CN105339467B - 油溶性硫化氢清除剂 - Google Patents
油溶性硫化氢清除剂 Download PDFInfo
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 22
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- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims abstract description 12
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Abstract
烃中硫化氢浓度可将通过粒状氧化锌与两种或更多种羧酸的混合物进行反应所制备的羧酸氧锌配合物组合物导入烃中来降低，其中所述羧酸氧锌配合物组合物溶于烃。有用的酸包括乙酸、油酸、异丁酸、亚油酸、cekanoic acid和新癸酸。
Description
背景
1.发明领域
本发明涉及降低烃中的硫化氢浓度。本发明特别涉及从烃中清除硫化氢。
2.发明背景
在石油和天然气的勘探和生产中常常会遇到硫化氢(H2S)。H2S的存在通常是令人讨厌的，因为它可以与其它烃或燃料系统组分发生反应。硫化氢令人讨厌的另一个原因是它可能是高腐蚀性的。不希望存在硫化氢的另一个原因是其会产生高度恶臭的气味。
解决这些问题的一种方法是“清除”H2S。已知金属基清除剂和某些三嗪类和醛类是适用于这些目的的。例如，乙二醛(OHCCHO)已在pH中性条件下被用作成功的清除剂。已知乙二醛和其它醛类如丙烯醛和甲醛应用于各种其它用途如杀菌剂、消毒剂等。
但有时使用这类醛本身就有问题。醛可以腐蚀金属如铝、铁和钢。
已知金属羧酸盐适用于降低烃中的硫化氢浓度。遗憾的是，许多先有技术的金属羧酸盐、特别是那些用乙酸制备的金属羧酸盐是不溶于烃的，必须以分散形式或其它类似方式使用。在本领域中期望制备一种与烃类、特别是原油、燃料油和沥青一起使用的油溶硫化氢抑制剂。
概述
在一个方面，本发明是制备用于从烃中清除硫化氢的羧酸氧锌配合物组合物的方法，包括将粒状氧化锌与两种或更多种羧酸的混合物进行反应，其中的酸都不是辛酸或辛酸异构体且所述羧酸氧锌配合物组合物溶于烃。
本发明的另一个方面是制备用于从烃中清除硫化氢的羧酸氧锌配合物组合物的方法，包括将粒状氧化锌与两种或更多种羧酸的混合物进行反应，其中所述羧酸氧锌配合物组合物溶于烃。
在另一个方面，本发明是降低烃中硫化氢浓度的方法，包括将所公开的羧酸氧锌配合物组合物导入烃中。
说明
在一个实施方案中，本公开内容涉及制备用于从烃中清除硫化氢的羧酸氧锌配合物组合物的方法。羧酸氧锌配合物是通过将粒状氧化锌与两种或更多种羧酸的混合物进行反应来制备的。在此过程中，羧酸兼作溶剂和反应物。反应中所用羧酸的总摩尔数约等于所加锌总摩尔数的1.5倍。
此反应途径导致最终锌产物具有约为2:3的锌/酸比。所选酸是可混溶的且结构和比例适合得到均相和可溶于有机溶剂的产物。所述酸可选自乙酸、油酸、异丁酸、亚油酸、cekanoic acid和新癸酸。在一些实施方案中，可使用乙基己酸，而在其它实施方案中则禁止使用乙基己酸。当酸混合物被加热时氧化锌溶解于酸混合物中使反应进行。反应生成前面提及的羧酸氧锌配合物还有水，所述水最终蒸馏除去以提纯羧酸氧锌产物。
在一些实施方案中，得到的配合物可溶于有机溶剂。
换句话说，本申请的方法包括合成式Zn4O(酸)6的锌氧配合物，其中术语“酸”是指带有-1电荷的羧酸根配体。羧酸根配体包括两或更多种不同类型的酸配体且所述配合物是采用氧化锌与羧酸的液体混合物进行无溶剂反应的方法合成的。在此实施方案中，组合多个酸物种作为配体使得配合物是油溶性的且适合注入烃料流中，而仅由一种类型酸配位体构成的类似配合物则不适于注入或根本不可能注入。在每种情况下，配合物中锌原子数与酸配体总数的比值约2:3，但锌原子数与每种个体酸配体数之比可在约4:5至约4:1范围。在此实施方案中，酸配体是由新癸酸、乙酸、油酸和亚油酸中的两种或更多种构成的。
尽管不希望受任何理论的束缚，但相信所述清除剂在含硫烃料流中保持可溶性的原因是由于与锌原子结合的大部分配体具有高支化性质。通过合成配位到混合酸配体的配合物，可以引入低分子量酸分子，从而获取总体较低分子量的配合物。氧锌配合物总分子量的降低导致配合物具有较高的锌含量(质量)，这改善了最终产品在H2S清除功效方面的成本效益。使用低分子量酸不会影响产品清除H2S的功效，因为清除反应的驱动力是生成硫化锌和质子酸分子：
Zn4O(酸)6+4H2S→4ZnS+6H-酸+H2O
硫化氢清除剂可以适合生产油气领域普通技术人员采用的已知任何方式应用于所公开的过程。例如，可将其雾化并引入到气体料流中或者与原油料流直接液-液混合。可以在溶剂中引入粘稠相如沥青。
实施例
提供以下实施例来例示说明本发明。这些实施例不是要限制本发明范围且不应如此解读。量为重量份或重量百分数，除非另有说明。
实施例1
将53.2克新癸酸和3.7克乙酸装入反应器中，加热至60℃并搅拌。达到温度后，将20克氧化锌粉末以小量等分方式缓慢加入酸混合物中。待所有氧化锌粉末加入并溶解后，将反应器温度升高至100℃并搅拌1小时。此搅拌时间后，将反应器温度再提高至110℃并将氮气鼓泡加入以除去夹带在反应混合物中的水。收集水之后，将反应器温度降低到80℃，此时加入27.6克芳香族馏分溶剂并将反应混合物再搅拌30分钟。
实施例2
将26.5克新癸酸、9.3克乙酸和17.4克油酸装入反应器中，加热至60℃并搅拌。达到温度后，将20克氧化锌粉末以小量等分方式缓慢加入酸混合物中。待所有氧化锌粉末加入并溶解后，将反应器温度升高至100℃并搅拌1小时。此搅拌时间后，将反应器温度再提高至110℃并将氮气鼓泡加入以除去夹带在反应混合物中的水。收集水之后，将反应器温度降低到80℃，此时加入27.6克芳香族馏分溶剂并将反应混合物再搅拌30分钟。
