氢而进行处理以获得合成煤气。
在根据本发明的方法的一个实施方案中，将残余气体与一部分具有产品纯度的氢馏份混合以生产第二气体产品。该第二气体产品优选为甲醇合成气。
此外还建议，以如下方式实施转化和／或去除酸性气体，产生富含氢的气体混合物，其具有确定的一氧化碳含量和／或二氧化碳含量。以此方式可以控制残余气体的组成和量。优选以如下方式调节富含氢的气体混合物的组成，使产生的残余气体的组成对应于在经济上可利用的合成煤气的组成。为此，转化过程例如可以分为两步进行，其中在第一转化步骤之后将合成气分离成第一和第二支流。为了降低一氧化碳浓度，随后将第一支流在第二步骤中实施进一步转化，而第二支流最终与在第二转化步骤中得到的气体混合物合并成为部分转化的气体混合物。在此，这两股支流的体积流量以如下方式加以调节，使部分转化的气体混合物的氢／一氧化碳比例符合规定。
若二氧化碳在含有氢和一氧化碳的第二气体产品中是需要的，则可以在去除酸性气体的过程中仅不完全地并以可调节的分离程度将二氧化碳从已转化的气体混合物分离出。去除酸性气体的过程优选通过物理洗气装置进行，其中特别优选使用深冷的甲醇作为以物理方式发挥作用的洗涤剂。此类洗气装置可以所谓的“CO2滑动”的方式运行，其中与技术上可能达到的程度相比，不太彻底地将二氧化碳从待洗涤的气体混合物分离出，并将洗涤的气体的二氧化碳含量调节至预定的数值。
优选对通过去除酸性气体的过程获得的富含氢的气体混合物实施变压吸附过程，其中分离出具有产品纯度的氢馏份并产生含有氢的残余气体。但也可以将该气体混合物在低温过程中实施分离。将至少一部分量的氢馏份作为第一气体产品在设备边缘处排放出。
此外，本发明还涉及用于获得主要由氢组成的第一气体产品和含有氢和一氧化碳的第二气体产品的设备，该设备具有：气化装置，于其中可以由含有煤和／或重油的进料通过部分氧化产生合成气；转化反应器，于其中可以对合成气实施转化；由通过转化过程获得的气体混合物分离出水和酸性气体的装置；以及分离装置，于其中将通过分离出水和酸性气体获得的气体混合物分离成为具有产品纯度的氢馏份和含有氢的残余气体。
所提出的目的在设备方面是通过如下方式实现的，该设备具有用于处理残余气体的装置，于其中可由残余气体产生含有氢和一氧化碳的第二气体产品。
用于处理残余气体的装置例如可以包括分离装置，于其中可以从残余气体分离出组分。其优选具有混合装置，可以将残余气体导入其中，并以受控制的量送入一部分具有产品纯度的氢馏份。
根据本发明的设备优选包括转化装置，于其中可以产生具有确定的一氧化碳含量的气体混合物。该转化装置例如包括第一转化反应器以及与其以串联方式排列的第二转化反应器，在第一转化反应器中可以对全部的合成气实施转化，其中产生第一转化气体混合物。在第一转化反应器下游设置调节装置，于其中可以将第一转化气体混合物分离成为第一支流和第二支流。将第一支流导入第二转化反应器并在此转化成为第二转化气体混合物，同时可以将第二支流经由旁路管线绕过第二转化反应器，并与第二转化气体混合物合并成为部分转化的气体混合物。这两股支流的参数可以通过调节装置以如下方式加以控制，使部分转化的气体混合物的氢／一氧化碳比例符合规定。
在根据本发明的设备的一个实施方案中，设置有用于分离出酸性气体的装置，其允许调节分离出二氧化碳的程度。该用于分离出酸性气体的装置优选为物理洗气装置，于其中特别优选可以使用深冷的甲醇作为以物理方式发挥作用的洗涤剂。
根据本发明的设备的分离装置例如可以是低温气体分离装置的形式。但其优选为变压吸附器。
本发明除了允许生产氢气产品，还允许在不产生或仅产生小的额外成本的情况下生产合成煤气作为产品。在氢气产品的需要量明显高于合成煤气时，使用本发明是特别有利的。
下面依照图1中所图示的实施例更详细地阐述本发明。
附图说明
图1所示为用于由煤和／或重油产生氢气产品和合成煤气的设备。
具体实施方式
