CN101516775B - 用于制备二硫化碳的方法 - Google Patents
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Abstract
一种用于制备二硫化碳的方法，所述方法包括以下步骤：(a)使一氧化碳与硫化氢反应形成硫化羰和氢；(b)使步骤(a)中形成的硫化羰与有效使硫化羰歧化成二硫化碳和二氧化碳的催化剂接触。
Description
技术领域
本发明提供从一氧化碳和硫化氢制备二硫化碳的方法。本方法另外制得氢和二氧化碳。
背景技术
通常根据下面的反应方程式，通过使轻质饱和烃与在气相中的元素硫反应来制备二硫化碳：
CnH2(n+1)+(3n+1)S→nCS2+(n+1)H2S
例如，GB 1,173,344中公开了一种在不存在催化剂的条件下、在不超过10个大气压的压力下、于温度维持在550-850℃的反应区中使气相硫和丙烷反应的方法。
US 3,087,788中公开了一种在优选与随后的催化反应阶段组合的非催化反应阶段中从烃气和气态硫生产二硫化碳的方法，其中两个阶段都在2-20个大气压的压力和400-750℃的温度下操作。
也已知通过使液体硫与烃催化反应而制备二硫化碳。例如，US2,492,719中公开了一种用于制备二硫化碳的方法，其中在约500-700℃的温度下、在足以使硫保持在液相中的压力下使催化剂于熔态硫中的悬浮体与烃气接触。
使用烃作为制备二硫化碳的碳源的缺点是烃中的氢原子与元素硫反应形成硫化氢。因为将硫化氢排放至大气中是非常不理想的和几乎一直不被允许，因此需要昂贵的处理过程，通常使其转化成元素硫。因此，使用不含氢原子的碳源以制备二硫化碳将是有利的。
1960年以前，将固体碳质材料例如木炭用作二硫化碳制备的碳源。在非常高的温度下使固体碳质材料与气化的元素硫接触。然而出于对环境和安全的考虑，这些使用固体碳质材料的方法被上述使用轻质烃(例如甲烷和丙烷)作为碳源的方法所替代。
已知使用一氧化碳作为二硫化碳制备的碳源。例如在US
2004/0146450中公开了从一氧化碳和二氧化硫制备二硫化碳的使用两个反应器的方法。两个催化反应一前一后进行。在第一反应器中，在不存在催化剂的条件下使一氧化碳和二氧化硫反应以形成硫化羰和二氧化碳。在第二反应器中，将在第一反应器中形成的硫化羰催化转化成二硫化碳和二氧化碳。利用溶剂从第二反应器连续移除二硫化碳。
在US 4,122,156中也公开了从一氧化碳和二氧化硫制备二硫化碳的使用两个反应器的方法。
U.S.2,767,059中描述的一步法将H2S和CO转化成CS2。该方法中的唯一产物是CS2。
U.S.4,999,178中描述了用于将H2S转化成氢和硫的方法流程。该方法没有产出任何的二硫化碳。在第一步中，H2S与含H2S、COS和CS2的循环气以及纯CO2物流反应。其中没有描述H2S和CO之间的反应。反应中生成的氢经过下面的变换反应制得：
CO+H2O→CO2+H2。
发明内容
目前已发现可以通过使一氧化碳与硫化氢反应形成硫化羰和氢和随后使形成的硫化羰歧化成二硫化碳和二氧化碳，从而从一氧化碳制备二硫化碳。
因此，本发明提供用于制备二硫化碳的方法，所述方法包括以下步骤：
(a)使一氧化碳与硫化氢反应形成硫化羰和氢；
(b)使步骤(a)中形成的硫化羰与有效使硫化羰歧化成二硫化碳和二氧化碳的催化剂接触。
与使用烃作为碳源的常规二硫化碳制备方法相比，本发明的方法的优点是没有形成必须再循环至克劳斯装置以被转化成硫的硫化氢。
与已知的使用一氧化碳作为碳源的二硫化碳制备方法(即US2004/0146450和US 4,122,156中公开的方法，其中使一氧化碳与二氧化硫反应)相比，本发明的方法的优点是该方法副产更少的二氧化碳。本发明的方法中1摩尔二硫化碳副产1摩尔二氧化碳，而US2004/0146450和US 4,122,156的方法中1摩尔二硫化碳副产5摩尔二氧化碳。在本发明方法中副产氢，当在其它工艺中应用或与之整合时将带来明显的设计和成本的有益效果。
当与烃质原料转化成合成气(即主要含一氧化碳和氢的气态混合物)组合操作时，本发明的方法具有特别的优势。制得的合成气通常用于后续的通过费-托法的烃合成、其它化学合成法(例如合成甲醇或合成氨)、在燃气涡轮中发电或用于生产氢。经常地，对于设想的用途而言合成气中一氧化碳与氢的比太大，和因此通常通过使合成气进行水煤气变换反应将合成气中的部分一氧化碳转化成氢。解决这个问题的另一种方法是生产过量的氢，例如通过重整，特别是蒸汽甲烷重整。将本发明的方法与合成气制备组合的优点在于将部分一氧化碳用于二硫化碳制备，从而将剩余合成气中一氧化碳与氢的比降低至更理想的水平。此外，在一氧化碳与硫化氢的反应中副产了另外的氢。这些另外的氢可有利地用于进一步降低剩余合成气中的一氧化碳与氢的比。本发明方法制得的氢也可用于改质重油馏分例如通过加氢裂化、加氢等，或用于发电。
