CN110049965A - 具有低盐腐蚀的油溶性硫化物清除剂以及制备和使用这些清除剂的方法 - Google Patents

具有低盐腐蚀的油溶性硫化物清除剂以及制备和使用这些清除剂的方法 Download PDF

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CN110049965A
CN110049965A CN201680091445.2A CN201680091445A CN110049965A CN 110049965 A CN110049965 A CN 110049965A CN 201680091445 A CN201680091445 A CN 201680091445A CN 110049965 A CN110049965 A CN 110049965A
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formaldehyde
azanol
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H.G.巴加里亚
G.卡普兰
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BL Technologies Inc
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Abstract

本发明涉及可用于减少流体流中硫化物浓度的硫化物清除剂和使用这些清除剂的方法。所述清除剂包括甲醛/N‑取代的羟胺的油溶性反应产物，并且可用于减少例如在粘性烃油流中的H2S含量。

Description

具有低盐腐蚀的油溶性硫化物清除剂以及制备和使用这些清 除剂的方法
发明领域
本发明涉及油溶性N-取代的羟胺/甲醛反应产物(下文中有时称为AHAF)、其制备方法和使用其来降低流体(即气体或液体)流中的硫化物含量的方法。
发明背景
硫化氢即H2S，是一种具有恶臭的透澈、有毒气体。它也是高度可燃的。环境保护署和全球其他监管机构严格控制H2S向环境中的释放。H2S可以存在于井水、废水和其他含水体系中。H2S经常存在于原油和天然气储量中并且必须在商业使用这种储量之前将其降低。处理前在这些储量中的H2S浓度通常随地点而变化，并且天然气中的H2S浓度通常高于在原油储量中的H2S浓度。例如，在天然气储量中，H2S可以从小于100ppm到3000ppm变化。允许的H2S水平也会因地点而异。美国将天然气管道中的H2S限制为每100标准立方英尺4 ppm(0.3gr/100scf)。
一般而言，通过使用将与硫化物反应的化学品对烃流进行处理，以减少硫化物包括有机硫化物、硫醇(mercaptans)、硫醇(thiols)、COS和H2S。这些化学品被称为清除剂或脱硫剂。
单乙醇胺(MEA)三嗪是一种广泛使用的H2S清除剂；然而，高胺盐腐蚀潜力是炼油厂运行的主要问题。由于它是水基产品，MEA三嗪具有传质限制，这限制了其在高粘度流中的应用。
大多数烃储量在源头附近连续处理，尽管在其他地方分批处理烃或类似应用并不少见。源头附近的连续处理设施将硫化物清除剂直接注入烃管道。注射系统通常包含化学注射泵和管道三通或雾化喷嘴以将清除剂引入到管道。所需清除剂的量将根据各种因素而变化，包括所用清除剂的类型、井中H2S的量、允许的H2S限值和井流速。因此，添加用于处理烃管道的清除剂的量通常在烃流的约1ppm至约100,000ppm体积的范围内。提供的管道长度允许清除剂和硫化物之间的接触。
