CN103796948B - 制备合成气的方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 37
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 70
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 60
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 21
- 239000000571 coke Substances 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000003345 natural gas Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 3
- 239000002802 bituminous coal Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000003077 lignite Substances 0.000 claims description 3
- 239000003034 coal gas Substances 0.000 claims description 2
- 229960004424 carbon dioxide Drugs 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
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- 230000008569 process Effects 0.000 description 5
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- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910003080 TiO4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 238000010744 Boudouard reaction Methods 0.000 description 1
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
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- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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Abstract
本发明提供了制备合成气(3)的方法，其中将甲烷和二氧化碳(2)引入反应空间(R)并使之在升高的温度下在固体(W)的存在下生成氢和一氧化碳。使所述甲烷和二氧化碳通过含碳的颗粒材料(W)并在高温区(H)反应。
Description
本发明涉及制备合成气的方法，其中将甲烷和二氧化碳引入反应室，并使之在固体的存在下反应生成氢和一氧化碳。
合成气是由氢和一氧化碳组成的组合物，其可在多种工业操作中用作基础化学物质。例如，合成气为现有的生产甲醇、二甲醚或费-托产物的石油化工过程提供理想的交叉点(Schnittstelle)。
例如，可从专利申请US2009203519和US2011089378中获知这些方法。这两个申请都描述了甲烷和二氧化碳流经催化剂并通过干法重整进行反应的方法。由于Boudouard平衡和甲烷的热分解，形成了碳，其中一些碳沉积在催化剂上并使催化剂中毒。
为了解决这一问题，US2009203519提出了使用含铁沉积催化剂，形成的碳沉积于其上。然而，沉积催化剂的容量是有限的，因此必须定期，例如在流体的辅助下，进行催化剂再生。US2009203519没有公开关于为强吸热的重整反应提供热量的技术方案。
例如，US20110089378描述了催化剂如BaCO3-Ba2TiO4(1∶1)/NiO(催化剂A)、Sr2TiO4/NiO(催化剂B)和BaCO3-BaAl2O4(2∶1)/NiO的制备方法，及其在干法重整甲烷中的应用。该催化剂耐焦化至少8个小时，原则上适合于连续状态的实现。但是，这种解决方案被高催化剂成本所阻碍。
鉴于上述缺点，迄今一直未能在所述现有技术的基础上，开发通过甲烷与二氧化碳的反应工业规模生产合成气。
本发明的一个目的是具体说明使用甲烷和二氧化碳作为反应物制备合成气的方法。本发明的再一个目的是获得基本上不含固体颗粒的气体产物流。本发明的另一个目的是具体说明无需催化剂再生的连续状态的合成气制备。
根据本发明，通过甲烷和二氧化碳在含碳固体的存在下进行反应来实现这些目的。
甲烷和二氧化碳反应物优选在800℃至1600℃，更优选在900℃至1400℃的温度下进行反应。
根据本发明，所用的含碳固体有利的是含碳颗粒的形式。