另一个优点是因为烃质原料通常含有硫化合物，所以在合成气生产场所通常可以获得硫化氢。如果硫化合物是硫化氢，例如当是含硫天然气时，通常在气化前使硫化氢与烃质原料分离。如果原料含有其它硫化合物，则可在气化前使原料加氢脱硫，从而生产硫化氢。另外的优点是使烃质化合物的氢原子转化成有用的氢。副产的一氧化碳用作制备二硫化碳的无氢原料，和因此避免了形成硫化氢。
附图说明
图1中显示了从含硫天然气制备二硫化碳和液体烃的工艺流程图。
图2中显示了从含硫天然气制备二硫化碳和用于发电的氢的工艺流程图。
图3中显示了从含硫天然气制备二硫化碳、氨和硫代碳酸铵的工艺流程图。
具体实施方式
在本发明的方法中，首先根据下面的反应方程式使一氧化碳与硫化氢反应形成硫化羰和氢：
CO+H2S→COS+H2(1)
本领域中已知该反应，例如由US 5,609,845和US 6,497,855B1中可知。可以以本领域中已知的任意适合的方式进行该反应。通常，通过使气态一氧化碳和气态硫化氢与催化剂接触进行该反应。适合的催化剂是例如US 5,609,845中描述的那些(该专利的公开内容经此引用并入本文)，例如混合金属硫化物、过渡金属硫化物，特别是二氧化硅载带的金属硫化物。步骤(a)的典型反应温度是120-750℃。
随后在步骤(b)中，使本发明的方法的步骤(a)中形成的硫化羰与有效使硫化羰歧化成二硫化碳和二氧化碳的催化剂接触，发生如下反应：
优选地，在使硫化羰歧化前，使步骤(a)中形成的氢与步骤(a)中形成的硫化羰分离。可以通过任意适合的常规技术例如通过选择性吸收、吸附、精馏或分子筛分离实现上述分离。变压吸收(PSA)和膜分离是特别适合的分离方法。另一适合的方法是低温分离，例如低温蒸馏。
本领域中已知有效使硫化羰歧化的催化剂，例如由US2004/0146450和US 4,122,156中可知。优选地，催化剂含有一种或多种金属氧化物。适合的催化剂的实例是氧化铝、二氧化钛、氧化铝-二氧化钛、二氧化硅-氧化铝、石英或粘土例如高岭土。催化剂优选比表面积是至少50m2/g，更优选至少100m2/g，甚至更优选至少200m2/g。特别优选的催化剂是γ-氧化铝、二氧化钛、氧化铝-二氧化钛或二氧化硅-氧化铝。
硫化羰与歧化催化剂接触的反应条件可以是任意已知适用于该反应的反应条件，例如US 2004/0146450和US 4,122,156中描述的条件。
歧化反应(2)是热力学不利的可逆反应。因为反应热接近0，平衡常数随温度变化不大。必要时，可通过从反应混合物中移除二硫化碳(例如通过溶剂提取或冷凝)增大硫化羰的转化率。
步骤(a)中与硫化氢反应的一氧化碳可以是来自任意适合来源的一氧化碳。优选一氧化碳来自合成气物流。因此，本发明的方法优选还包括以下步骤：
(c)使烃质原料部分氧化以获得含一氧化碳和氢的合成气；其中步骤(a)中反应的一氧化碳是步骤(c)中获得的一氧化碳。
本领域中已知使烃质原料部分氧化以生产合成气。烃质原料可以是任意适合的原料，例如含气态、液态或固态烃的物流，例如天然气、馏出物物流、原油的常压蒸馏或真空蒸馏的渣油、焦油砂衍生沥青、焦油砂衍生沥青的常压蒸馏或真空蒸馏的渣油或煤。同样，木质纤维素生物质物流例如木材、稻草、玉米杆、甘蔗渣或类似物也可用作烃质原料。
在烃质原料的部分氧化中，形成合成气。合成气主要含有一氧化碳和氢，如果将空气用作部分氧化反应的氧化剂，则也含有氮。合成气可含有少量的其它气态化合物，例如二氧化碳、蒸汽、硫化氢和硫化羰。
如果步骤(a)中反应的一氧化碳通过使烃质原料部分氧化获得和将通过部分氧化生产的合成气用于合成烃或合成甲醇或需要合成气的一氧化碳与氢的比低于通过部分氧化步骤获得的比的其它用途中，则本发明的方法具有特别的优势。通过将部分一氧化碳用于制备二硫化碳，剩余合成气中的一氧化碳与氢的比降低至更需要的水平。通过将本发明方法的步骤(a)中形成的氢加入剩余合成气中，可以进一步降低该比值。因此，无需通过水煤气变换将部分一氧化碳转化成氢和/或通过例如蒸汽甲烷重整生产另外的氢。
因此，在本发明的优选实施方案中，在步骤(a)中使步骤(c)中获得的部分一氧化碳与硫化氢反应，和将步骤(c)中获得的一氧化碳的剩余部分和氢用于费-托法中合成烃或用于甲醇合成。更优选地，将步骤(a)中形成的氢与步骤(c)中获得的一氧化碳的剩余部分和氢用于费-托法中合成烃或用于甲醇合成。上述技术方案特别适用于使用低H/C比的初始原料例如煤的的方法中。
可通过在用于步骤(a)的反应器中使步骤(c)中获得的部分合成气物流与硫化氢接触而使步骤(c)中获得的部分一氧化碳与硫化氢进行反应。优选地，在步骤(a)中与硫化氢反应之前，首先使步骤(c)中获得的合成气物流中的部分一氧化碳与合成气物流分离。可通过将至少部分合成气物流分离成富含氢的物流和富含一氧化碳的物流而实现这一点。可以通过本领域已知的任意适合的方式例如变压吸收或膜分离进行该分离。富含氢的物流可以基本上是纯氢，例如当使用氢选择性膜用于分离的情况下。随后在本发明的方法的步骤(a)中使富含一氧化碳的物流与硫化氢接触。物流中的一氧化碳浓度可以根据合成气的组成和所用的分离方法而变化。优选地，富含一氧化碳的物流中的一氧化碳浓度是70-100vol％。
