CN103380197B - 通过加氢处理反应使用催化剂同时除去烃类材料中的硫和汞的方法 - Google Patents

通过加氢处理反应使用催化剂同时除去烃类材料中的硫和汞的方法 Download PDF

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CN103380197B
CN103380197B CN201280007589.7A CN201280007589A CN103380197B CN 103380197 B CN103380197 B CN 103380197B CN 201280007589 A CN201280007589 A CN 201280007589A CN 103380197 B CN103380197 B CN 103380197B
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mercury
sulphur
hydrocarbon materials
catalyzer
carrier
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CN103380197A (zh
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金度京
金度完
李相日
吴承勋
金偶经
潘汉承
金佑荣
全敬秀
崔先
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SK Innovation Co Ltd
SK Energy Co Ltd
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SK Energy Co Ltd
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Abstract

本发明公开了一种同时除去烃类材料中的硫和汞的方法，包括：在包含担载于载体上的金属的催化剂的存在下，对含有硫和汞的烃类材料进行加氢处理，从而将硫转化为硫化氢，以及将汞以硫化汞的形式吸附于所述催化剂的金属活性位点或载体上。

Description

通过加氢处理反应使用催化剂同时除去烃类材料中的硫和汞的方法
技术领域
本发明涉及一种通过加氢处理反应使用催化剂同时除去烃类材料中的硫和汞的方法。
背景技术
根据材料的来源和种类，烃类材料(如原油、天然气和天然气凝析油，以及由其制得的汽油、轻质石脑油、重质石脑油、煤油、轻瓦斯油(LGO)、重瓦斯油(HGO)和常压渣油等)含有不同含量的硫、汞、以及硫和/或汞化合物。
当烃类材料中所含的硫被排放到空气中时，可能导致诸如空气污染、酸雨等的危害。由于在绝大多数的石油化工工艺中，硫会使裂化催化剂和重整催化剂中毒，因此必须在进行所述石油化工工艺之前除去硫。特别是，由于重整催化剂(贵金属催化剂)对硫非常敏感，因而在重整工艺中包含在原料中的硫通常被限定在小于1ppm。因此，为了除去烃中的硫，在催化剂的存在下，在氢气氛围中并在高温和高压下使硫与氢反应以使硫转化为硫化氢，然后使用分离器将硫化氢与烃分离。
同时，当烃类材料中所含的汞被排放到空气中时，即使是排放了少量的汞也会造成环境和安全问题。此外，在石油化工工艺中，当汞与催化剂接触时，汞会成为使催化剂中毒的材料，导致催化剂失活，从而破坏该石油化工工艺。特别是，由于重整催化剂(贵金属催化剂)对汞非常敏感，因而在重整工艺中包含在原料中的汞通常被限定在小于1ppb。因此，已经研究了从烃类材料中除去汞的各种方法。
通常，已经使用的除汞方法包括以下步骤：在催化剂的存在下，在相对高温下使氢与含汞的原料反应；以及在相对低温下使用捕集剂捕集反应产物中的汞。然而，该方法的问题在于：为了除去汞必需进行额外的两步工艺，因此需要额外的设备和操作成本。
发明内容
技术问题
因此，本发明人已经发现，在从含有硫和汞的烃类材料中除去硫的常规工艺中，如果通过将汞以硫化汞的形式吸附于催化剂的金属活性位点或载体上，从而在一个步骤中同时除去硫和汞时，那么可以容易且以低成本除去烃类材料中的硫和汞，而无需进行额外的除汞工艺。基于这一发现完成了本发明。
解决问题的方案
本发明的一个方面提供了一种从烃类材料中同时除去硫和汞的方法，包括：在包含担载于载体上的金属的催化剂的存在下，对含有硫和汞的烃类材料进行加氢处理，以将硫转化为硫化氢，并将汞以硫化汞的形式吸附于所述催化剂的金属活性位点或载体上。
在这一方法中，烃类材料可为选自以下材料所构成的组中的至少一者：原油、天然气和天然气凝析油；以及由其制得的汽油、轻质石脑油、重质石脑油、煤油、轻瓦斯油(LGO)、重瓦斯油(HGO)和常压渣油。
此外，烃类材料可以是沸点为约60℃～180℃的重质石脑油。