实施例3
将23.9克新癸酸、10.19克乙酸和18克油酸装入反应器中，加热至60℃并搅拌。达到温度后，将20克氧化锌粉末以小量等分方式缓慢加入酸混合物中。待所有氧化锌粉末加入并溶解后，将反应器温度升高至100℃并搅拌1小时。此搅拌时间后，将反应器温度再提高至110℃并将氮气鼓泡加入以除去夹带在反应混合物中的水。收集水之后，将反应器温度降低到80℃，此时加入27.6克芳香族馏分溶剂并将反应混合物再搅拌30分钟。
实施例4
将26.58克新癸酸、9.27克乙酸和17.312克亚油酸装入反应器中，加热至60℃并搅拌。达到温度后，将20克氧化锌粉末以小量等分方式缓慢加入酸混合物中。待所有氧化锌粉末加入并溶解后，将反应器温度升高至100℃并搅拌1小时。此搅拌时间后，将反应器温度再提高至110℃并将氮气鼓泡加入以除去夹带在反应混合物中的水。收集水之后，将反应器温度降低到80℃，此时加入27.6克芳香族馏分溶剂并将反应混合物再搅拌30分钟。
实施例5-8和对比实施例A&B
采用实施例1步骤但使用如下表所示酸制备的氧配合物进行测试。添加剂以2000ppm浓度引入烃中，所述烃为ISOPAR M(EXXON MOBIL CHEMICALS的商品名)，已用硫化氢处理，处理后2小时具有28000ppm和处理24小时后22500ppm的空白值。结果显示在下表。
表
实施例讨论
这些实施例清楚地显示出可制备有效和可溶性的硫化氢清除剂。
Claims (12)
1.降低烃中硫化氢浓度的方法，包括将羧酸氧锌配合物组合物导入烃中；其中所述羧酸氧锌配合物组合物是通过粒状氧化锌与两种或更多种羧酸的混合物进行反应的反应产物；其中所述羧酸氧锌配合物组合物溶于烃；并且其中所述羧酸都不是辛酸或辛酸异构体,其中至少一种羧酸是乙酸。
2.权利要求1的方法，其中所述羧酸氧锌配合物组合物中锌原子与总酸配体之比为2:3。
3.权利要求2的方法，其中所述羧酸氧锌配合物组合物中锌原子与每种个体酸配体之比在4:5到4:1范围。
4.降低烃中硫化氢浓度的方法，包括将羧酸氧锌配合物组合物导入烃中；其中所述羧酸氧锌配合物组合物是通过下列方法获得的反应产物：
将两种或更多种羧酸混合在一起形成羧酸混合物；其中所述羧酸都不是辛酸或辛酸异构体；并且其中所述两种或更多种羧酸选自乙酸、异丁酸和新癸酸；和
将粒状氧化锌与所述羧酸混合物反应形成所述羧酸氧锌配合物组合物；其中所述羧酸氧锌配合物组合物溶于烃。
5.权利要求4的方法，其中至少一种羧酸是乙酸。
6.权利要求4的方法，其中所述羧酸氧锌配合物组合物中锌原子与总酸配体之比为2:3。
7.权利要求6的方法，其中所述羧酸氧锌配合物组合物中锌原子与每种个体酸配体之比在4:5到4:1范围。
8.权利要求1的方法，其中至少一种羧酸是异丁酸。
9.权利要求4的方法，其中至少一种羧酸是异丁酸。
10.降低烃中硫化氢浓度的方法，包括将羧酸氧锌配合物组合物导入烃中；其中所述羧酸氧锌配合物组合物是通过粒状氧化锌与两种或更多种羧酸的混合物进行反应的反应产物；其中所述羧酸氧锌配合物组合物溶于烃；并且所述羧酸都不是辛酸或辛酸异构体；并且其中所述羧酸中至少两种是新癸酸和异丁酸。
11.权利要求10的方法，其中所述羧酸氧锌配合物组合物中锌原子与总酸配体之比为2:3。
12.权利要求10的方法，其中所述羧酸氧锌配合物组合物中锌原子与每种个体酸配体之比在4:5到4:1范围。
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| US13/946,836 US9353026B2 (en) | 2013-07-19 | 2013-07-19 | Oil soluble hydrogen sulfide scavenger |
| US13/946,836 | 2013-07-19 | ||
| PCT/US2014/044559 WO2015009429A1 (en) | 2013-07-19 | 2014-06-27 | Oil soluble hydrogen sulfide scavenger |
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| US10577542B2 (en) * | 2013-02-19 | 2020-03-03 | Baker Hughes, A Ge Company, Llc | Low viscosity metal-based hydrogen sulfide scavengers |
| WO2016180563A1 (en) | 2015-05-14 | 2016-11-17 | Clariant International Ltd | Composition and method for scavenging sulfides and mercaptans |
| BR112017028362A2 (pt) * | 2015-07-03 | 2018-09-04 | Dorf Ketal Chemicals India Private Ltd | composições aditivas para a eliminação de sulfeto de hidrogênio, e o meio compreendendo as mesmas |
| EP3400260B1 (en) * | 2016-01-08 | 2021-06-02 | Innophos, Inc. | Scavenger compositions for sulfur species |
| WO2018207657A1 (ja) | 2017-05-12 | 2018-11-15 | 株式会社クラレ | 含硫黄化合物除去装置および含硫黄化合物除去方法 |