发明概述
在一些实施方案中，本发明涉及一种用于减少流体流中的硫化物的方法，所述方法包括使流体流与具有下式的N-取代的羟胺/甲醛反应产物接触，
其中n是约0-10的整数且R1和R2各自独立地选自H；C1-C10直链、支链和环状烷基、烯基；或芳基；条件是R1和R2不都是H。硫化物可以例如包含一种或多种选自以下的成员：有机硫化物、硫醇(mercaptans)、硫醇(thiols)、COS和H2S。流体流可以包括烃流或含水流。
使约1-100,000ppm体积的反应产物与流体流接触，基于一百万份所述流体流。在其他实施方案中，使约500-3,000ppm的反应产物与流体流接触。
在其他示例性实施方案中，上式的R1和R2均为C1-C10烷基。在一些实施方案中，R1和R2均为乙基。
本发明的其他实施方案涉及用于制备N-取代的羟胺/甲醛反应产物的方法，所述方法包括使式RR'NOH的N-取代的羟胺与甲醛反应，其中R和R'各自独立地选自H；直链、支链和环状C1-C10烷基、烯基；或芳基；条件是R和R'不都是H。所述方法在高于约60℃的温度下进行约0.5-2.0小时。在一些实施方案中，反应在有机溶剂的存在下进行，并且在其他实施方案中，反应在约80-90℃的温度下进行。
在一些实施方案中，N-取代的羟胺选自一种或多种选自以下的成员：N, N-二甲基羟胺、N, N-二乙基羟胺、N, N-二苄基羟胺、N-乙基羟胺、N-丙基羟胺、N-异丙基羟胺、N-丁基羟胺、N-苯基羟胺、N-环己基羟胺、N-叔丁基羟胺、N-苄基羟胺。
在一些实施方案中，甲醛与N-取代的羟胺的摩尔比为约0.5-5mol甲醛比N-取代的羟胺。在其他实施方案中，甲醛与N-取代的羟胺的摩尔比为约1-3mol甲醛比约1mol N-取代的羟胺。在一些实施方案中，甲醛以多聚甲醛的形式。
在其他实施方案中，N-取代的羟胺/甲醛反应产物(AHAF)具有以下结构：
其中n是0-10的整数；R1和R2各自独立地选自H；C1-C10直链、支链和环状烷基、烯基；或芳基；条件是R1和R2不都是H。在一些实施方案中，反应产物是油溶性的。在一些实施方案中，R1和R2均为C1-C10烷基，如乙基。
详细描述
本发明的一个方面涉及制备N-取代的羟胺/甲醛反应产物(AHAF)的方法，其中式RR'NOH的N-取代的羟胺与甲醛(例如多聚甲醛)以纯形式或在有机溶剂存在下反应。反应可在高于约60℃的温度下进行约0.5-2.0小时。在一些实施方案中，反应可在约80-90℃的温度下进行约1小时。在上述的N-取代的羟胺式中，R和R'独立地选自H；直链、支链和环状C1-C10烷基、烯基；或芳基；条件是R和R'不都是H。R和R'的实例包括甲基、乙基、丙基、丁基、戊基、己基、辛基和癸基。特别值得注意的是二乙基羟胺(DEHA)。
在一些实施方案中，羟胺选自N, N-二甲基羟胺、N, N-二乙基羟胺、N, N-二苄基羟胺、N-乙基羟胺、N-丙基羟胺、N-异丙基羟胺、N-丁基羟胺、N-苯基羟胺、N-环己基羟胺、N-叔丁基羟胺、N-苄基羟胺。
在使用有机溶剂的那些实施方案中，作为示例可提及重质芳族石脑油(naptha)溶剂。加成反应产物可以保留在溶剂中，它可以原样使用以减少烃流体流中的硫化物含量，或加成物可以通过常规分离技术与反应介质分离并随后用作硫化物清除剂。可提及的其他有机溶剂包括戊烷、己烷、环己烷、苯、甲苯、氯仿、乙醚、二氯甲烷、四氢呋喃(THF)、乙酸乙酯等。反应物的摩尔比即甲醛：N-取代的羟胺可以为约0.5-5:1，作为示例，还可提及约1-3:1的比率。
