CN104220144B - 从气态或液态物流中除去汞的方法 - Google Patents
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Abstract
本发明涉及从含汞材料例如进料流、天然气物流、天然气冷凝物等中除去汞的方法。该方法包括使含汞流体(例如气体或液体)物流流过聚合型膜接触组件，同时清洁或洗涤溶液流过该膜的另一侧。洗涤溶液促进从第一溶液中借助例如其中所含的与汞具有反应性的组分除去汞。
Description
相关申请
本申请要求2012年3月22日提交的美国临时申请61/614,209的优先权，其整体引入作为参考。
发明领域
本发明涉及从流体例如液体、气体和气态冷凝物中除去汞或含汞化合物的装置和方法。更具体地，涉及级联使用的多孔膜和洗涤溶液从前述流体中除去汞的用途。
背景和现有技术
汞(Hg)是许多天然产品包括烃燃料的杂质。它以多种形式如单质汞存在。有机和无机化合物也含有它。在本文提及的烃燃料的情况中，据信汞来自于获取燃料如天然气之处的地质沉积物。
公知即使极小量的含汞化合物的毒性。并且重要的是，当单质汞存在于工业物质或天然气物流中时，由于冶金化学的问题，它危害处理这些物流的装置和管线的安全性和整体性。参见例如Audeh的美国专利4,880,527，其整体引入作为参考。
考虑到汞在工业生产中的威胁和普遍存在，有大量文献试图从含有该物质的材料中除去它。就此问题，参见例如Al-Faqeer的美国专利7,476,365，其整体引入作为参考。另外的教导从材料中除去汞的参考文献包括美国专利DeBerry的7,306,774；Winkler等的7,727,307；Jansen等的6,197,269；Chao等的4,474,896；Cooper等的7,381,388；Cooper等的6,872,370；Alper等的6,491,822；Jansen等的6,355,092；DenBoestert等的WO 2008/116864；和Durante等的U.S. 2006/0116287。其全部引入本文作为参考
这些参考文献大多教导将杂质如单质汞吸附到固体材料上。没有教导构成本文所述发明的特征的装置或方法。
发明概述
本发明涉及从液态或气态物流如进料流或工艺物流(下称“第一物流”)中除去汞的方法和装置，其通过使该物质经过多孔膜的一侧，同时使能够从该样品、第一物进料流或工艺物流中除去该汞的第二物流例如“洗涤物流”经过该膜的另一侧。洗涤可以通过使汞溶解到第二物流中，使其与“洗涤”或“第二”物流或者二者中的反应性组分进行反应来进行。
汞的转移基本上通过多孔膜的孔来进行。孔的尺寸并不重要。涉及纳滤、超滤和微滤的膜均处于本发明的范围内；但是，孔尺寸和数量(表面孔隙率)提供了控制汞跨越物流转移的速率和第一和第二物流之间的界面稳定性的手段。
洗涤溶液也称为“吸收剂液体”可以是任何能够溶解汞或与汞反应或者实现两种作用的溶液。可以包含在该溶液中的示例性材料为碱金属硫化物、硫氢化铵盐、二硫化物盐、多硫化物盐(含有Sx，其中x>2的盐)、过氧化氢、高氯酸盐和本领域技术人员已知的其他材料。
洗涤溶液可以经处理，例如以除去固体沉淀物，和/或添加相关化学物质以补充该溶液，并且然后进行再循环。当然，本领域技术人员将会认识到，可以是使用全新的溶液。
本文所述的发明提供了所述两种物流之间的非分散接触，这是相比于现在采用的常规分散相体系(包括液/液萃取，和气/液洗涤和吸收)的显著优势。
本领域遇到的问题，包括溶剂滞留(holdup)、形成乳液、起泡、放空(unloading)和液泛(flooding)，均得以避免。
并且，本发明允许膜的高填充密度，并且结果是采用的装置远小于现在产业实践中所见的装置。
并且，与本领域的状况相比，膜水平放置和竖直放置均起作用，与仅竖直放置相比，这是在标准系统中布置方面的优势。
本发明的特征将见于以下公开内容中。
附图说明
图1显示了本发明的一个实施方案。
图2显示了本发明的第二实施方案。
优选实施方案详述