在本发明的另一优选实施方案中，在步骤(a)中使步骤(c)中获得的基本上全部的一氧化碳与硫化氢反应。本文中“基本上全部的一氧化碳”表示至少95vol％的一氧化碳，优选至少99vol％。随后可以将步骤(c)中获得的氢有利地用于需要相对纯的氢物流的用途中，例如在氢气透平中或在燃料电池中发电或用于生产氨。更优选地，步骤(a)中形成的氢与步骤(c)中获得的氢一起用于这些用途中。
因此，在本发明的优选实施方案中，在步骤(a)中使步骤(c)中获得的基本上全部的一氧化碳与硫化氢反应和将步骤(c)中获得的氢用于在氢气透平或燃料电池中发电。更优选地，步骤(a)中形成的氢与步骤(c)中获得的氢一起用于在氢气透平或在燃料电池中发电。
可通过在用于步骤(a)的反应器中使步骤(c)中获得的全部合成气物流与硫化氢接触或通过首先将所述合成气物流分离成含有步骤(c)中形成的基本上所有的一氧化碳的富含一氧化碳的物流和富含氢的物流，而在步骤(a)中使步骤(c)中获得的基本上所有的一氧化碳与硫化氢反应。随后在用于步骤(a)的反应器中使富含一氧化碳的物流与硫化氢接触。在这种情况下，富含氢的物流基本不含一氧化碳和可适当地任选在进一步纯化步骤之后用于在氢气透平或燃料电池中发电、生产氨或用于原油炼制的加氢转化法例如加氢裂化、加氢脱硫、加氢中或其它用于相对纯的氢的已知用途中。
如果使步骤(c)中获得的全部合成气物流与硫化氢反应，则步骤(c)中获得的氢将与步骤(a)中形成的氢一起存在于步骤(a)的反应流出物中。优选地，随后使流出物中的氢与硫化羰和未转化的反应物分离，和任选在进一步的纯化步骤之后用于需要相对纯的氢物流的用途中。
步骤(a)中与一氧化碳反应的硫化氢可以是来自任意来源的硫化氢。当一氧化碳是通过部分氧化步骤(c)获得时，硫化氢优选是从烃质原料分离的硫化氢或从烃质原料中的硫化合物获得的硫化氢。例如，可以通过使原料加氢脱硫或在部分氧化步骤(c)中从这些硫化合物获得硫化氢。也可以使用从含硫天然气中提取的硫化氢。
在本发明的优选实施方案中，烃质原料是含硫化氢的天然气即含硫天然气，和在步骤(a)与一氧化碳反应的至少部分硫化氢是从所述天然气分离的硫化氢。可通过本领域已知的任意适合的技术例如通过在有机溶剂中物理吸收之后进行溶剂再生而从含硫化氢的烃质原料中分离硫化氢。
在本发明的方法的步骤(b)中，形成二硫化碳和二氧化碳。可以使二硫化碳与二氧化碳及未反应的硫化羰分离，例如通过冷凝或溶剂提取进行。作为替代，可以获得含二硫化碳、二氧化碳和未反应的硫化羰的混合物。与二氧化碳及未反应的硫化羰分离的二硫化碳可以用于二硫化碳的常规用途，例如作为生产人造纤维的原料或作为溶剂。
已知二硫化碳可用作通过混相驱油强化油采收的溶剂。在通过混相驱油强化油采收中，将用于油的溶剂加入油储层中和驱动所述溶剂通过储层以与通过常规方式可获得的油采收相比从储层增大油采收。例如US 3,847,221中公开了使用二硫化碳从焦油砂强化油采收。
优选地，本发明的方法还包括将步骤(b)中形成的至少部分二硫化碳注入油储层中以强化油采收。注入的二硫化碳可以是与所形成的二氧化碳及与未反应的硫化羰分离的相对纯的二硫化碳。然而，为了强化油采收，并不必须使用纯二硫化碳。强化油采收的溶剂可以例如包含大量的二氧化碳。因此，注入的二硫化碳优选是与步骤(b)中形成的二氧化碳以及未反应的硫化羰的混合物形式。同样，在将二硫化碳注入油储层中之前，可以使其它液体组分或物流与二硫化碳混合。
本发明的方法特别适用于强化在部分氧化步骤(c)中使用的烃质原料的采收。特别当是固态或半固态烃质原料例如煤或焦油砂沥青的情况下，可以将制备的二硫化碳有利地用于采收所述烃质原料。
作为将步骤(b)形成的二硫化碳直接注入油储层中的替代，可以将全部或部分步骤(b)中形成的二硫化碳首先转化成三硫代碳酸或四硫代碳酸的盐。随后可以在导致这些盐分解成自由的二硫化碳的条件下将这些盐加入油储层中以强化油采收。本领域中已知通过使用三硫代碳酸或四硫代碳酸的盐以强化油采收，例如由US 5,076,358中可知。在本发明的优选实施方案中，使部分步骤(b)中形成的二硫化碳与硫化氢和氨反应以形成硫代碳酸铵，其中所述氨用部分氧化步骤(c)和/或一氧化碳转化步骤(a)中获得的氢形成。例如，可以如US 4,476,113中所公开的制备硫代碳酸铵。
附图详细说明
现在参照图1-3进一步说明本发明，其中图1-3各自图示了本发明的实施方案的工艺流程图。对于方法的相同部件，这三个图中使用相同的附图标记。
图1中显示了从含硫天然气同时制备二硫化碳和液体烃的工艺流程图。将含硫化氢的天然气物流1即含硫天然气供应至脱硫化氢装置2。脱硫天然气3和含分子氧的气体4供应至部分氧化装置5。在部分氧化装置5中，天然气进料3部分氧化和获得主要含一氧化碳和氢的合成气物流6。将合成气物流6的一部分6a供应至分离器7和分离成富含一氧化碳的气体物流8和富含氢的气体物流9。