此外，所述金属可以是选自由钴、钼、镍、钨、钴-钼、镍-钼、镍-钨和钴-钨所构成的组中的至少一者。
此外，所述载体可以是选自由氧化铝、活性炭、二氧化硅、二氧化硅-氧化铝、氧化锆和二氧化钛所构成的组中的至少一者。
此外，加氢处理反应可在200℃～400℃的温度下进行。
根据权利要求1所述的方法可还包括：向所述烃类材料中加入硫化合物。
在本文中，所述硫化合物可由下式表示：
R1-(S)x-R2，
其中X为1至7的整数，并且R1和R2各自独立地为选自由氢、烷基、烯基、炔基和芳基所构成的组中的至少一者。
此外，所述硫化合物可以是选自由硫化氢、二甲基硫醚(DMS)、二甲基二硫醚(DMDS)、二乙硫醚(DES)、二乙基二硫醚(DEDS)和含硫气体所构成的组中的至少一者。
此外，加入所述烃类材料中的硫化合物的量为每公斤所述烃类材料中加入1mg～10000mg，所述硫化合物的量是以硫原子计的。
此外，加入所述烃类材料中的硫化合物的量为每公斤所述烃类材料中加入1mg～3000mg，所述硫化合物的量是以硫原子计的。
根据权利要求1所述的方法，可还包括：在装有催化剂的反应器的后端提供吸附材料。
在本文中，所述吸附材料可以为选自由氧化铝、活性炭、二氧化硅、二氧化硅-氧化铝、氧化锆和二氧化钛所构成的组中的至少一者。
本发明的有益效果
根据本发明，在从含有硫和汞的烃类材料中除去硫化合物的工艺中，同时除去了硫化合物和汞化合物，从而能够容易且以低成本除去汞而无需进行额外的除汞工艺。
此外，根据本发明，在烃类材料中包含相对少量(若干ppm)的硫化合物的情况中，当向烃类材料中加入硫化合物、或是向烃类材料中引入含有硫化合物的含硫气体时，所述烃类材料中的硫化合物的含量增加，从而能更有效地除去汞。
具体实施方式
下文将更详细地描述本发明。
在本说明书中，硫的含义包括硫和硫化合物，并且汞的含义包括汞和汞化合物。
通常，在除硫工艺中，催化剂中的金属以金属硫化物的形式存在。在本发明中，在硫化催化剂的存在下，烃类材料中所包含的硫被转化为硫化氢，并且烃类材料中所包含的汞被转化为金属汞。转化形成的金属汞与催化剂中的金属硫化物活性位点反应或与硫化氢反应，从而转化为硫化汞(HgS)，该硫化汞(HgS)可被吸附在催化剂的金属活性位点上或吸附在催化剂的载体上，由此被除去。由于该反应是在同一催化剂层中连续进行的，因此在常规除硫工艺中可将汞与硫一起除去。吸附在催化剂上的硫化汞(HgS)会影响该催化剂的钝化。然而，由于烃类材料中汞的量与催化剂中金属活性位点的数目相比是非常少的，因此硫化汞(HgS)不会显著影响催化剂的钝化。
根据本发明的一个实施方案，含有硫和汞的烃类材料可以为选自由如下材料所构成的组中的至少一者：原油、天然气和天然气凝析油；以及由其制得的汽油(C1～C4)、轻质石脑油(C5～C6)、重质石脑油(C7～C12)、煤油(C12～C17)、轻瓦斯油(LGO，(C17～C26))、重瓦斯油(HGO)和常压渣油(C26或更多)。更具体而言，沸点为约60℃～180℃的重质石脑油可以用作烃类材料。
根据本发明的一个实施方案，在本发明所用的催化剂中，载体可以担载选自钴(Co)、钼(Mo)、镍(Ni)、钨(W)、钴-钼(Co-Mo)、镍-钼(Ni-Mo)、镍-钨(Ni-W)和钴-钨(Co-W)所构成的组中的至少一种金属。在本文中，在诸如钴(Co)、钼(Mo)、镍(Ni)等金属的情况下，可以使用其各种前体。例如，四水合七钼酸铵(以下称为“AHM”)可以用作钼(Mo)前体，六水合硝酸钴(以下称为“CNH”)可以用作钴(Co)前体，并且六水合硝酸镍(以下称为“NNH”)可以用作镍(Ni)前体。此外，载体可以为选自由氧化铝、活性炭、二氧化硅、二氧化硅-氧化铝、氧化锆和二氧化钛所构成的组中的至少一者。更具体而言，所述载体可具有足够的表面积、孔体积和平均孔径以吸附硫化汞，并且可具有30m2/g或更大的BET表面积，优选具有100m2/g至500m2/g的BET表面积。此外，所述载体的孔容积为0.3ml/g或更大，优选为0.4ml/g至1.2ml/g，平均孔径可为5nm或更大。所述金属的量可以占所述催化剂总重量的1重量％至80重量％，优选为5重量％至60重量％，更优选为10重量％至40重量％。
根据本发明的一个实施方案，所述催化剂可通过以下方式制备：使氧化铝载体担载占所述催化剂总重量的1重量％～10重量％的钴和5重量％～30重量％的钼。
此外，所述催化剂还可通过以下方式制备：使氧化铝载体担载占所述催化剂总重量的1重量％～10重量％的镍和5重量％～30重量％的钼。
根据本发明的一个实施方案，可以通过在反应前进行硫化作用而活化本发明的催化剂。可使用如下方法来进行催化剂的硫化：在反应器中对含有硫化合物的催化剂进行加氢处理的同时对催化剂进行硫化的方法；或者在使催化剂与硫化合物反应或与含有硫化合物的原料反应的同时对催化剂进行硫化的方法，但并不仅限于此。