本申请的图1显示了本发明的一个实施方案。参照该图，冷凝物储存器“100”含有需要处理的富汞材料。该材料可以是例如天然气、天然气的冷凝物、液态烃或任何其他含汞材料。该材料经由例如管装置“101”或任何其他类型的导管传送到形式为例如膜接触器模块“102”的多孔膜(以下详述)，并且通过导管“105”回到储存器“100”。膜接触器模块102中的该多孔膜可以采用平片材、中空纤维、圆盘、螺旋缠绕或其他本领域技术人员公知的构型的形式。用来制造膜的材料可以不同。示例性材料为聚乙烯、聚醚醚酮(PEEK)、特氟隆(PTFE)、聚偏氟乙稀(PVDF)以及任何其他与第一和第二物流相容的聚合型中空纤维材料。该材料经过多孔膜接触区模块102并在膜的孔内与洗涤溶液接触。洗涤溶液从洗涤溶液储存器“103”通过导管“104”和多孔膜接触器“102”，然后再通过导管“106”再循环回到储存器“103”。
流体可以以逆流方向(如本实例中)，或者以并流方向流动。
汞从富汞物流在膜接触器模块102的孔内转移到与富汞物流直接接触的洗涤溶液物流。因此，物流“105”将更贫含汞，而物流“106”将更富含汞。
本发明的第二实施方案示于图2。在该图中，富汞物流“108”经由膜接触器区块111与洗涤溶液“109”接触，在两种物流流经膜接触区“111”后，得到“贫汞”物流“110”。将得到的富汞洗涤溶液物流“112”再循环回到“洗涤溶液处理区113”。
“洗涤溶液处理区”113可以含有另外的材料和装置，例如一种或多种储槽，用于新鲜洗涤溶液、已经用过并经处理以除去汞的洗涤溶液、或者将要进行处理或进行处置的用过的洗涤溶液。也可以为这些的每一种提供储槽。该区可以还包括例如用于处理溶液如含汞洗涤物流以过滤固体(这些汞化合物或其他固体)的装置，沉降或偏析装置，以及补充和/或调节洗涤溶液的装置。
实施例
1
使用如图1中所示的系统。将稳定化的冷凝物掺有汞，以获得3ppm的富汞样品。
通过捆束7个中空的多孔聚丙烯纤维并用环氧树脂将它们粘结成聚丙烯管和PVC-Y接头，以形成壳和入口/出口，来构成中空纤维膜组件类型。该纤维的相关性质包括OD为～2500μm，孔尺寸为2-20μm。
然后将经掺杂的冷凝物从冷凝物储存器通过中空纤维的内腔侧，然后回到该储存器来循环。同时，将由15.6wt％的NaOH、6.3wt％的S8和78.1wt％的H2O组成的多硫化物溶液从它自己的储存器通过中空纤维模块内腔外侧(即壳侧)循环。
通过具有塑料软管的校准的、内部加衬的齿轮泵促进两种流体的循环。
使用标准冷蒸气原子荧光(“CVAF”)对样品进行经时分析。随着经掺杂的冷凝物和多硫化物溶液在系统中循环，对它们进行取样以追踪冷凝物中的汞含量。结果示于下面，作为具有分析标准偏差的各样品的多次分析的平均值。
| 时间(分钟) | [Hg](ppb) | SD％ |
| 1 | 3001 | 0.8 |
| 90 | 850 | 6.8 |
| 190 | 749 | 2.9 |
实施例
2
下表显示了同样使用图1的实施方案，汞通过获自Millipore Company的不同超滤膜的孔的传质。
本发明的其他特征对本领域技术人员将是清楚的，在此无需赘述。
采用的术语和表达以说明而非限制的方式使用，不希望使用这些术语和表达排除所示和所述特征或其部分的任何等价物，应当认识到不同的变型可能处于本发明的范围内。
Claims (13)
1.减少液体中汞的量的方法，其包括使含汞液体第一物流流过多孔膜的一侧，同时使含有至少一种与所述汞反应或溶解所述汞的化合物的第二物流流过所述多孔膜的另一侧，以使第一和第二物流经由所述孔接触，从而从所述液体第一物流中除去汞。
2.根据权利要求1所述的方法，其中所述多孔膜包括聚合型材料。
3.根据权利要求1所述的方法，其中所述多孔膜包括聚丙烯、聚醚醚酮(PEEK)、特氟隆(PTFE)或聚偏氟乙稀(PVDF)。
4.根据权利要求1所述的方法，其中所述多孔膜包括非聚合型材料。
5.根据权利要求4所述的方法，其中所述多孔膜包括尺寸有用于纳滤或超滤或微滤的孔。
6.根据权利要求1所述的方法，其中所述多孔膜包括中空纤维、平片材或圆盘。
7.根据权利要求1所述的方法，其包括使液体第一物流与第二物流在中空纤维膜组件中或者在螺旋缠绕膜组件中接触。
8.根据权利要求1所述的方法，其中所述第二物流包括碱金属硫化物、硫氢化铵盐、二硫化物盐、多硫化物盐、过氧化氢或高氯酸盐。
9.根据权利要求8所述的方法，其中所述第二物流包括碱金属硫化物、硫氢化铵盐、二硫化物盐或多硫化物盐。
10.根据权利要求9所述的方法，其中所述多硫化物盐是S8。