将富含一氧化碳的气体物流8与从含硫天然气1分离的硫化氢10一起供应至反应器11以将一氧化碳和硫化氢转化成硫化羰和氢。将在反应器11形成的含硫化羰和氢的混合物12供应至分离步骤13和分离成含硫化羰的物流14和氢15。将氢15加入来自分离器7的富含氢的气体物流9中并与没有送至分离器7的合成气物流6的一部分6b组合。将组合的物流6b、9和15供应至用于合成烃的反应器16以通过费-托法制备烃。作为替代可以将组合物流6b、9和15供应至用于甲醇合成的反应器中(未显示)。在本发明的另一替代实施方案(未显示)中，将物流6b和9组合并供应至用于合成烃的反应器中，和将物流15供应至燃料电池或氢气透平进行发电。
将含硫化羰的物流14供应至歧化反应器18。在反应器18中，形成含二硫化碳、二氧化碳和未转化的硫化羰的反应混合物。从反应器18排出反应混合物19。可通过常规分离装置(未显示)从混合物19分离二硫化碳，和随后例如将其用于强化油采收。作为替代，可将混合物19用作例如用于强化油采收的溶剂。
图2中显示了从含硫天然气同时制备二硫化碳和用于发电的氢的工艺流程图。在图2中所示的本发明的实施方案中，在分离器7中将全部合成气物流6分离成富含一氧化碳的气体物流8和富含氢的气体物流9。使氢15即反应器11中的过程的步骤(a)中形成并随后与硫化羰分离的氢与富含氢的气体物流9组合，和将组合物流供应至燃料电池20进行发电。作为替代，可以将组合物流供应至氢气透平(未显示)进行发电。
图3中显示了从含硫天然气制备二硫化碳、氨和硫代碳酸铵的工艺流程图。
在图3中所示的本发明的实施方案中，在分离器7中将全部合成气物流6分离成富含一氧化碳的气体物流8和富含氢的气体物流9。使氢15即反应器11中的过程的步骤(a)中形成并随后与硫化羰分离的氢与富含氢的气体物流9组合。将组合的氢物流和氮物流22供应至铵反应器23以形成氨24。从过程中回收一部分氨24a，例如用于生产肥料。在反应器27中使一部分氨24b与硫化氢25和二硫化碳26反应以形成硫代碳酸铵28。在分离器29中从反应混合物19中分离二硫化碳26。反应混合物19的剩余部分30如果仍然含有二硫化碳，则可用作用于强化油采收的溶剂。作为替代，可以将部分分离的二硫化碳26直接注入油储层中以强化油采收，和将部分分离的二硫化碳26供应至反应器27以转化成硫代碳酸铵。
可通过将在脱硫化氢装置2中从含硫天然气1分离的硫化氢用作制备硫代碳酸铵的硫化氢25而进行另外的过程整合。供应至铵反应器23的氮物流22可通过空气分离(未显示)获得。随后可将由此获得的氧作为含分子氧的气体4供应至部分氧化装置5。
Claims (8)
1.一种用于制备二硫化碳的方法，所述方法包括以下步骤：
(a)使一氧化碳与硫化氢反应形成硫化羰和氢；
(b)使步骤(a)中形成的硫化羰与有效使硫化羰歧化成二硫化碳和二氧化碳的催化剂接触；
(c)使烃质原料部分氧化以获得含一氧化碳和氢的合成气；
其中步骤(a)中反应的一氧化碳是步骤(c)中获得的一氧化碳。
2.权利要求1的方法，其中在步骤(a)中使步骤(c)中获得的部分一氧化碳与硫化氢反应，和将步骤(c)中获得的一氧化碳的剩余部分和氢用于在费-托法中合成烃或用于甲醇合成。
3.权利要求2的方法，其中将步骤(a)中形成的氢与步骤(c)中获得的一氧化碳的剩余部分和氢一起用于在费-托法中合成烃或用于甲醇合成。
4.权利要求1的方法，其中在步骤(a)中使步骤(c)中获得的基本上全部的一氧化碳与硫化氢反应，和将步骤(c)中获得的氢用于在氢气透平或燃料电池中发电。
5.权利要求4的方法，其中将步骤(a)中形成的氢与步骤(c)中获得的氢一起用于在氢气透平中或在燃料电池中发电。
6.权利要求1-5任一项的方法，其中所述烃质原料含有硫化氢，和在步骤(a)中与一氧化碳反应的至少部分硫化氢是从所述烃质原料中分离的硫化氢。
7.权利要求6的方法，其中所述烃质原料是天然气。
8.前述权利要求任一项的方法，还包括将至少部分步骤(b)中形成的二硫化碳注入油储层中以强化油采收。
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| EP06120802.1 | 2006-09-18 | ||
| EP06120802 | 2006-09-18 | ||
| PCT/EP2007/059746 WO2008034777A1 (en) | 2006-09-18 | 2007-09-17 | A process for the manufacture of carbon disulphide |
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| Publication Number | Publication Date |
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| CN101516775A CN101516775A (zh) | 2009-08-26 |
| CN101516775B true CN101516775B (zh) | 2011-12-28 |