所述AHAF反应产物具有以下结构：
其中n是约0-10的整数；R1和R2各自独立地选自H；C1-C10直链、支链和环状烷基、烯基；或芳基；条件是R1和R2不都为H。在其中DEHA与甲醛(例如多聚甲醛)反应的情况下，R1和R2均为乙基。
在本发明的其他方面，公开了一种用于从流体流还原硫化物的方法，其中使AHAF反应产物与这样的包含一种或多种有机硫化物、硫醇(mercaptans)、硫醇(thiols)、COS和H2S的流体流接触。流体流可包括液体和气体介质，并且这些流可以是烃流或含水流。反应产物可以流体流的约1至100, 000 ppm体积的量使用。可提及的其他示例性剂量范围包括500-3,000ppm，尤其是约1,000ppm。
AHAF反应产物具有的优点在于，它们对与流体流接触的冶金的胺盐腐蚀呈现出低风险，并且与胺如二丙胺和二丁胺相比具有更高的闪点；因此减轻安全和处理问题。加成物具有低PPI(盐沉淀指数)，因此降低了盐腐蚀风险。加成物是油溶性并因此可以用在重质粘性烃流中。
在其他示例性实施方案中，处理的流体流可包含流体烃流或含水流体流。这些流体流可以例如包括来自油田工艺、管道、罐、油罐车、精炼厂和化学工厂的气/液混合物。另外，流体流可包括农场排放物、城市用水等。其他另外的流体流包括水、废水和含H2S的工艺水。
将结合以下说明的实施例进一步描述本发明，所述实施例不应解释为限制本发明。
实施例
实施例1
甲醛:DEHA加成物(摩尔比为2:1)，纯。
将45g固体多聚甲醛放入烧瓶中。加入无水DEHA(65g)。将该混合物搅拌并加热至90℃保持1小时，直至多聚甲醛完全溶解。冷却至室温，收集110g加成物(100％)。
实施例2
甲醛:DEHA加成物(摩尔比为2:1)，在溶剂中。
将65g固体多聚甲醛放入烧瓶中。加入无水DEHA(89g)和51g Aromatic A-150溶剂。搅拌混合物并加热至90℃保持1小时，直至多聚甲醛完全溶解。Aromatic A-150是一种重质芳烃溶剂石脑油。冷却至室温，收集205g加成物(100％)。
实施例3
甲醛:DEHA加成物(摩尔比1:1)，纯。
将23g固体多聚甲醛放入烧瓶中。加入无水DEHA(65g)。搅拌混合物并加热至90℃保持1小时，直至多聚甲醛完全溶解。冷却至室温，收集88g加成物(100％)。
实施例4
甲醛:DEHA加成物(摩尔比为1:1)，在溶剂中。
将33g固体多聚甲醛放入烧瓶中。加入无水DEHA(89g)和51g Aromatic A-150溶剂。搅拌混合物并加热至90℃保持1小时，直至多聚甲醛完全溶解。冷却至室温，收集173g加成物(100％)。
实施例5
为了证明N-取代的羟胺-甲醛加成物在降低烃介质中的H2S方面的功效，在含有或不含硫化物清除剂候选化学品的情况下，将150ml燃料仓燃料在500ml中混合并加热至75℃。2小时后使用染色/牵引管(stain/dragger tube)测量顶空H2S蒸气浓度。下表示出了所得数据。
表
虽然已经描述了本发明的说明性实施方案，但是应该理解，本发明不限于此，并且可以在不脱离本发明的情况下进行修改。本发明的范围由所附权利要求限定，所述权利要求在字面侵权或等同物分析原则下来考察。

