CN109152986A - 用于从工业气体中除去氧气的方法 - Google Patents

用于从工业气体中除去氧气的方法 Download PDF

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CN109152986A
CN109152986A CN201780031896.1A CN201780031896A CN109152986A CN 109152986 A CN109152986 A CN 109152986A CN 201780031896 A CN201780031896 A CN 201780031896A CN 109152986 A CN109152986 A CN 109152986A
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gas
oxygen
siloxanes
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N·B·贾科布森
K·埃格布拉德
J·H·措伊滕
R·特灵-瑞斯托普
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Topsoe AS
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Abstract

通过从进料气体中除去含硫化合物和硅氧烷，加热进料气体，向加热的进料气体中注入一种或多种用于氧气转化的反应物，在至少一个合适的反应器中进行选择性催化氧气转化，和清洁所得的贫氧气体，从气体进料如垃圾填埋气体、蒸煮器气体或工业CO2废气中除去氧气。待注入的反应物包括H2、CO、氨、尿素、甲醇、乙醇和二甲醚(DME)中的一种或多种。

Description

用于从工业气体中除去氧气的方法
本发明涉及一种通过经由反应物注入的选择性催化氧化而从工业气体中除去氧气的新方法。
更具体地，本发明涉及降低工业气体中氧气含量的可替代途径，其中氧气含量的降低对于气体的增值是至关重要的。本发明的方法集中于填埋气体、蒸煮器气体和工业CO2废气。如今，通过PSA(变压吸附)、膜或洗涤器技术来实现氧气的去除，上述技术具有非常高的资本支出(CAPEX)以及有价值的组分(例如进入含氧废气的主气体中的甲烷)的大量损失。本发明包括向主气体流中添加组分，例如H2、CO、甲醇、氨或乙醇，并将所得气流引入到至少一个催化反应器。在所述反应器中，氧气通过催化剂被选择性地转化为CO2和水。
从燃料气体流中除去氧气通常是天然气网中气体分配的要求，并且当使用该气体作为车辆运输燃料时也有这样的要求。此外，除去氧气对于利用其他工业气体流，例如从含氧废气中生产商业级或工业级CO2，也是至关重要的。
US 3.361.531描述了通过在固体材料接触物质中的吸收而从含氧环境和气体混合物中除去氧气。更具体地，使选自碳酸铜、碳酸锰和碳酸铁的化合物在低于约500℃的升高温度下与含氢气体接触，从而将碳酸盐还原成相应的氧化物化合物。使该氧化物化合物在大约环境温度与所述含氧环境接触，从而吸收氧气并氧化该氧化物化合物。
在中小型项目中(通常至多10,000Nm3/h气体)，当今工业中占主导地位的技术是基于PSA和膜的技术，而蒸馏和低温分离是更大规模应用中的主要技术。
对于蒸煮器气体和填埋气体净化工业中的应用，气体流量在500至10,000Nm3/h的范围内，并且基于PSA和膜的技术占主导地位。除了通常禁止性的CAPEX之外，PSA和膜技术具有高的操作成本，这是由于其复杂性和气体压缩以及从进料气流进入含氧废气流的有价值的烃(例如甲烷)的大量损失。
在根据本发明的方法中，在从气体中除去含硫化合物和硅氧烷之后，将一种或多种适于催化氧化的组分注入到含氧的主气流中。选择组分和催化剂，使得催化剂使用料流中的氧气来氧化注入的组分，且基本上不氧化气流中的有价值组分，例如甲烷。
待注入的组分可以包括H2、CO、氨、尿素、乙醇和二甲醚(DME)等中的一种或多种。
活性催化剂可以包括金属形式或金属氧化物形式的选自钒、钨、铬、铜、锰、钼、铂、钯、铑和钌中的金属，其负载在选自氧化铝、二氧化钛、二氧化硅和二氧化铈及其组合的载体上。
工业气体中的硫杂质会在发电设备内部产生腐蚀性环境，或者甚至使可能存在的催化剂中毒。此外，存在于燃气发动机的进料气体中的硫化氢会引起润滑油的降解，并导致需要频繁维护。此外，如果要将气体输送到天然气管道或用作车辆燃料，则需要去除H2S。
清洁气体的另一个原因是其他杂质，例如硅氧烷，可能沉积在发热和发电设备中，并对内部部件造成严重损坏。
硅氧烷是包含硅、碳、氢和氧的有机硅化合物，其具有Si-O-Si键。硅氧烷既可以是线性的，也可以是环状的。它们可以存在于沼气中，因为它们用于各种美容产品，例如化妆品和洗发水，其被冲洗至下水道或以其他方式处理，使得它们最终进入城市废水和垃圾填埋场。硅氧烷在厌氧消化过程中不会分解，因此，从处理厂和垃圾填埋场捕获的废气通常会被这些化合物严重污染。已知使用具有活性炭或多孔二氧化硅作为吸附剂的非再生填充床吸附可以除去硅氧烷。也可以使用再生吸附剂以及基于气体冷却至非常低温度以将硅氧烷从气体中沉淀出来的单元。此外，使用液体提取技术。此外，这些技术可以组合使用。