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| CN2007800344252A Expired - Fee Related CN101516775B (zh) | 2006-09-18 | 2007-09-17 | 用于制备二硫化碳的方法 |
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| US (1) | US7763227B2 (zh) |
| EP (1) | EP2064150A1 (zh) |
| CN (1) | CN101516775B (zh) |
| AU (1) | AU2007299081A1 (zh) |
| BR (1) | BRPI0716921A2 (zh) |
| CA (1) | CA2663757C (zh) |
| EA (1) | EA016030B1 (zh) |
| MX (1) | MX2009002537A (zh) |
| WO (1) | WO2008034777A1 (zh) |
Families Citing this family (79)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090200018A1 (en) | 2006-04-27 | 2009-08-13 | Ayca Sivrikoz | Systems and methods for producing oil and/or gas |
| CA2652002C (en) | 2006-05-16 | 2015-01-06 | Shell Internationale Research Maatschappij B.V. | A process for the manufacture of carbon disulphide |
| US8136590B2 (en) | 2006-05-22 | 2012-03-20 | Shell Oil Company | Systems and methods for producing oil and/or gas |
| MX2008016422A (es) | 2006-07-07 | 2009-01-19 | Shell Int Research | Proceso para producir disulfuro de carbono y uso de una corriente liquida de disulfuro de carbono para la recuperacion mejorada de combustible. |
| EP2049767A1 (en) | 2006-08-10 | 2009-04-22 | Shell Internationale Research Maatschappij B.V. | Methods for producing oil and/or gas |
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| CA2693942C (en) | 2007-07-19 | 2016-02-02 | Shell Internationale Research Maatschappij B.V. | Methods for producing oil and/or gas |
| RU2475632C2 (ru) | 2007-10-31 | 2013-02-20 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Система и способ добычи нефти и/или газа (варианты) |
| US9057257B2 (en) | 2007-11-19 | 2015-06-16 | Shell Oil Company | Producing oil and/or gas with emulsion comprising miscible solvent |
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| US10145269B2 (en) | 2015-03-04 | 2018-12-04 | General Electric Company | System and method for cooling discharge flow |
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| CN109095468A (zh) * | 2017-12-27 | 2018-12-28 | 山西铁峰化工有限公司 | 一种以硫化氢为原料制备二硫化碳的方法 |