本发明的含碳颗粒应理解为由含有至少50重量％，优选至少80重量％，并且更具体地为至少90重量％的碳的固体颗粒组成的材料。含碳颗粒有利地具有粒度(即可由具有限定的筛目尺寸筛分而确定的等效粒径)为0.5至100mm，优选1至80mm。含碳颗粒有利的是球形。多种不同的含碳颗粒可以用于本发明的方法。例如，此类颗粒可以由木炭、焦炭、焦炭屑和/或它们的混合物组成。焦炭屑一般具有小于20mm的粒度。基于颗粒总质量，含碳颗粒可进一步包含0％至15％重量，优选0％至5％重量的金属、金属氧化物和/或陶瓷。特别优选使用包含焦炭屑和/或低品级焦炭的颗粒，即，不直接适用于冶炼操作的焦炭、基于褐煤或烟煤的焦化厂焦炭和/或从生物质得到的焦炭。
与所制备的合成气的质量相比，有利的是使用1至3倍质量，优选1.8至2.5倍质量的含碳固体。
基于所形成的碳的总质量，有利的是至少90重量％，并且优选至少95重量％的由本发明的反应所形成的碳沉积在含碳固体上，更特别地在含碳颗粒上。
气体产物流有利地具有小于10mg固体/g气体的固体含量，优选小于5mg固体/g气体，更特别地小于1mg固体/g气体。
在本发明的方法的实施过程中，形成的碳不构成问题，因为它主要沉积在含碳固体上并仅仅改变其大小、结构和强度。更具体地，含碳颗粒从气相中过滤碳，从而使制备的合成气从所述反应室中除去而基本上不含碳颗粒。本发明的方法的一个实施方案利用了向反应室引入原子碳/氧比C/O＞1的气体反应物的碳沉积机制，这意味着，除了合成气，碳专门生成并沉积在含碳固体上。可选地，如果设置碳/氧比C/O＜1，可以从固体中除去碳。例如，通过将密度特别设置为0.7至1.4g/cm3，优选为0.8至1.4g/cm3的范围，这种方式可以采用低品级的颗粒，以制备可从反应室中去除并用于如鼓风炉的高品级焦炭产物。
在一个优选的实施方案中，本发明的方法的实施所需要的热能由包括烃和/或氢气的燃料的氧化或部分氧化生成。所用的氧化剂优选空气和/或富氧空气和/或工业纯氧气。通过使燃料与氧化剂混合并进行反应，可以在反应室外面进行氧化或部分氧化。然后将形成的热气体引入反应室并引导至含碳固体，向含碳固体和/或将参与反应的气体释放其相当部分的热量。可选地，可将氧化剂引入反应室中，在其中与现有的燃料混合，并使其反应。其中，含碳固体包括基于褐煤、烟煤或生物质的低品级焦化厂焦炭(其可能在升高的温度下放出热解气体)，供应所述含碳固体以回收能量，在热解区之后输入氧并至少部分氧化所述热解气体。
在另一个实施方案中，通过布置在反应室外部的电加热器产生热气体，引导气体流通过电加热器并在光弧的辅助下加热，然后在3000K到10000K，优选4000K到10000K的温度下引入高温区，将其热量释放给一种或多种反应物。例如，气体流可以由例如烃的分解过程中所得的氢组成，将氢从反应室中除去，随后可以对其进行清洗(如除尘)，将其输送到电加热器并至少部分地离子化。
在本发明的方法的另一个优选实施方案中，在反应室中由电磁感应产生热能。为了达到这个目的，将一个或多个导电元件以能够与将进行反应的气体和/或含碳固体热连通的方式布置在反应室中。通过交变电磁场在导电元件中产生涡电流，使其升温。将以这种方式产生的热量直接或间接地传递至将进行反应的气体，并因此满足合成气的形成所需的至少部分能量需求。导电元件位于反应室内的固定装置中和/或以颗粒形式分布在含碳固体中，更特别地是在含碳颗粒中，并因此与碳源一起被引入反应室以及从反应室中除去。可选地，含碳固体的阻抗可以用于直接感应加热。
还可以设想，通过使电流穿过含碳固体并将其加热以在反应室中产生热能。
对于每摩尔反应的甲烷，本发明的方法所提供的能量不超过150KJ，有利地不超过120KJ，优选不超过100KJ。
根据本发明，有利的是在大气压至50巴，优选10至50巴的压力下进行烃的热分解反应。
在本发明的分解反应过程中，在反应区中的停留时间有利的是0.5秒至25分钟，优选1至60秒，更特别地1～30秒。
含碳固体，更具体地，含碳颗粒优选以移动床的形式通过反应室，甲烷和二氧化碳有利地以逆流通过固体。为了达到这个目的，将反应室合理地设计成竖井，这意味着仅在重力的作用下发生移动床的移动。有利地，通过移动床的气流流动能够均匀发生。然而，也可以将含碳固体作为流化床引导通过反应室。这两种方案都允许进行连续或拟连续操作。
然后，在本发明的方法一个特别优选的方案中，当含碳固体作为移动床被引导通过反应室时，将其在环境温度下引入反应室，首先加热到最高温度，并随后再次冷却，最高温度位于温度在1000℃以上区域的高温区。冷却可进行至高于环境温度最大500K，优选300K，更优选50K，这意味着没有必要对从反应室中除去的含碳固体进行冷却或淬火。为了形成和保持所述的温度曲线，一个建议是在环境温度下将包含甲烷和二氧化碳的气体混合物引入反应室，并引导其逆流通过移动床。在其通过反应室的路径上，气体混合物与移动床直接接触进行热交换，气体混合物被加热到高达1000℃，同时移动床被冷却。进一步引导在高温区形成的热合成气逆流通过移动床并与所述床直接热交换进行冷却，从而使氢和一氧化碳以接近环境温度的温度从反应室中除去。由于高的能量聚集水平，可以补偿由于不存在特定的、高活性的催化剂而导致的整体能量需求的缺点。更特别地，制备合成气所需的热量在高温区生成和/或将其引入高温区。然而，并不排除热量在反应室中的其他位置产生和/或将其引入反应室的其他位置。