11.根据权利要求1所述的方法，其中所述方法连续进行。
12.根据权利要求1所述的方法，其中所述方法以间歇模式进行。
13.根据权利要求1所述的方法，其进一步包括处理所述含汞第二物流溶液以从中除去汞。
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| PCT/US2013/032072 WO2013142325A1 (en) | 2012-03-22 | 2013-03-15 | Method for removing mercury from a gaseous or liquid stream |
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| CN104220144B true CN104220144B (zh) | 2016-08-17 |
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| CN (1) | CN104220144B (zh) |
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| WO (1) | WO2013142325A1 (zh) |
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| RU2570281C1 (ru) * | 2014-08-12 | 2015-12-10 | Дмитрий Юрьевич Мартынов | Газоразделительная теплообменная установка |
| CN104722188A (zh) * | 2015-03-02 | 2015-06-24 | 江苏汇维特新材料科技有限公司 | 汞蒸气吸收装置及吸收方法 |
| WO2022015516A1 (en) | 2020-07-14 | 2022-01-20 | Exxonmobil Upstream Research Company | Methods and apparatus for offshore power generation and ammonia production |
| WO2022015515A1 (en) | 2020-07-14 | 2022-01-20 | Exxonmobil Upstream Research Company | Methods and apparatus for offshore power generation from a gas reservoir |
| US20240066435A1 (en) * | 2022-08-26 | 2024-02-29 | Hamilton Sundstrand Corporation | Membrane bundle for fuel deoxygenation with enhanced durability |
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| KR20170116233A (ko) | 2017-10-18 |
| WO2013142325A1 (en) | 2013-09-26 |
| SG11201405122QA (en) | 2014-10-30 |
| JP2015514002A (ja) | 2015-05-18 |
| KR20140137434A (ko) | 2014-12-02 |
| CN104220144A (zh) | 2014-12-17 |
| JP6163536B2 (ja) | 2017-07-12 |
| US20130287655A1 (en) | 2013-10-31 |
| EP2827970B1 (en) | 2017-11-01 |
| EP2827970A1 (en) | 2015-01-28 |
| US8641890B2 (en) | 2014-02-04 |
| KR101898409B1 (ko) | 2018-09-12 |
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