| CN110724079A (zh) * | 2019-11-07 | 2020-01-24 | 山东益丰生化环保股份有限公司 | 一种利用石化废气合成硫脲的方法 |
| US11505462B2 (en) | 2021-02-15 | 2022-11-22 | Fluor Technologies Corporation | Pre-combustion CO2 removal in a natural gas fed steam methane reformer (SMR) based hydrogen plant |
| WO2022178439A1 (en) * | 2021-02-22 | 2022-08-25 | Fluor Technologies Corporation | Improved gas reformer for producing hydrogen |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2767059A (en) * | 1953-05-29 | 1956-10-16 | Stanolind Oil & Gas Co | Carbon disulfide manufacture |
| US3847221A (en) * | 1973-05-04 | 1974-11-12 | Texaco Inc | Miscible displacement of petroleum using carbon disulfide and a hydrocarbon solvent |
| US3856925A (en) * | 1971-08-19 | 1974-12-24 | Agency Ind Science Techn | Method for manufacture of hydrogen and carbonyl sulfide from hydrogen sulfide and carbon monoxide |
| US4999178A (en) * | 1988-12-08 | 1991-03-12 | Bowman Melvin G | Thermochemical cycle for splitting hydrogen sulfide |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2492719A (en) | 1943-06-26 | 1949-12-27 | Pure Oil Co | Preparation of carbon disulfide |
| US3087788A (en) | 1959-04-06 | 1963-04-30 | Fmc Corp | Combined catalytic and non-catalytic process of producing hydrogen sulfide and carbon disulfide |
| FR1493586A (fr) | 1966-06-15 | 1967-09-01 | Progil | Procédé de fabrication de sulfure de carbone |
| US4122156A (en) | 1975-08-13 | 1978-10-24 | New England Power Company | Process for the production of carbon disulfide from sulfur dioxide removed from a flue gas |
| US4476113A (en) | 1981-10-27 | 1984-10-09 | Union Oil Company Of California | Stabilized fumigant composition comprising an aqueous solution of ammonia, hydrogen sulfide, carbon disulfide and sulfur |
| US5076358A (en) | 1988-07-22 | 1991-12-31 | Union Oil Company Of California | Petroleum recovery with organonitrogen thiocarbonates |
| US5609845A (en) | 1995-02-08 | 1997-03-11 | Mobil Oil Corporation | Catalytic production of hydrogen from hydrogen sulfide and carbon monoxide |
| US6497855B1 (en) | 2000-03-22 | 2002-12-24 | Lehigh University | Process for the production of hydrogen from hydrogen sulfide |