将氧经由管线1，水蒸汽经由管线2，煤或重油或煤和重油的混合物经由管线3作为进料物质送至气化装置POX。在气化装置POX的反应室内，通过部分氧化使进料物质转化为含有水、氢和一氧化碳及酸性气体的合成气4。将该合成气4导入转化反应器S，在此在两步转化过程中使受控制的量的一氧化碳与水完全反应生成氢和二氧化碳，从而可以排出具有确定的氢／一氧化碳比例的流5。为了分离出水和酸性气体，将该流5导入酸性气体洗气装置A，例如甲醇洗涤器，于其中获得富含氢的还含有一氧化碳的气体混合物6。将该气体混合物6送至变压吸附器DWA中，于其中以吸附方式分离成为具有产品纯度的氢馏份7以及含有一氧化碳和氢的残余气体8，其已经具有与合成煤气相似的组成。将一小部分氢馏份7经由管线9分流，并与在压缩机P1中压缩的残余气体10一起按计量导入混合装置M，并合并成为具有产品组成的合成煤气11。在压缩P2之后，将合成煤气11以及氢馏份7的剩余部分13作为产品12引导至设备边缘。
Claims (10)
1.用于获得主要由氢组成的第一气体产品(13)和含有氢和一氧化碳的第二气体产品(12)的方法，其中通过部分氧化(POX)由含有煤和／或重油的进料(3)产生的合成气(4)通过转化过程(S)、随后的干燥过程及去除酸性气体的过程(A)而反应生成富含氢的气体混合物(6)，该气体混合物被分离成为具有产品纯度的氢馏份(7)以及含有氢和一氧化碳的残余气体(8)，其特征在于，将所述含有氢和一氧化碳的残余气体(8)的至少一部分(10)用于获得含有氢和一氧化碳的第二气体产品(12)。
2.根据权利要求1的方法，其特征在于，为了产生所述第二气体产品(12)，将残余气体(8)与所述具有产品纯度的氢馏份(7)的一部分(9)混合。
3.根据权利要求1或2的方法，其特征在于，通过所述转化过程(S)产生具有确定的氢／一氧化碳比例的部分转化的气体混合物(5)。
4.根据权利要求1至3之一的方法，其特征在于，在所述去除酸性气体的过程(A)中仅不完全地并以可调节的分离程度将二氧化碳从所述部分转化的气体混合物(5)分离出。
5.根据权利要求1至4之一的方法，其特征在于，通过变压吸附将具有产品纯度的氢馏份(7)从所述富含氢的气体混合物(6)分离出。
6.用于获得主要由氢组成的第一气体产品(12)和含有氢和一氧化碳的第二气体产品(11)的设备，该设备具有：气化装置(POX)，于其中可以由含有煤和／或重油的进料(3)通过部分氧化产生合成气(4)；转化装置(S)，于其中可以对所述合成气实施转化过程；由通过转化过程获得的气体混合物分离出水和酸性气体的装置(A)；以及分离装置(DWA)，于其中可以将通过分离出水和酸性气体获得的气体混合物(6)分离成为具有产品纯度的氢馏份(7)和含有氢的残余气体(8)，其特征在于，该设备具有用于处理所述残余气体(8)的装置，于其中可由所述残余气体(8)产生含有氢和一氧化碳的第二气体产品(12)。
7.根据权利要求6的设备，其特征在于，所述用于处理所述残余气体(8)的装置(P1，M，P2)具有混合装置(M)，可以将残余气体(10)导入其中，并以受控制的量送入一部分(9)具有产品纯度的氢馏份(7)。
8.根据权利要求6或7的设备，其特征在于，所述转化装置(S)包括第一转化反应器及与其以串联方式排列的第二转化反应器以及具有调节装置的旁路管线，将一部分在所述第一转化反应器中产生的气体混合物经由所述旁路管线以受控制的方式绕过所述第二转化反应器，并与在所述第二转化反应器中产生的气体混合物合并成为具有确定的氢／一氧化碳比例的部分转化的气体混合物(5)。
9.根据权利要求6至8之一的设备，其特征在于，该设备包括用于分离出酸性气体的装置(A)，其允许调节分离出二氧化碳的程度。
10.根据权利要求6至9之一的设备，其特征在于，所述分离装置(DWA)是变压吸附器的形式。
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| CN112714749A (zh) * | 2018-10-05 | 2021-04-27 | 林德有限责任公司 | 用于使用转移变换器来生成气体产物的方法和装置 |
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| CN112714749A (zh) * | 2018-10-05 | 2021-04-27 | 林德有限责任公司 | 用于使用转移变换器来生成气体产物的方法和装置 |
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