根据本发明的一个实施方案，在本发明的加氢处理反应中，反应温度可以为200℃至400℃，优选为270℃至360℃，氢压力可以为10kg/cm2至150kg/cm2，优选为25kg/cm2至90kg/cm2，液空速可以为0.3hr-1至12hr-1，并且每单位体积催化剂的氢流速可以为5vol/hr至500vol/hr。
根据本发明的一个实施方案，诸如天然气凝析油之类的烃类材料具有若干ppb的相对高的汞化合物含量，但是具有若干ppm的相对低的硫化合物含量。因此，可能存在这样的情况，其中，通过由烃类材料中存在的硫化合物形成硫化氢，存在于这样的烃类材料中的汞不能被完全除去。在这种情况下，如果将硫化合物直接加入到烃类材料中，或是通过循环含有硫化合物的含硫气体而将硫化合物加入到烃类材料中，那么可提高烃类材料中的硫化合物的含量，从而能够更有效地除去烃类材料中的汞。
根据本发明的一个实施方案，硫化合物由下式表示：
R1-(S)x-R2，
其中X为1至7的整数，并且R1和R2各自独立地为选自由氢、烷基、烯基、炔基和芳基所构成的组中的至少一者。
此外，额外使用的硫化合物可以为选自由硫化氢、二甲基硫醚(DMS)、二甲基二硫醚(DMDS)、二乙硫醚(DES)、二乙基二硫醚(DEDS)和含硫气体所构成的组中的至少一者。
根据本发明的一个实施方案，每公斤所述烃类材料额外使用的硫化合物的量可以为1mg～10000mg，优选为1mg～3000mg，所述硫化合物的量是以硫原子计的。当向烃类材料中额外加入硫化合物时，可以在一步反应中同时除去烃类材料中的硫和汞。
根据本发明的一个实施方案，硫和汞分别转化为硫化氢和金属汞，并且转化形成的金属汞和包含在烃类材料中的金属汞与催化剂中的金属硫化物活性位点反应或与硫化氢反应，从而转化为硫化汞(HgS)，最终硫化汞(HgS)被吸附在所述催化剂的活性位点或载体上。在本文中，为了加速硫化汞(HgS)的吸附，可以在装有催化剂的反应器的后端提供吸附材料，从而更容易地吸附氢物质中的汞。所述吸附材料可为选自由氧化铝、活性炭、二氧化硅、二氧化硅-氧化铝、氧化锆和二氧化钛所构成的组中的至少一者。
本发明的最佳实施方式
以下将结合以下制备例和实施例对本发明进行详细描述。这些例子用于示例本发明，而本发明的范围不应限于此。
制备例1：CoMo/Al 2 O 3 催化剂的制备
使用直径为1mm、表面积为260m2/g、平均孔径为10nm且总孔体积为约0.83ml/g的γ-晶型Al2O3作为载体来制备CoMo/Al2O3催化剂，该催化剂包含约10重量％的钼(Mo)和约3重量％的钴(Co)。在CoMo/Al2O3催化剂的制备中，使用Mo的前体AHM和Co的前体CNH。
按照以下顺序制备CoMo/Al2O3催化剂。
首先，将AHM溶于蒸馏水中制得水溶液，将Al2O3载体浸入该水溶液中，然后在150℃下干燥2小时，随后在500℃下连续煅烧2小时，从而制得Mo/Al2O3催化剂。
随后，将CNH溶于蒸馏水中制得水溶液，将Mo/Al2O3催化剂浸入该水溶液中，然后在150℃下干燥2小时，随后在500℃下连续煅烧2小时，从而制得CoMo/Al2O3催化剂。
将以这种方式制得的2.6cc的CoMo/Al2O3催化剂装入圆筒形反应器中，随后在以100cc/分钟的流速供给含有10％的H2S和90％的H2的混合气体的同时，在400℃下硫化5小时。
制备例2：NiMo/Al 2 O 3 催化剂的制备
使用直径为1mm、表面积为260m2/g、平均孔径为10nm且总孔体积为约0.83ml/g的γ-晶型Al2O3作为载体来制备NiMo/Al2O3催化剂，该催化剂包含约10重量％钼(Mo)和约3重量％镍(Ni)。在NiMo/Al2O3催化剂的制备中，使用Mo的前体AHM和Ni的前体NNH。除了上述条件不同之外，按照与制备例1相同的方式制备NiMo/Al2O3催化剂和进行后处理。
实施例1至4：根据原料中的硫含量和反应温度来除去重质石脑油 中的汞
在反应压力为31巴、氢气流速为60cc/分钟的条件下，使用制备例1中制得的CoMo/Al2O3催化剂，使作为原料的重质石脑油与供料流速为0.26cc/分钟(LHSV＝5.1hr-1)的氢反应。实施例1至4中使用的重质石脑油均为沸点在60℃～180℃范围的组分，并且均是在原油分馏过程中从常压蒸馏塔获得的。在实施例1中，重质石脑油中的硫含量为3ppm，并且重质石脑油中的汞含量为2.9ppb。然而，在实施例2至4中，重质石脑油中的硫含量分别为9ppm、188ppm和277ppm。在实施例2至4中，为了测量重质石脑油中硫和汞的去除对重质石脑油中硫含量的依赖程度，在原料中混入二甲基二硫醚(DMDS)，并对其含量进行调整。为了测量重质石脑油中硫的转化率以及重质石脑油中汞的去除率对反应温度的依赖性，将反应温度改变为290℃、310℃和330℃，同时进行测试。每3天获取与反应温度相应的样品，并分别使用硫分析仪和汞分析仪来评价所得样品中的硫转化率和汞去除度，其结果在下表1中示出。