| US7090818B2 (en) | 2003-01-24 | 2006-08-15 | Stauffer John E | Carbon disulfide process |
| EP1871988A2 (en) * | 2005-04-21 | 2008-01-02 | Shell Internationale Research Maatschappij B.V. | Systems and methods for producing oil and/or gas |
-
2007
- 2007-09-17 WO PCT/EP2007/059746 patent/WO2008034777A1/en active Search and Examination
- 2007-09-17 CA CA2663757A patent/CA2663757C/en not_active Expired - Fee Related
- 2007-09-17 EA EA200900469A patent/EA016030B1/ru not_active IP Right Cessation
- 2007-09-17 AU AU2007299081A patent/AU2007299081A1/en not_active Abandoned
- 2007-09-17 MX MX2009002537A patent/MX2009002537A/es not_active Application Discontinuation
- 2007-09-17 EP EP07803511A patent/EP2064150A1/en not_active Withdrawn
- 2007-09-17 US US12/441,172 patent/US7763227B2/en not_active Expired - Fee Related
- 2007-09-17 BR BRPI0716921-3A patent/BRPI0716921A2/pt not_active Application Discontinuation
- 2007-09-17 CN CN2007800344252A patent/CN101516775B/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2767059A (en) * | 1953-05-29 | 1956-10-16 | Stanolind Oil & Gas Co | Carbon disulfide manufacture |
| US3856925A (en) * | 1971-08-19 | 1974-12-24 | Agency Ind Science Techn | Method for manufacture of hydrogen and carbonyl sulfide from hydrogen sulfide and carbon monoxide |
| US3847221A (en) * | 1973-05-04 | 1974-11-12 | Texaco Inc | Miscible displacement of petroleum using carbon disulfide and a hydrocarbon solvent |
| US4999178A (en) * | 1988-12-08 | 1991-03-12 | Bowman Melvin G | Thermochemical cycle for splitting hydrogen sulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2663757C (en) | 2014-12-09 |
| CA2663757A1 (en) | 2008-03-27 |
| WO2008034777A1 (en) | 2008-03-27 |
| EA016030B1 (ru) | 2012-01-30 |
| EP2064150A1 (en) | 2009-06-03 |
| MX2009002537A (es) | 2009-03-20 |
| US20100028243A1 (en) | 2010-02-04 |
| US7763227B2 (en) | 2010-07-27 |
| BRPI0716921A2 (pt) | 2013-11-12 |
| EA200900469A1 (ru) | 2009-06-30 |
| CN101516775A (zh) | 2009-08-26 |
| AU2007299081A1 (en) | 2008-03-27 |
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