CN102656121A - 一种净化工艺冷凝液的方法 - Google Patents

一种净化工艺冷凝液的方法 Download PDF

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CN102656121A
CN102656121A CN2010800334445A CN201080033444A CN102656121A CN 102656121 A CN102656121 A CN 102656121A CN 2010800334445 A CN2010800334445 A CN 2010800334445A CN 201080033444 A CN201080033444 A CN 201080033444A CN 102656121 A CN102656121 A CN 102656121A
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L·法尔卡斯
L·绍隆陶伊
S·布兰德斯
W·奥特
T·菲尔施蒂希尔
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Abstract

本发明公开了一种净化来自蒸汽重整工艺或蒸汽裂解工艺的工艺冷凝液17的方法。将工艺冷凝液17输送到电去离子工艺7中进行净化。

Description

一种净化工艺冷凝液的方法
本发明涉及一种净化来自蒸汽重整工艺或蒸汽裂解工艺的工艺冷凝液的方法。
在蒸汽重整工艺中，含碳氢化合物的原料例如天然气、石油醚或石脑油与蒸汽混合并且在蒸汽重整器中反应生成合成气，即主要是一氧化碳(CO)和氢气(H2)的气体混合物。通过在进一步处理步骤中的净化和分馏，由合成气获得物质如CO、H2或含氧气体(一种明确的H2和CO的混合物)，并作为产物放出。
该碳氢化合物可以发生高度转化反应。因此蒸汽重整工艺通常在蒸汽过量下实施。为去除过量的水，用这种方式生成的合成气被冷却到水蒸汽的露点以下。因此蒸汽冷凝出，并形成所谓的工艺冷凝液，其主要由水构成，并且通常带有杂质如甲醇、氨、二氧化碳、甲酸和乙酸。
在蒸汽裂解工艺中，含碳氢化合物的原料例如长链烃如石脑油、以及丁烷、丙烷和乙烷，或者柴油或者水基蜡与蒸汽混合且热裂解为短链烃。产生的粗气体主要包含氢气(H2)、甲烷(CH4)、乙烯(C2H4)和丙烯(C3H6)。所述粗气体通过低温分馏工艺进行分馏，从而主要获得有价值的产物乙烯和丙烯。
蒸汽裂解工艺通常在蒸汽过量下实施，以避免裂解的短链烃凝聚。蒸汽裂解工艺后粗气体经淬火和干燥。从而获得工艺冷凝液，其主要由水构成，并且通常带有多种杂质如裂解工艺中包含未裂解的长链烃、芳烃或其它重质烃的副产物和一些短链烃。
在本申请中，来源于蒸汽重整工艺或蒸汽裂解工艺的主要由水构成的冷凝液被称为工艺冷凝液。
根据现有技术，工艺冷凝液与通常从外部供给的软化水混合。这样形成的混合水随后逆着蒸汽重整或蒸汽裂解工艺中冷却的物质流进行脱气和汽化。蒸汽逆着冷却的废气过热之后，其部分蒸汽(工艺蒸汽)在工艺中内部使用，而剩余部分(出口蒸汽)不在蒸汽重整或蒸汽裂解工艺中使用，而在外部工艺中使用。出口蒸汽的产生使得不能在蒸汽重整工艺或蒸汽裂解工艺中利用但能在外部工艺中利用的热量得以利用，并增加了蒸汽重整工艺或蒸汽裂解工艺的经济效益。
通常，用户对出口蒸汽的品质要求很高，用上述方法产生的出口蒸汽不能满足他们的需要。例如，待用于冷凝式汽轮机中的出口蒸汽的电导率不应超过0.3μs/cm，由于工艺冷凝液中杂质的存在使其经常超过该数值。为了维持出口蒸汽的生产，存在多种工艺用于对工艺冷凝液在与软化水混合之前进行净化。
为净化工艺冷凝液，通过在汽提塔中汽提使杂质分离掉的工艺是已知的。包含空气或碳氢化合物的物质流(例如天然气)在这种情况下用作汽提气体。
在其它工艺中，工艺冷凝液膨胀，并且随后在洗涤塔中用低压蒸汽、空气或氮气脱气。杂质和汽提剂被排放到工厂外。为了满足对所产生的出口蒸汽的高纯度要求，这些工艺通过在相应的反应器中进行离子交换提供进一步的净化步骤。
在DE102006019100中公开了另一种在蒸汽重整工艺中生产蒸汽的工艺。根据在DE102006019100中公开的工艺和设备，产生了两种蒸汽流。第一种蒸汽流(工艺蒸汽)优选完全用于蒸汽重整工艺，而第二种蒸汽流(出口蒸汽)可以在外部使用。出口蒸汽优选仅通过汽化脱气的软化水(高纯度水)来产生。该工艺可以产生非常纯的洁净的出口蒸汽因此可以很好地利用蒸汽重整工艺的能量。该工艺的缺点是：为生产第二种洁净的蒸汽流需要第二汽鼓和用于输入软化水的第二脱气器。
本发明的目的是提供另一种净化工艺冷凝液的方法，其可用于净化源自蒸汽重整工艺或蒸汽裂解工艺的工艺冷凝液。
该目的通过将所述工艺冷凝液送到电去离子工艺中来实现。
本发明采用一种完全不同的方法净化来自蒸汽重整工艺或蒸汽裂解工艺的工艺冷凝液。电去离子工艺是一种用于净化水的基于膜的电化学方法。通过使用电活性介质和电压来影响离子传输，从而使可电离的杂质从液体中去除。通过电去离子工艺，产生净化水相和含可电离杂质的液相。
获得的洁净水可用于用已知方法生产洁净的蒸汽。根据本发明通过用电去离子工艺净化工艺冷凝液的方法，可获得理论电导率为0.06μs/cm的洁净蒸汽。这远低于冷凝式汽轮机对洁净蒸汽的要求。根据反复测试使用根据本发明的电去离子工艺，获得低于0.3μs/cm的电导率。该电导率足够满足洁净蒸汽的需要。因此本发明的工艺是从源自蒸汽重整工艺或蒸汽裂解工艺的工艺冷凝液中生产洁净蒸汽的好方法。