因此，利用来自垃圾填埋场和厌氧蒸煮器的原料气的一个主要问题是提供具有低硫含量(即低于几百ppm)和具有非常低的硅氧烷(通常为线性或环状二甲基Si-O-Si化合物)含量的气流。用于天然气管道的规定更加严格。在这种情况下，必须将H2S除去至低于5ppm的残留浓度，并且还需要除去CO2和N2。含硫化合物的燃烧导致形成三氧化硫，其将与气体中的水分反应形成硫酸，硫酸可在冷点中冷凝并导致腐蚀。然而，特别地，硅氧烷会产生问题，因为它们在燃烧过程中转化为SiO2，导致发动机内部的磨料固体沉积物的累积，并造成损坏，缩短使用时间并增加对许多部件(如锅炉中的压缩机、风扇、鼓风机、燃烧器喷嘴、热回收表面)以及燃气发动机部件(如火花塞、阀门、活塞等)的维护要求。除了造成损坏和减少发动机的使用时间之外，为控制废气排放而安装的任何催化剂还对气流中夹带的SiO2敏感，实际上甚至比发动机本身更为敏感。例如，对于SCR(选择性催化还原)催化剂，SiO2耐受性可能低至250ppb。
由于上述原因，非常希望从气流中除去硅氧烷和含硫化合物。
因此，本发明涉及一种用于从工业气体进料中除去氧气的方法，所述方法包括以下步骤：
(a)从进料气体中除去含硫化合物和硅氧烷，
(b)向加热的进料气体中注入一种或多种用于氧气转化的反应物，
(c)在至少一个合适的反应器中进行选择性催化氧气转化，和
(d)清洁所得的贫氧气体，
其中在步骤(a)之前或之后加热进料气体。
通常，已经在低温下，即在加热气流之前，从气流中除去硅氧烷和含硫化合物。然而，也可以将氧气转化更紧密地配合到这样的设计中，其中从进料气体中除去含硫化合物和硅氧烷是热回路的一部分，即，在从气流中除去硅氧烷和含硫化合物之前将其加热。
优选地，要从中除去氧气的气体进料是垃圾填埋气体、蒸煮器气体或工业CO2废气。
在本发明的方法的一个优选实施方案中，处理气流，例如含有H2S和有机硫以及硅氧烷、CO2、H2O、甲烷和各种VOC(挥发性有机碳)化合物的垃圾填埋气体。
在步骤(c)中待注入的组分包括H2、CO、氨、尿素、甲醇、乙醇和二甲醚(DME)中的一种或多种。
与具有较低氮和氧含量的气体相比，将低质量(即，具有高含量的氮和氧)的垃圾填埋气体升级到管道质量更加困难和昂贵。使用反应物注入从低质量垃圾填埋气体中除去氧气将导致反应器中高的温升，这反过来又将损坏催化剂。然而，如果是在两个不同的位点而不是在一个位点处加入反应物，则可以使用两个串联的反应器，其间具有冷却和反应物注入。该方法具有额外的益处，即，在每个反应器之后回收的能量可以用于CO2分离单元(胺洗涤)中的再沸器以再生胺，并且它还可用作进料预热器。否则的话，用于再沸器和进料预热的能量必须来自电力或来自垃圾填埋气体或天然气的燃烧。
可以将来自氧化的热量转移到油回路中，该油回路用于在随后的CO2去除中在胺洗涤中运行再沸器以及用于预热进料。
参考附图进一步说明本发明，其中图1示出了该方法的一般概述，而图2示出了更具吸引力的配置。
在图1所示的一般情况下，上述方法在使用再生或非再生吸附技术以及气体冷却和冷冻除去硫和硅氧烷之后应用。在除去硫和硅氧烷之后，将气体加热至150-450℃，然后向主料流中注入H2、CO、氨、尿素、甲醇、乙醇、DME或其任何组合。然后将该料流导入选择性催化氧气去除反应器，其中氧气与注入的组分反应以形成CO2和水。热的反应器出口气体可以用于通过使用进料-流出物热交换器来加热反应器入口气体。
此外，来自催化反应器的热的出口气体可以用于加热进入硫和硅氧烷去除步骤的进料气体，使得这些步骤可以在升高的温度下操作。
在催化反应器的下游，使用基于胺的CO2去除技术、CO2水洗涤技术或基于溶剂的CO2去除技术去除CO2。或者，可以使用PSA或膜技术去除CO2。
在另一配置中，氮去除单元位于水去除单元的下游。
可以通过基于PSA或膜的技术除去氮，并且通过冷却和冷凝然后通过分子筛单元或者通过以TSA(变温吸附)配置进行操作除去水。
在图2所示的更具吸引力的配置中，对于硅氧烷和硫的去除，本发明与申请人用于蒸煮器和垃圾填埋气体调节的GECCOTM技术相结合。将进料气体加热至200-450℃并进料至硅氧烷吸收床，该吸收床包含氧化铝、氧化铝和镍、二氧化硅、或其组合。
除去硅氧烷后，将气体进料至催化反应器，该反应器含有负载在TiO2载体上的金属或金属氧化物形式的选自钨、钒、钼、铂和钯的催化剂。在该催化反应器中，催化剂将硫化合物转化为SO2，并且将VOC化合物(不是甲烷和轻质的[即C3和更低碳数]的烃)转化为CO2和水以及还有卤化氢，如果一些VOC被卤化的话。
向含有氧气的主气流中注入一种或多种适用于催化氧化的组分，即H2、CO、氨、尿素、甲醇、乙醇和DME等，并将该气流进料至含有催化剂的催化反应器中，所述催化剂例如负载在选自氧化铝、二氧化钛、二氧化硅和二氧化铈或其组合的载体上的金属或金属氧化物形式的钒、钨、铬、铜、锰、钼、铂、钯、铑或钌。在反应器中，注入的组分被选择性地氧化成H2O和CO2，而有价值的烃，如甲烷和轻质的[即C3和更低碳数]的烃基本上不转化。优选地，催化剂包含负载在TiO2载体上的金属或金属氧化物形式的钨、钒、钼、铂或钯。
热的反应器出口气体可以用于通过使用进料-流出物热交换器来加热反应器入口气体。
在氧去除步骤中产生的额外热量将为进料-流出物热交换器提供更高的温差，这降低了CAPEX。
在热交换器的下游，在湿的苛性或H2O2洗涤器中或在使用苛性吸附剂的干洗涤器中除去SO2。在除去SO2之后，通过使用基于胺的技术、基于溶剂的CO2去除技术、基于水的CO2去除技术或者PSA和/或膜技术来去除CO2。
可以使用基于膜或PSA的技术完成氮的去除。然后通过使用冷却和冷凝然后使用分子筛或者在TSA设置中除去水。或者，氮去除单元位于水去除单元的下游。
进一步优选的是，催化剂是整料式的。

