CN108495914A - 具有一定量的3,3’-亚甲基双(5-甲基噁唑烷)的组合物在从工艺流去除硫化合物中的用途 - Google Patents
具有一定量的3,3’-亚甲基双(5-甲基噁唑烷)的组合物在从工艺流去除硫化合物中的用途 Download PDFInfo
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Abstract
本发明涉及一种组合物在从工艺流去除硫化合物中的用途,该组合物包含a)3,3’‑亚甲基双(5‑甲基噁唑烷)和b)一种或多种选自以下各项的添加剂:(i)脲、脲衍生物、氨基酸、胍以及胍衍生物和(ii)1,2‑二元醇。该组合物优选被用于从工艺流中去除硫化氢。
Description
本发明涉及一种组合物在从工艺流去除硫化合物中的用途,该组合物包含a)3,3’-亚甲基双(5-甲基噁唑烷)和b)一种或多种添加剂。
硫化氢(H2S)是一种具有令人不愉快的气味的有毒气体,其对健康有很大危害并且在工业厂房中会导致严重的腐蚀现象。因此立法者已经制定了严格义务以减少H2S含量。OX(3,3’-亚甲基双(5-甲基噁唑烷),甲醛与异丙醇胺(以3:2的摩尔比)的无水缩合产物)在H2S的化学中和中展示了良好的有效性。
WO 02/051968 A1披露了一种用于通过用H2S清除产品进行处理而减少液体或气体中的硫化氢的量的方法。该H2S清除产品是通过i)具有羰基的化合物与ii)醇、硫醇、酰胺、硫代酰胺、脲或硫脲的反应获得的。该产品优选是通过使甲醛与不含胺的醇或脲反应来制备的。不含胺的醇的实例是乙二醇。H2S清除剂可以任选地与胺、特别是单乙醇胺一起使用。
WO98/02501披露了双噁唑烷可被用作巯基化合物的清除剂。双噁唑烷的实例是3,3’-亚甲基双(5-甲基噁唑烷),其通过异丙醇胺与甲醛(以2:3的摩尔比)的反应获得。然而,3,3’-亚甲基双(5-甲基噁唑烷)(下文中MBO)对硫化合物的清除作用需要改进,尤其是在具有低水含量的工艺流中。此类工艺流经常基于烃类进行配制。
根据DE 197 22 858 A1,基于丁基氨基甲酸碘代丙炔酯和甲醛储存化合物的组合物被用作防腐剂。特定的二醇、优选1,2-丙二醇的添加对组合物的气味有积极影响,并且减少了挥发性材料(如甲醛)的排放。
DE 102 44 442 A1披露了一种防腐剂,该防腐剂具有减少的甲醛排放并且包含a)至少一种缩甲醛和b)至少一种选自脲、脲衍生物、氨基酸、胍以及胍衍生物的减少排放的添加剂。
DE 10 2004 014 447 A1中所述的防腐剂包含a)至少N-缩甲醛、b)至少一种减少排放的添加剂以及c)单乙二醇。
DE 10 2012 203 003 A1披露了一种用于减少游离氧并保存水的液体制剂。该制剂包含a)至少一种N-缩甲醛和b)至少一种具有式RR’NOH(其中R和R’独立地选自C1-C10-烷基基团)的二烷基羟胺。
因此,本发明的目的是提供从工艺流、包括从优选含有极少水或不含水的工艺流中去除硫化合物的组合物。特别地,寻求具有改进的使用效率和优势并且此外还更经济的H2S清除剂组合物。这些组合物还应该避免或减少沉淀物。
这些目的通过使用组合物来实现,该组合物包含a)3,3’-亚甲基双(5-甲基噁唑烷)和b)一种或多种选自以下各项的添加剂:(i)脲、脲衍生物、氨基酸、胍以及胍衍生物和(ii)1,2-二元醇。根据本发明,该组合物被用于从工艺流中去除硫化合物。
根据本发明,该组合物优选被用于从工艺流中去除硫化氢。
根据本发明已发现,与单独使用3,3’-亚甲基双(5-甲基噁唑烷)(即不含提及的添加剂)相比,添加提及的添加剂提高了含有3,3’-亚甲基双(5-甲基噁唑烷)的组合物在从工艺流去除硫化合物中的有效性。根据本发明从工艺流中去除的或其在工艺流中的含量减少的硫化合物的实例是H2S、硫醇、硫醇盐、无机硫化物和有机硫化物以及其他硫醇化合物。
因此,在第一方面,本发明提供了组合物在从工艺流去除硫化合物中的用途,该组合物包含:
a)3,3’-亚甲基双(5-甲基噁唑烷)以及
b)一种或多种选自以下各项的添加剂:
(i)脲、脲衍生物、氨基酸、胍以及胍衍生物,以及
(ii)1,2-二元醇。
根据本发明使用的组合物优选是呈浓缩物的形式并且包含按重量计从60%至99%、优选按重量计从70%至97%、特别是按重量计从80%至92%的3,3’-亚甲基双(5-甲基噁唑烷)。
在第一优选的实施例中,该组合物包含:
b)一种或多种选自脲、脲衍生物、氨基酸、胍以及胍衍生物的添加剂。此类添加剂的实例是甘脲、四羟甲基甘脲、二甲基乙内酰脲、二羟甲基二甲基乙内酰脲、二羟甲基脲、四羟甲基脲、咪唑烷基脲以及重氮烷基脲。