表1
如上表1所示，在实施例1中，使用CoMo/Al2O3时的硫去除度为约58％～79％，其根据反应温度的不同而改变。为了观测通过原料中所含的硫化物与氢反应而生成的硫化氢(H2S)是否溶于产物中，使用GC-SCD分析产物中所含的硫组分。结果可以确定，产物中包含的大部分硫组分以硫化氢(H2S)的形式存在，而不以未转化的硫组分的形式存在。事实上，由于在氢化反应后能够利用分离器将硫化氢(H2S)完全分离，因此可以看出，相比于上表1所示的硫转化率，更大量的硫化合物转化为硫化氢(H2S)。在实施例1中，在原料中含有3ppm的硫化合物的情况中，原料中所含的2.9ppb的汞在290℃和310℃的反应温度下被完全除去，而在330℃的反应温度下仅除去了62％的汞。
参照实施例2至4的结果，可以看出，即使当原料中的硫含量为高于3ppm的9ppm、188ppm和277ppm时，硫的去除度也很高。此外，通过使用GC-SCD分析产物中所含的硫组分得知，产物中所包含的大部分硫组分为硫化氢(H2S)的形式存在，而不是以未转化的硫组分或二甲基二硫醚(DMDS)的形式存在，由这一事实可以看出，相比于上表1给出的硫转化率，更大量的硫化合物被转化为硫化氢(H2S)。
此外，根据实施例1和2，当包含在原料中的硫化合物的量为3ppm或9ppm的较低量时，可以看出，即使在310℃或330℃的相对高温下，汞的去除度也会降低。相反，当包含在原料中的硫化合物的量为188ppm或277ppm的相对高的量时，可以看出，在全部温度范围内汞均被完全去除。
空白试验
进行空白试验以确认不通过催化反应，而是通过诸如在原料泵中使用过滤器来捕集汞或者使汞附着至反应器的壁等方法而去除汞的可能性。按照与实施例1相同的方式进行空白试验，不同之处在于反应器中不存在催化剂。结果可以看出，重质石脑油原料中所包含的硫含量(3ppm)和重质石脑油原料中所包含的汞含量(2.9ppb)即使在反应后也没有改变。这表明可以排除硫和汞由于催化反应以外的外部因素而被除去的可能性。
尽管为了示意性的目的公开了本发明的优选实施方案，但是本领域技术人员将理解的是，在不脱离由所附权利要求书所公开的本发明的范围和精神的情况下，可以进行各种不同的修改、添加和替换。

Claims (9)

1.一种在一步反应中同时除去烃类材料中的硫和汞的方法，包括：
在包含担载于载体上的金属硫化物的单一催化剂的存在下，对含有硫和汞的烃类材料进行加氢处理，其中所述烃类材料中的硫和汞分别转化为硫化氢和金属汞，并且转化的金属汞与所述催化剂中的金属硫化物活性位点反应或与转化的硫化氢反应，从而形成硫化汞；以及将硫化汞吸附于所述催化剂的金属硫化物活性位点或载体上，
其中所述催化剂中的金属为选自由钴、钼、镍、钨、钴-钼、镍-钼、镍-钨和钴-钨所构成的组中的至少一者，
其中所述载体具有100m2/g-500m2/g的BET表面积，孔容积为0.4ml/g至1.2ml/g，平均孔径为5nm或更大，并且
其中所述金属的量占所述催化剂总重量的5重量％-60重量％。
2.根据权利要求1所述的方法，其中所述烃类材料为选自由原油、天然气和天然气凝析油；以及由其制得的汽油、轻质石脑油、重质石脑油、煤油、轻瓦斯油(LGO)、重瓦斯油(HGO)和常压渣油构成的组中的至少一者。
3.根据权利要求1所述的方法，其中所述烃类材料是沸点为60℃～180℃的重质石脑油。
4.根据权利要求1所述的方法，其中所述载体为选自由氧化铝、活性炭、二氧化硅、二氧化硅-氧化铝、氧化锆和二氧化钛所构成的组中的至少一者。
5.根据权利要求1所述的方法，其中所述加氢处理反应是在如下条件下进行的：温度为270℃-360℃，氢压力为25kg/cm2-90kg/cm2，液空速为0.3hr-1-12hr-1，且每单位体积催化剂的氢流速为5vol/hr-500vol/hr。
6.根据权利要求1所述的方法，还包括：
向所述烃类材料中加入硫化合物，其中以硫原子计，所述硫化合物的量为每公斤所述烃类材料中添加1-10000mg，
其中所述硫化合物为选自由二甲基硫醚(DMS)、二甲基二硫醚(DMDS)、二乙硫醚(DES)和二乙基二硫醚(DEDS)所构成的组中的至少一者。
7.根据权利要求6所述的方法，其中以硫原子计，添加至所述烃类材料的硫化合物的量为每公斤所述烃类材料中添加1mg～3000mg。
8.根据权利要求1所述的方法，
其中还在装有所述催化剂的反应器的后端提供吸附材料。
9.根据权利要求8所述的方法，其中所述吸附材料为选自由氧化铝、活性炭、二氧化硅、二氧化硅-氧化铝、氧化锆和二氧化钛所构成的组中的至少一者。