在高温区形成的合成气应尽可能地迅速冷却，从而可以有效抑制Boudouard反应和甲烷化，在此，一方面是一氧化碳、二氧化碳和碳形成甲烷，另一方面是氢和碳，或氢和一氧化碳形成甲烷。在某些情况下，移动床通过高温区的体积流率不足以实现这一目的。在这种情况下，本发明设想由含碳颗粒形成回路，逆流引导高温区中形成的一些合成气通过这个回路并在此过程中将其冷却。同样也可使用热交换管，由此从合成气中除去热量。经由颗粒回路除去的热量和经热交换管除去的热量可用于反应物的预热。
从反应室中除去的含碳颗粒的尺寸和密度分布比较分散，因此，这些颗粒不能直接用作例如所需粒度为35至80mm的高炉焦炭的颗粒。因此，根据本发明，通过筛分和/或分选和/或筛选对从反应室中除去的含碳颗粒进行分级。符合规格的颗粒作为产物排出。对于预期的应用而言，直径过小或密度太低的颗粒优选返回同一反应室或平行操作的反应室中。直径过大的颗粒在返回之前先碾碎，细小的颗粒被返回。
为了制备高纯度的合成气，可能需要清洁待引入反应室中的物质流，以除去合成气中的不需要的物质或者可能在反应室中转变为不需要的物质的物质。另外或可选地，也可以从由反应室中除去的气体中除去不需要的物质。不需要的物质包括，例如，硫化合物、单环或多环芳族化合物如苯、甲苯、二甲苯和/或萘，以及其他烃，例如，可以存在于其他原料中的天然气体。
因此，在本发明的方法的一个实施方案中，方法中产生的气体通过使其流过焦炭床来进行清洗，在此过程中除去合成气中的不需要的物质或者可能在反应室中转换为不需要的物质的物质。根据其品质，在气体净化过程中负载了不需要的物质的焦炭可以通过燃烧废弃或者作为进料提供给焦化厂。
更特别的，本发明的方法适用于天然气转化为合成气，取决于天然气矿床，其中天然气中的甲烷含量通常介于75％至99％摩尔分数。在这种情况下，二氧化碳和天然气可一起引入或分别从至少一个位置进入反应室。然而，也可以进行包含甲烷和二氧化碳气体的偶合气体的反应，偶合气体例如焦炉煤气和/或转炉煤气和/或来自熔铁炉的气体。特别合适的是使用工业纯氧气或富氧空气操作的熔铁炉炉气。考虑到其低的氮含量，在这种情况下获得的炉气含有相对较高含量的一氧化碳和二氧化碳。
与现有技术相反，在实施本发明的过程中，可以制备合成气而不会出现显著的固体负载。
尽管根据本发明的温度范围超出了现有技术中所述的范围，但这在经济上并不是缺点，因为此处描述的本发明的方案实现了迄今尚未达到的热量回收程度。
在下面的说明书中，通过在图1中示意性地描绘的工作实施例来更详细地阐明本发明。
图1显示了本发明方法的一种方案，其中甲烷和二氧化碳在连续操作中进行反应，得到合成气和碳产物，例如用于高炉的喷煤。
经进料管线1，将包含例如焦屑的含碳颗粒在环境温度下从上方引入反应室R，随后使这些颗粒在重力的作用下向下通过反应室进入移动床W。包含例如天然气和二氧化碳的混合物的含甲烷的气体2同时从下方通入反应室R，并向上逆流通过移动床W。气体2在进入反应室R时具有环境温度，在上升过程中与移动床W进行直接热交换。温度超过100℃的高温区H中的主要反应是甲烷和二氧化碳反应产生氢和一氧化碳，从而形成合成气。然而，由于甲烷的热分解和Boudouard反应，还形成了碳，并在移动床W的含碳颗粒上累积超过95％。形成的热合成气继续向上流动，并与移动床W直接热交换进行冷却，从而使合成气在高于环境温度但至少低于反应温度500K的温度下通过管线3除去。在分离装置T中，从合成气中除去氢气4，并随后在电加热器P中，在光弧的辅助下将其转换成热气体5。将具有3000K至10000K的温度的热气体5传递到高温区H，提供合成气制备所需的能量。由于积累了高的碳含量、低的灰分含量和硫含量，可以将颗粒6从反应室R的下部除去并用作例如，焦化厂佐剂或铸造厂合金铸铁的渗碳剂。不符合品质要求的颗粒6，例如因为其直径过大或过小，或密度太低，在分离装置S中通过筛分和/或分级和/或筛选去除，并且可以在粉碎后，经管线7返回到反应室R。剩余的残余物8是高炉焦炭，其作为高品级产物提供。
Claims (13)
1.制备合成气的方法，其中将甲烷和二氧化碳引入反应室中，并在含碳固体床中反应以得到氢和一氧化碳，其特征在于，引导所述含碳固体床作为移动床通过反应室，其中与所述移动床逆流引导在反应室中形成的合成气并与含碳固体直接热交换以冷却，使用具有0.1mm至100mm粒度的含碳颗粒作为含碳固体。
2.根据权利要求1的方法，其特征在于，甲烷和二氧化碳在800℃至1600℃的温度下进行反应。
3.根据权利要求2的方法，其特征在于，甲烷和二氧化碳在900℃至1400℃的温度下进行反应。
4.根据权利要求1至3中任一项的方法，其特征在于，所述含碳颗粒包含至少80重量％的碳。
5.根据权利要求1至3中任一项的方法，其特征在于，特别设定气体反应物的氧/碳比，使得碳在反应室中形成或从含碳固体中除去。
6.根据权利要求1至3中任一项的方法，其特征在于，至少一些合成气制备所需的热能在反应室中产生和/或经由热气体引入反应室中。
7.根据权利要求1至3中任一项的方法，其特征在于，连续地引导作为移动床的含碳固体通过反应室。