Claims (25)

1.一种用于减少流体中的硫化物的方法，所述方法包括使所述流体与N-取代的羟胺与甲醛的反应产物(AHAF)接触。
2. 根据权利要求1所述的方法，其中所述N-取代的羟胺包括一种或多种选自以下的成员：N, N-二甲基羟胺、N, N-二乙基羟胺、N, N-二苄基羟胺、N-乙基羟胺、N-丙基羟胺、N-异丙基羟胺、N-丁基羟胺、N-苯基羟胺、N-环己基羟胺、N-叔丁基羟胺、N-苄基羟胺。
3.根据权利要求1所述的方法，其中所述反应产物(AHAF)具有下式：
其中n为约0-10且R1和R2各自独立地选自H；C1-C10直链、支链和环状烷基、烯基；或芳基；条件是R1和R2不都是H。
4.根据权利要求1所述的方法，其中所述硫化物包括一种或多种选自以下的成员：有机硫化物、硫醇(mercaptans)、硫醇(thiols)、COS和H2S。
5.根据权利要求1所述的方法，其中所述流体是烃。
6.根据权利要求1所述的方法，其中所述流体是天然气。
7.根据权利要求1所述的方法，其中所述流体是水。
8.根据权利要求1所述的方法，其中所述流体是烃、水和气体的多相混合物。
9.根据权利要求5所述的方法，其中所述烃是选自以下的烃油：原油、石脑油、瓦斯油、燃料仓燃料、船用柴油、沥青质和沥青。
10.根据权利要求1所述的方法，其中使约1至100,000ppm体积的所述反应产物与所述流体接触，基于一百万份所述流体。
11.根据权利要求10所述的方法，其中使约500至3,000ppm的所述反应产物与所述流体接触。
12.根据权利要求3所述的方法，其中R1和R2均为C1-C10烷基。
13.根据权利要求12所述的方法，其中R1和R2均为乙基。
14.一种用于制备二烷基羟胺/甲醛反应产物的方法，所述方法包括使式RR'NOH的羟胺与甲醛反应，其中R和R'各自独立地选自H；直链、支链和环状C1-C10烷基、烯基；或芳基；条件是R1和R2不都是H；所述方法在高于约60℃的温度下进行约0.5-2.0小时。
15.根据权利要求14所述的方法，其中所述反应在有机溶剂的存在下进行。
16.根据权利要求14所述的方法，其中所述反应在约80-90℃的温度下进行。
17.根据权利要求14所述的方法，其中R和R'均为C1-C10烷基。
18.根据权利要求17所述的方法，其中R和R'均为乙基。
19. 根据权利要求14所述的方法，其中甲醛与N-取代的羟胺的摩尔比为约0.5-5mol甲醛比约1mol N-取代的羟胺。
20. 根据权利要求19所述的方法，其中甲醛与N-取代的羟胺的摩尔比为约1-3mol甲醛比约1mol N-取代的羟胺。
21.根据权利要求19所述的方法，其中所述甲醛是多聚甲醛。
22.具有以下结构的N-取代的羟胺/甲醛反应产物：
其中n为0-10的整数；R1和R2各自独立地选自H；C1-C10直链、支链和环状烷基、烯基；或芳基；条件是R1和R2不都是H。
23.根据权利要求22所述的反应产物，其中所述反应产物是油溶性的。
24.根据权利要求23所述的反应产物，其中R1和R2均为C1-C10烷基。
25.根据权利要求24所述的反应产物，其中R1和R2均为乙基。
CN201680091445.2A 2016-12-07 2016-12-07 具有低盐腐蚀的油溶性硫化物清除剂以及制备和使用这些清除剂的方法 Pending CN110049965A (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63167356A (ja) * 1986-12-27 1988-07-11 Konica Corp 安全性、保恒性等が改良されたハロゲン化銀カラ−写真感光材料用発色現像液
US4757102A (en) * 1986-05-12 1988-07-12 Ciba-Geigy Corporation Compositions stabilized with aminoxy alkylamine derivatives
WO2013077949A1 (en) * 2011-11-23 2013-05-30 General Electric Company Amine sulfide scavengers, methods of using, and methods of making

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4757102A (en) * 1986-05-12 1988-07-12 Ciba-Geigy Corporation Compositions stabilized with aminoxy alkylamine derivatives
JPS63167356A (ja) * 1986-12-27 1988-07-11 Konica Corp 安全性、保恒性等が改良されたハロゲン化銀カラ−写真感光材料用発色現像液
WO2013077949A1 (en) * 2011-11-23 2013-05-30 General Electric Company Amine sulfide scavengers, methods of using, and methods of making

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
MAKAROV, S. P.ETAL: "Bis(trifluoromethyl) nitrogen monoxide reactions. II. Reactions with methanol, benzene and fluorobenzene", 《ZHURNAL OBSHCHEI KHIMII》 *
MATEUSZ KUPRIANOWICZ ETAL: "The nitrogen inversion in fused isoxazolidinyl derivatives of substituted uracil: synthesis, NMR and computational analysis", 《STRUCT CHEM》 *
P. H. MORGANT ETAL: "SYNTHESIS OF SOME N-OXYGENATED PRODUCTS OF 3,4-DIMETHOXYAMPETAMINE AND ITS N-ALKYL DERIVATIVES", 《TETRAHEDRON》 *
RYUTA TOBA ETAL: "Scavenging and Characterization of Short-Lived Radicals Using a Novel Stable Nitroxide Radical with a Characteristic UV-vis Absorption Spectrum", 《ORG. LETT.》 *
SK. ASROF ALI ETAL: "Regiochemistry of Mercury(II) oxide Oxidation of Unsymmetrical N,N-Disubstituted Hydroxylamines", 《TETRAHEDRON》 *

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