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US9370757B2 (en) 2012-08-21 2016-06-21 Uop Llc Pyrolytic reactor
US9308513B2 (en) 2012-08-21 2016-04-12 Uop Llc Production of vinyl chloride from a methane conversion process
US20140058089A1 (en) * 2012-08-21 2014-02-27 Uop Llc Sulfur removal and methane conversion process using a supersonic flow reactor
US9707530B2 (en) 2012-08-21 2017-07-18 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US9689615B2 (en) 2012-08-21 2017-06-27 Uop Llc Steady state high temperature reactor
US9434663B2 (en) 2012-08-21 2016-09-06 Uop Llc Glycols removal and methane conversion process using a supersonic flow reactor
US8927769B2 (en) 2012-08-21 2015-01-06 Uop Llc Production of acrylic acid from a methane conversion process
US9205398B2 (en) 2012-08-21 2015-12-08 Uop Llc Production of butanediol from a methane conversion process
US9327265B2 (en) 2012-08-21 2016-05-03 Uop Llc Production of aromatics from a methane conversion process
US8933275B2 (en) 2012-08-21 2015-01-13 Uop Llc Production of oxygenates from a methane conversion process
US8937186B2 (en) 2012-08-21 2015-01-20 Uop Llc Acids removal and methane conversion process using a supersonic flow reactor
US9656229B2 (en) 2012-08-21 2017-05-23 Uop Llc Methane conversion apparatus and process using a supersonic flow reactor
US9023255B2 (en) 2012-08-21 2015-05-05 Uop Llc Production of nitrogen compounds from a methane conversion process
JP6145619B2 (ja) * 2013-08-29 2017-06-14 日本インスツルメンツ株式会社 還元気化水銀測定装置
US10953389B2 (en) * 2016-02-01 2021-03-23 Albemarle Europe Sprl Nickel containing mixed metal-oxide/carbon bulk hydroprocessing catalysts and their applications
US11697538B2 (en) 2018-06-21 2023-07-11 First Quality Tissue, Llc Bundled product and system and method for forming the same
US11738927B2 (en) 2018-06-21 2023-08-29 First Quality Tissue, Llc Bundled product and system and method for forming the same
CN115698231A (zh) * 2020-05-29 2023-02-03 埃克森美孚化学专利公司 含汞进料的烃热解
WO2024035875A1 (en) * 2022-08-12 2024-02-15 Championx Llc Development of hydrogen compatible chemicals and test methods for energy sector application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045596A (zh) * 1989-03-16 1990-09-26 法国石油公司 从烃中除去汞或许砷的方法