此外，本发明的工艺所需要的设备成本与现有技术相比低得多。用于汽提塔或建立第二蒸汽发生循环的成本要比简单的电去离子设备高很多。
在本发明一个优选的实施方案中，所述工艺冷凝液来自蒸汽重整工艺产生的工艺气体的干燥过程，蒸汽重整工艺之后进行水煤气转换反应产生的工艺气体的干燥过程或蒸汽裂解工艺产生的工艺气体的干燥过程。经过蒸汽重整炉后的工艺气体被冷却。从而形成混合相流。该混合相流在至少一个分离器中被分离成包含蒸汽重整工艺的反应产物的气相、和水相即工艺冷凝液。在本发明的该实施方案中，用电去离子工艺处理来自分离器底部的所述工艺冷凝液。如果蒸汽重整工艺是设计为生产尽可能多的氢气，则将来自蒸汽重整炉的工艺气体供应到中间水煤气转换反应过程中。在水煤气转换反应过程中，工艺气体中的一氧化碳与水反应生成二氧化碳(CO2)和氢气(H2)。产生的工艺气体通过上述方法冷却，从而产生除了在甲醇和乙醇含量上有一些区别之外的类似的工艺冷凝液。在本发明的该实施方案中将产生的工艺冷凝液送到电去离子工艺中。
在本发明最优选的实施方案中，在将工艺冷凝液输送到电去离子工艺中之前，先输送到预过滤器、热交换器、机械净化工艺、化学催化预处理和/或反渗透工艺中。根据该实施方案，在电去离子工艺的上游对工艺冷凝液进行预处理。将工艺冷凝液供应到由单独的预净化步骤组成的预净化工艺中。预过滤器和/或机械净化工艺可用于去除工艺冷凝液中的颗粒、团聚体或其它固体。通过热交换器可以将工艺冷凝液有利地调整到电去离子工艺的最佳操作温度。反渗透工艺对工艺冷凝液的预净化来说是一种合适的、简单且便宜的方法。对于由水煤气转换反应产生的工艺冷凝液，任选使用化学催化预处理也有利于将工艺冷凝液中的醇类转化为在工艺冷凝液中易于离解的有机酸，从而可用电去离子工艺处理。在本发明的电去离子工艺的上游使用上述全部或至少一个预处理工艺是有利的。
在电去离子工艺中得到的洁净的工艺冷凝液可有利地用作蒸汽重整工艺或蒸汽裂化工艺外部的洁净蒸汽。将该洁净的工艺冷凝液供应到汽鼓中，在这里利用蒸汽重整炉的热量产生蒸汽。通常加入一定量的软化水来弥补由于蒸汽重整或蒸汽裂解反应造成的损失。由本发明的工艺获得的洁净工艺冷凝液不含杂质并且满足洁净蒸汽的需要。因此在汽鼓中产生洁净蒸汽，并可以用于蒸汽重整或蒸汽裂解工艺外部例如冷凝式汽轮机中。产生的洁净蒸汽也可以有利地用于包括热电联产单元、汽轮机如背压式汽轮机或冷凝式汽轮机的外部蒸汽网。这种工艺蒸汽网通常要求一定程度的蒸汽质量以保证大型蒸汽系统的可靠性和避免操作事故。
根据本发明的另一个实施方案，在电去离子工艺中得到的洁净工艺冷凝液被循环用作蒸汽重整工艺或蒸汽裂解工艺的原料流的一部分。根据蒸汽重整工艺或蒸汽裂解工艺外部工艺的需要，部分洁净工艺冷凝液可用作蒸汽重整工艺或蒸汽裂解工艺的蒸汽。在本发明的该实施方案中循环的工艺冷凝液的量取决于蒸汽重整工艺或蒸汽裂解工艺外部需要的洁净蒸汽的量。
本发明具有多个优点。本发明从来自蒸汽重整或蒸汽裂解工艺的工艺冷凝液中生产出非常洁净的蒸汽。由这种工艺冷凝液生产洁净蒸汽所需的设备投资与现有技术相比有极大的降低。电去离子工艺需要的设备比汽提塔或具有独立进料循环的第二汽鼓更简单和更便宜。
为进一步说明本发明，对附图中所示的一个实施方案进行详细说明。
图1为本发明净化来自蒸汽重整工艺的工艺冷凝液的一个实施方案。
图2为电去离子工艺的任选进行的预处理的实施方案细节。
图1显示了本发明净化来自蒸汽重整工艺的工艺冷凝液的方法的一个实施方案。含碳氢化合物的原料2通过热交换器10进入蒸汽重整炉11的预加热部分11a。含碳氢化合物的原料与工艺蒸汽14在蒸汽重整炉的预加热部分11a中混合。蒸汽原料混合物通过管路15进入蒸汽重整炉11的重整部分11b。工艺气体通过一些容器16和一系列热交换器10进入分离器9。工艺气体通过热交换器10持续冷却，从而产生两相混合物。该两相混合物在分离器9中分离成气相产物5和液相17，所述气相产物被输送到进一步处理中，所述液相收集在分离器9的底部。液相17就是待净化的工艺冷凝液。工艺冷凝液17被输送到电去离子工艺7中。作为电去离子工艺产物，得到了洁净的工艺冷凝液18。洁净的工艺冷凝液18与一定量的软化水1一起供应到脱气器8中以补偿由于蒸汽重整工艺产生的损失。来自脱气器8的经脱气的洁净水相19通过换热器10进入汽鼓12中，其通过蒸汽重整炉11的预加热部分11a中的热交换产生出口的洁净蒸汽6。蒸汽重整炉11通过含碳氢化合物的燃料4与空气3的燃烧而加热。废气通过烟道13排入大气中。
图2显示了具有所有任选的预处理的电去离子工艺7的实施方案。工艺冷凝液17通过预过滤器20、热交换器21、机械净化22、化学/催化处理23和反渗透工艺24进入电去离子化7。预过滤器20用于去除工艺冷凝液17中的固体颗粒和较大的杂质。在热交换器21中调整工艺冷凝液17的温度至电去离子化最佳的操作温度。由于机械净化22，杂质如烟灰和尘土被去除。在化学/催化预处理23中杂质如醇类被转化为可离解并且因此能被随后的电去离子工艺处理的有机酸。反渗透工艺24产生软化的脱盐水相。工艺冷凝液17最终被电去离子工艺7净化到满足洁净蒸汽的要求，通过所述电去离子工艺剩下的杂质如离解的有机酸或碳酸根离子被去除。洁净工艺冷凝液18从电去离子工艺7被输送到脱气器8中。