Claims (13)

1.一种用于从工业气体进料中除去氧气的方法，所述方法包括以下步骤：
(a)从进料气体中除去含硫化合物和硅氧烷，
(b)向加热的进料气体中注入一种或多种用于氧气转化的反应物，
(c)在至少一个合适的反应器中进行选择性催化氧气转化，和
(d)清洁所得的贫氧气体，
其中在步骤(a)之前或之后加热进料气体。
2.根据权利要求1所述的方法，其中要从中除去氧气的气体进料是垃圾填埋气体、蒸煮器气体或工业CO2废气。
3.根据权利要求1或2所述的方法，其中步骤(e)中的清洁包括在分离单元中除去CO2，除去N2以及干燥经清洁的气体。
4.根据权利要求1-3中任一项所述的方法，其中所述气体具有高含量的氮和氧，并且其中两个反应器用于步骤(d)中的选择性催化氧气转化，且在两个反应器之间具有冷却。
5.根据权利要求4所述的方法，其中将在每个反应器之后回收的能量用于CO2分离单元中的再沸器。
6.根据权利要求1或2所述的方法，其中将除去硫和硅氧烷后的进料气体加热至150-450℃的温度。
7.根据权利要求1或2所述的方法，其中将进料气体加热至150-450℃的温度，然后进料至硫和硅氧烷去除单元。
8.根据权利要求7所述的方法，其中通过与来自氧气去除步骤的流出物气体进行热交换来加热进入硫和硅氧烷去除单元的进料气体。
9.根据前述权利要求中任一项的方法，其中待注入的组分包括H2、CO、氨、尿素、甲醇、乙醇和二甲醚(DME)中的一种或多种。
10.根据权利要求2所述的方法，其中所述垃圾填埋气体含有H2S和有机硫以及硅氧烷、CO2、H2O、甲烷和各种VOC(挥发性有机碳)化合物。
11.根据前述权利要求中任一项所述的方法，其中用于氧气转化的催化剂包括负载在选自氧化铝、二氧化钛、二氧化硅和二氧化铈的载体上的金属或金属氧化物形式的选自钒、钨、铬、铜、锰、钼、铂、钯、铑和钌的金属。
12.根据权利要求1所述的方法，其中硫去除步骤包括通过选择性催化转化将硫组分转化为SO2，并且在洗涤器中除去SO2。
13.根据权利要求12所述的方法，其中在湿的苛性或H2O2洗涤器中或在使用苛性吸附剂的干洗涤器中除去SO2。
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