CN1024135C (zh) * 1988-10-04 1994-04-06 切夫尔昂研究公司 使用大孔隙催化剂加氧脱金属和加氢脱硫的方法
WO2008023563A1 (fr) * 2006-08-22 2008-02-28 Sumitomo Metal Industries, Ltd. installation de nettoyage de barre de mandrin

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4814152A (en) * 1987-10-13 1989-03-21 Mobil Oil Corporation Process for removing mercury vapor and chemisorbent composition therefor
FR2628338B1 (fr) * 1988-03-10 1991-01-04 Inst Francais Du Petrole Procede pour l'elimination du mercure dans les hydrocarbures
US4966683A (en) * 1989-04-27 1990-10-30 Mobil Oil Corporation Process for the removal of mercury from natural gas condensate
FR2690923B1 (fr) 1992-05-11 1994-07-22 Inst Francais Du Petrole Procede de captation de mercure et d'arsenic dans une coupe d'hydrocarbure.
FR2701270B1 (fr) 1993-02-08 1995-04-14 Inst Francais Du Petrole Procédé d'élimination du mercure dans les hydrocarbures par passage sur un catalyseur présulfuré.
JP3624671B2 (ja) * 1997-01-13 2005-03-02 太陽テクノサービス株式会社 炭化水素留分中の微量金属の吸着除去方法
GB2365874B (en) * 2000-06-29 2004-12-08 Wcp Internat Ltd Purifying hydrocarbons
WO2002036717A1 (fr) 2000-10-30 2002-05-10 Idemitsu Petrochemical Co., Ltd. Procede de recuperation du mercure compris dans un hydrocarbure liquide
GB0616343D0 (en) 2006-08-17 2006-09-27 Johnson Matthey Plc Mercury removal
FR2923837B1 (fr) * 2007-11-19 2009-11-20 Inst Francais Du Petrole Procede de desulfuration en deux etapes d'essences olefiniques comprenant de l'arsenic.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1024135C (zh) * 1988-10-04 1994-04-06 切夫尔昂研究公司 使用大孔隙催化剂加氧脱金属和加氢脱硫的方法
CN1045596A (zh) * 1989-03-16 1990-09-26 法国石油公司 从烃中除去汞或许砷的方法
WO2008023563A1 (fr) * 2006-08-22 2008-02-28 Sumitomo Metal Industries, Ltd. installation de nettoyage de barre de mandrin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
天然气和烃油脱汞技术研究进展;汪祥胜;《化学工业与工程技术》;20090630;第31卷(第3期);29-32 *

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