8.根据权利要求1至3中任一项的方法，其特征在于，在反应室中形成的合成气经热交换管进行冷却。
9.根据权利要求1至3中任一项的方法，其特征在于，使用基于高度多孔的褐煤或烟煤和/或从生物质得到的焦炭的低品级焦化厂焦炭和/或焦炭屑的颗粒作为含碳固体。
10.根据权利要求4的方法，其特征在于，将一些从反应室中除去的含碳颗粒返回到反应室。
11.根据权利要求1至3中任一项的方法，其特征在于，至少在一个位置将天然气和/或焦炉煤气和/或转炉煤气和/或熔铁炉或鼓风炉炉气引入反应室中，并进行反应以得到合成气。
12.根据权利要求1至3中任一项的方法，其特征在于，通过使所述方法中产生的气体通过焦炭床以除去所述气体中的不需要的物质。
13.根据权利要求1至3中任一项的方法，其特征在于，连续进行所述方法。
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2011
- 2011-07-05 DE DE102011106642A patent/DE102011106642A1/de not_active Withdrawn
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- 2012-07-05 KR KR1020147003076A patent/KR101909626B1/ko active IP Right Grant
- 2012-07-05 JP JP2014517518A patent/JP6133283B2/ja not_active Expired - Fee Related
- 2012-07-05 UA UAA201401061A patent/UA110840C2/uk unknown
- 2012-07-05 BR BR112014000094A patent/BR112014000094A2/pt not_active IP Right Cessation
- 2012-07-05 CN CN201280033368.7A patent/CN103796948B/zh active Active
- 2012-07-05 AU AU2012280624A patent/AU2012280624B2/en active Active
- 2012-07-05 WO PCT/EP2012/002837 patent/WO2013004391A1/de active Application Filing
- 2012-07-05 CA CA2839717A patent/CA2839717C/en active Active
- 2012-07-05 EP EP12734811.8A patent/EP2729405B1/de active Active
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- 2012-07-05 RU RU2014103786A patent/RU2610082C2/ru active
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101909626B1 (ko) | 2018-10-18 |
| CN103796948A (zh) | 2014-05-14 |
| JP6133283B2 (ja) | 2017-05-24 |
| RU2610082C2 (ru) | 2017-02-07 |
| EP2729405A1 (de) | 2014-05-14 |
| CA2839717C (en) | 2022-03-29 |
| EP2729405B1 (de) | 2015-08-19 |
| KR20140078603A (ko) | 2014-06-25 |
| US9266731B2 (en) | 2016-02-23 |
| AU2012280624B2 (en) | 2015-10-08 |
| ZA201309699B (en) | 2015-05-27 |
| RU2014103786A (ru) | 2015-08-10 |
| DE102011106642A1 (de) | 2013-01-10 |
| US20140217327A1 (en) | 2014-08-07 |
| PL2729405T3 (pl) | 2016-01-29 |
| ES2552528T3 (es) | 2015-11-30 |
| UA110840C2 (uk) | 2016-02-25 |
| BR112014000094A2 (pt) | 2017-02-14 |
| WO2013004391A1 (de) | 2013-01-10 |
| JP2014520739A (ja) | 2014-08-25 |
| CA2839717A1 (en) | 2013-01-10 |
| AU2012280624A1 (en) | 2014-02-20 |
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