该组合物特别地优选包含b)脲。在此,优选的是呈浓缩物的形式并且包含b)按重量计从1%至20%的脲,优选按重量计从2%至14%、特别是按重量计从2.5%至8%、例如按重量计从3%至6%的脲的组合物。
在第二优选的实施例中,使用了包含b)一种或多种1,2-二元醇的组合物。在这个实施例中,优选的是呈浓缩物的形式并且包含b)按重量计从1%至25%的1,2-二元醇,优选按重量计从3%至20%、特别是按重量计从5%至15%的1,2-二元醇的组合物。根据本发明使用的优选的1,2-二元醇选自乙二醇、丙二醇及其混合物,其中组分b)优选地是乙二醇。
在第三优选的实施例中,根据本发明使用的组合物包含b)至少一种组分(i)和至少一种组分(ii)。在这个实施例中,再次优选的是呈浓缩物的形式并且包含b)(i)按重量计从1%至20%的脲,优选按重量计从2%至14%、特别是按重量计从2.5%至8%、例如按重量计从3%至6%的脲的组合物。在这个实施例中,进一步优选的是该组合物包含b)(ii)按重量计从1%至25%的1,2-二元醇,优选按重量计从3%至20%、特别是按重量计从5%至15%的1,2-二元醇。
因此,根据本发明特别优选的是使用包含以下各项的组合物:
a)按重量计从60%至99%的3,3’-亚甲基双(5-甲基噁唑烷),(优选按重量计从70%至97%、特别是按重量计从80%至92%的3,3’-亚甲基双(5-甲基噁唑烷)),
b)(i)按重量计从1%至20%的脲(优选按重量计从2%至14%、特别是按重量计从2.5%至8%、例如按重量计从3%至6%的脲)以及
b)(ii)按重量计从1%至25%的1,2-二元醇(优选按重量计从3%至20%、特别是按重量计从5%至15%的1,2-二元醇)。
除了必须的组分a)3,3’-亚甲基双(5-甲基噁唑烷)和b)一种或多种提及的添加剂之外,该组合物可以进一步包含c)具有式RR’NOH的N,N-二烷基羟胺,其中R和R’独立地选自直链的、支链的以及环状的C1-C10-烷基基团。优选的N,N-二烷基羟胺是N,N-二乙基羟胺。
根据本发明处理的工艺流是例如液态和气态的工艺流。
示例性工艺流包含按重量计不超过40%的水、优选按重量计不超过35%的水、特别优选按重量计不超过30%的水,例如按重量计不超过25%或按重量计不超过20%或按重量计不超过15%、例如按重量计不超过10%或按重量计不超过5%、例如按重量计不超过1%的水。
使用领域尤其是沼气工厂,石油和天然气提抽,化石能源载体的加工、储存和运输以及在厌氧条件下由硫酸盐还原菌释放的H2S的去除。含有H2S的流或产品的实例为石油、原油、矿物油、加热用油、柴油燃料、沥青、蒸馏残余物、钻井液以及废水。特别优选的是根据本发明组合物在工艺流(其为烃流)中的用途。
在第二实施例中,本发明涉及一种用于从工艺流中去除一种或多种硫化合物的方法,其中,使包含一种或多种硫化合物的工艺流与组合物接触,该组合物包含a)3,3’-亚甲基双(5-甲基噁唑烷)和b)一种或多种选自以下各项的添加剂:(i)脲、脲衍生物、氨基酸、胍以及胍衍生物和(ii)1,2-二元醇。
该用途优选地是在高温(例如50℃或以上,例如70℃或以上、90℃或甚至150℃或以上)下。H2S的随后释放有利地不会发生与在单独使用3,3’-亚甲基双(5-甲基噁唑烷)情况下相同的程度。根据本发明使用的组合物比单独的3,3’-亚甲基双(5-甲基噁唑烷)更好地适合于结合在长时间热储存期间随后逐渐形成的固有H2S。
根据本发明的成分可以在短时间段内或者在不同时间点单独地被引入含H2S的工艺流中。出人意料地,麻烦的不溶性沉积物或沉淀物的形成减少,有时此类沉淀物甚至被溶解。根据本发明使用的组合物还具有非常好的短期的以及特别是长期的作用。短接触时间下实现了H2S含量的快速且有效的降低。
本发明的优点可以特别地从以下实例中看出。除非另外指明,否则百分比是按重量计。
实例
组合物OX(对比):
形成了摩尔比为2:3的异丙醇胺和多聚甲醛(91%浓度)的反应产物。在此形成了3,3’-亚甲基双(5-甲基噁唑烷)。蒸馏出反应用水和来自多聚甲醇的水。
组合物OK(根据本发明):
形成了摩尔比为2:3的异丙醇胺和多聚甲醛(91%浓度)的反应产物。在此形成了3,3’-亚甲基双(5-甲基噁唑烷)。蒸馏出反应用水和来自多聚甲醇的水。添加脲和乙二醇(该混合物包含按重量计约4.6%的脲和按重量计约9.5%的乙二醇)。
测定硫化物浓度的方法(基于IP 570,矿物油中硫化氢的测定)
-在不同温度下以及持续不同时间使各种硫清除剂与样品接触
-用烷基苯稀释样品以使其在分析系统的线性工作范围内
-将测试样品(包含硫清除剂)注射到分析系统中
-添加酸(水中的2M H3PO4)并且任选地加热分析系统中的分析样品
-通过空气定量排出分析系统中所得的硫化氢,并且将硫化氢转移到分析仪器中的电化学测量电极中