Claims (5)

1.净化来自蒸汽重整工艺或蒸汽裂解工艺的工艺冷凝液(17)的方法，其特征在于，将所述工艺冷凝液输送到电去离子工艺(7)中。
2.根据权利要求1的方法，其特征在于，所述工艺冷凝液(17)来自蒸汽重整工艺产生的工艺气体的干燥过程、蒸汽重整工艺之后进行水煤气转换反应产生的工艺气体的干燥过程或蒸汽裂解工艺产生的工艺气体的干燥过程。
3.根据权利要求1或2的方法，其特征在于，在将所述工艺冷凝液(17)输送到电去离子工艺(7)中之前，先将其输送到预过滤器(20)、热交换器(21)、机械净化工艺(22)、化学催化预处理(23)和/或反渗透工艺(24)中。
4.根据权利要求1-3之一的方法，其特征在于，在电去离子工艺(7)中得到的洁净的工艺冷凝液(18)被用作蒸汽重整工艺或蒸汽裂解工艺外部的洁净蒸汽(6)，尤其用于包括热电联产单元和汽轮机的蒸汽网中。
5.根据权利要求1-4之一的方法，其特征在于，在电去离子工艺(7)中得到的洁净的工艺冷凝液(18)被循环用作蒸汽重整工艺或蒸汽裂解工艺的工艺蒸汽(14)的一部分。
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