| US20230390170A1 (en) * | 2020-09-24 | 2023-12-07 | Firmenich Sa | Consumer products containing pro-fragrances |
| CN113372894A (zh) * | 2021-06-11 | 2021-09-10 | 四川正蓉上之登科技有限公司 | 一种高效快速可溶性除硫缓蚀剂及其制备方法 |
| WO2023225494A1 (en) * | 2022-05-16 | 2023-11-23 | Heritage Research Group, Llc | Unrefined neodecanoic acid source as a raw material for h2s scavenging metal carboxylate |
| CN115678516A (zh) * | 2022-11-11 | 2023-02-03 | 西南石油大学 | 改性纳米氧化锌油基钻井液除硫剂的制备方法及其应用 |
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| US8246813B2 (en) * | 2009-12-15 | 2012-08-21 | Nalco Company | Method of removing hydrogen sulfide |
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| US2890232A (en) * | 1956-05-31 | 1959-06-09 | Swift & Co | Manufacture of metal soaps |
| GB1142195A (en) | 1965-06-18 | 1969-02-05 | British Petroleum Co | Alkaline lubricating oil |
| JPS6252610B2 (zh) | 1980-10-14 | 1987-11-06 | Yunion Oiru Co Obu Karifuorunia | |
| GB2137633B (en) * | 1983-03-31 | 1986-10-29 | Exxon Research Engineering Co | Decreasing h2s emission in bitumen/sulphur mixtures |
| US4871468A (en) | 1987-02-19 | 1989-10-03 | The Dow Chemical Company | Method and composition for the removal of hydrogen sulfide and carbon dioxide from gaseous streams |
| US4830838A (en) | 1988-11-01 | 1989-05-16 | The Dow Chemical Company | Removal of hydrogen sulfide from fluid streams with minimum production of solids |
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| US20050145137A1 (en) * | 2003-12-31 | 2005-07-07 | Buras Paul J. | Process for preparing bitumen compositions with reduced hydrogen sulfide emission |
| FR2882942B1 (fr) | 2005-03-09 | 2007-06-15 | Inst Francais Du Petrole | Procede perfectionne de traitement d'un gaz contenant de l'hydrogene sulfure et du dioxyde de soufre |
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| US6599472B1 (en) * | 2000-11-03 | 2003-07-29 | Surface Chemists Of Florida Inc. | Oil soluble scavengers for sulfides and mercaptans |
| US8246813B2 (en) * | 2009-12-15 | 2012-08-21 | Nalco Company | Method of removing hydrogen sulfide |
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| WO2015009429A1 (en) | 2015-01-22 |
| EP3022275A4 (en) | 2017-03-29 |
| US9353026B2 (en) | 2016-05-31 |
| CA2915247A1 (en) | 2015-01-22 |
| EP3022275B1 (en) | 2020-04-29 |
| US20150025258A1 (en) | 2015-01-22 |
| CA2915247C (en) | 2018-02-27 |
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