-硫化氢产生与在电化学测量电极处的硫化氢的各自的量成比例的测量信号。
-通过评估软件测定形成的峰面积(由测量信号强度对时间构成),并且基于校准线转化为硫化物含量。
a)H2S在C10-13-烷基苯中(硫化物浓度200ppm),20℃,2h
硫化物含量%的降低 | |
1000ppm OX(对比) | 8.8 |
1000ppm OK(本发明) | 11.6 |
b)H2S在C10-13-烷基苯中(硫化物浓度100ppm),50℃
c)H2S在C10-13-烷基苯中(硫化物浓度200ppm),50℃,2h
硫化物含量%的降低 | |
1000ppm OX(对比) | 10.0 |
1000ppm OK(本发明) | 15.4 |
这些实例证明根据本发明使用的组合物不仅比单独的3,3’-亚甲基双(5-甲基噁唑烷)更好地减少硫化物含量,而且这种改进的效果在升高的使用温度下甚至更显著。
Claims (22)
1.一种组合物在从工艺流去除硫化合物中的用途,该组合物包含:
a)3,3’-亚甲基双(5-甲基噁唑烷)以及
b)一种或多种选自以下各项的添加剂:
(i)脲、脲衍生物、氨基酸、胍以及胍衍生物,以及
(ii)1,2-二元醇。
2.根据权利要求1所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从60%至99%的3,3’-亚甲基双(5-甲基噁唑烷)。
3.根据权利要求2所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从70%至97%的3,3’-亚甲基双(5-甲基噁唑烷)。
4.根据权利要求3所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从80%至92%的3,3’-亚甲基双(5-甲基噁唑烷)。
5.根据权利要求1至4中任一项所述的用途,其特征在于,该组合物包含b)脲。
6.根据权利要求5所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从1%至20%的脲。
7.根据权利要求6所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从2%至14%的脲。
8.根据权利要求7所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从2.5%至8%的脲。
9.根据权利要求1至4中任一项所述的用途,其特征在于,该组合物包含b)一种或多种1,2-二元醇。
10.根据权利要求9所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从1%至25%的1,2-二元醇。
11.根据权利要求10所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从3%至20%的1,2-二元醇。
12.根据权利要求11所述的用途,其特征在于,该组合物是呈浓缩物的形式并且包含按重量计从5%至15%的1,2-二元醇。
13.根据权利要求9至12中任一项所述的用途,其特征在于,该1,2-二元醇选自乙二醇、丙二醇及其混合物。
14.根据权利要求13中任一项所述的用途,其特征在于,该1,2-二元醇是乙二醇。
15.根据权利要求1至14中任一项所述的用途,其特征在于,该组合物进一步包含c)具有式RR’NOH的N,N-二烷基羟胺,其中R和R’独立地选自直链的、支链的以及环状的C1-C10-烷基基团。
16.根据权利要求15所述的用途,其特征在于,该N,N-二烷基羟胺是N,N-二乙基羟胺。
17.根据权利要求1至16中任一项所述的用途,其特征在于,该工艺流选自液态和气态工艺流。
18.根据权利要求1至17中任一项所述的用途,其特征在于,该工艺流包含按重量计不超过40%的水。
19.根据权利要求1至18中任一项所述的用途,其特征在于,该工艺流是烃流。
20.根据权利要求1至19中任一项所述的用途,其特征在于,该硫化合物选自硫化氢、无机硫化物和有机硫化物、硫醇以及硫醇盐。
21.根据权利要求20所述的用途,其特征在于,该硫化合物是硫化氢。
22.一种用于从工艺流中去除一种或多种硫化合物的方法,其中,使该包含一种或多种硫化合物的工艺流与组合物接触,该组合物包含:
a)3,3’-亚甲基双(5-甲基噁唑烷)以及
b)一种或多种选自以下各项的添加剂:
(i)脲、脲衍生物、氨基酸、胍以及胍衍生物,以及
(ii)1,2-二元醇。
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