CN101443268A - 制备二硫化碳的方法 - Google Patents
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Abstract
本发明提供一种制备二硫化碳的方法，该方法包括：将含氧分子的气体和含烃类化合物的进料供应至含液态元素硫相的反应区域，在300－750℃的温度下于液态硫相中使烃类化合物与元素硫进行反应以形成二硫化碳和硫化氢，和将至少部分所形成的硫化氢氧化成元素硫和水。本发明还提供可通过该方法获得的含二硫化碳、硫化氢和硫化羰的液态物流用于强化油采收的用途。
Description
技术领域
本发明提供制备二硫化碳的方法和可通过该方法获得的包含二硫化碳、硫化氢和硫化羰的液态物流用于强化油采收的用途。
背景技术
通常根据以下的反应方程式通过将低级烃与气相中的元素硫进行反应制得二硫化碳：
CnH2(n+1)+(3n+1)S→nCS2+(n+1)H2S (1)
在GB 1,173,344中公开了一种用于在维持于550-850℃温度下的反应区域内、在不超过10大气压的压力下、不存在催化剂的条件下将气相硫和丙烷进行反应的方法。
在US 3,087,788中公开了一种在与优选随后的催化反应阶段相结合的非催化反应阶段中从烃气和硫蒸气生产二硫化碳的方法，其中两个阶段都在2-20大气压的压力和400-750℃的温度下进行。
还已知通过液体硫与烃的催化反应制备二硫化碳。例如，在US2,492,719中公开了一种制备二硫化碳方法，其中在足以将硫维持在液相下的压力下、在大约500-700℃的温度下将催化剂于熔融态硫中的悬浮体与烃气接触。
上述的现有技术方法的缺点在于所生产的硫化氢的摩尔量大于所形成的二硫化碳的摩尔量。
在US 3,345,135中公开了一种生产二硫化碳和碳氧化物的催化方法，其中含有1-20个碳原子的气态饱和或不饱和脂族烃、氧化气体(特别是氧气)和硫化氢在约100-700℃的温度下、在特定的硅铝酸盐催化剂存在下进行反应。形成了大量的二氧化碳和一氧化碳。从实施例可看出，所形成的碳氧化物的摩尔量远大于所形成的二硫化碳的摩尔量。
已知二硫化碳是用于通过混相驱强化油采收的适合溶剂。在通过混相驱强化油采收中，将用于油的溶剂加入油储层中和驱使溶剂通过储层，从而与常规方法相比提升从储层的油采收。例如在US 3,847,221中公开了二硫化碳用于从焦油砂的强化油采收的用途。
发明内容
目前已发现可在通过向反应混合物添加氧分子使所形成的硫化氢被选择性氧化成元素硫的条件下即共同产生最少的二氧化碳和一氧化碳的条件下，从烃类化合物和液态元素硫制得二硫化碳。
因此，本发明提供用于制备二硫化碳的方法，该方法包括：将含氧分子的气体和含烃类化合物的进料供应至含液态元素硫相的反应区域，在300-750℃的温度下于液态硫相中使烃类化合物与元素硫进行反应以形成二硫化碳和硫化氢，和将至少部分所形成的硫化氢氧化成元素硫和水。
本发明的方法的优点是仅形成非常少量的碳氧化物。另外的优点是本发明的方法的可在不存在催化剂的条件下进行。
与生产二硫化碳的常规气相法相比，本发明的方法具有数个优点。一个优点是仅有少量的硫化氢与二硫化碳一起获得。其结果是，如果高纯度的二硫化碳是所需产物，则仅需将少量硫化氢的物流再循环至硫化氢浓缩和转化处理单元例如克劳斯或SCOT单元。另一个优点是不需要使硫气化。另外的优点是放热的选择性氧化反应产生了烃类化合物和硫之间的吸热反应中所用的热量。
在本发明的方法中，获得了含二硫化碳和蒸汽的气相。该气相通常还包含硫化氢和硫化羰。该气相也可包含碳氧化物、硫氧化物、未转化的烃类化合物和元素硫。通过使气相经过单独或连续的冷凝步骤，本发明的方法获得含二硫化碳的液态物流。该液态物流也可包含其它化合物例如水、未转化的烃、碳氧化物、硫氧化物、硫化氢、硫化羰和/或元素硫。应该意识到准确的组成主要取决于进行冷凝步骤时的温度和压力。获得的液态物流通常包含一些溶解于二硫化碳中的硫化氢和硫化羰。本发明的方法中获得的含二硫化碳的液态物流可适用于强化油采收。
因此，本发明另外提供含二硫化碳、硫化氢和硫化羰的液态物流用于强化油采收的用途，所述液态物流可通过上述定义的方法获得。
在本发明的方法中，通过在含液态元素硫相的反应区域中使烃类化合物与元素硫进行反应制得二硫化碳。烃类化合物和元素硫之间的反应在液态硫相中进行。反应物在300-750℃的温度下和足以维持液态元素硫相的压力下相互反应。
将含氧分子的气体和含烃类化合物的进料同时供应至含液态元素硫相的反应区域。本文中烃类化合物是指含碳原子和氢原子以及任选的少量杂原子例如氧、硫或氮的化合物。在所应用的反应条件下，烃类化合物可为气态、液态或固态。适合的烃类化合物的实例是烃、沥青、硫醇、噻吩和烷基多硫化物。优选地，烃类化合物在所应用的反应条件下为气态。
烃类化合物优选是烃，更优选是饱和或不饱和脂族烃，更优选是含有1-20个碳原子的脂族烃。本发明的方法中，含有1-4个碳原子的饱和烃、特别是甲烷、乙烷和丙烷是特别适合的反应物。
在本发明的方法中，烃类化合物和元素硫互相反应。当烃类化合物是饱和脂族烃时，该反应适用总反应方程式(1)：
CnH2(n+1)+(3n+1)S→nCS2+(n+1)H2S (1)
将氧分子供应至反应区域以根据反应方程式(2)将至少部分所形成的硫化氢氧化成元素硫：
(n+1)H2S+1/2(n+1)O2→(n+1)H2O+(n+1)S (2)
反应方程式(1)和(2)的总结果为：
CnH2(n+1)+2nS+1/2(n+1)O2→nCS2+(n+1)H2O (3)
进料可包含一种以上烃类化合物。进料也可包含其它化合物，例如硫化氢、碳氧化物和惰性气体例如氮气和氦气。适用于本发明的方法的进料的实例是天然气、液化丙烷气(LPG)、常压或真空馏出物、重油物流例如原油常压和/或真空蒸馏后获得的残余物、来自硫醇吸收器的含硫醇的尾气。特别适用的含烃类化合物的进料是天然气。
优选地，进料还包含硫化氢。当进料包含硫化氢时，可通过根据反应方程式(2)选择性氧化外部供应的硫化氢在反应区域中生产根据方程式(1)的烃类化合物与元素硫的反应所需的部分或全部元素硫。如果随进料将足够的硫化氢供应至反应区域，则该方法可在无净消耗元素硫的条件下进行。
供应至反应区域的含氧分子的气体优选为纯氧、空气或富含氧的空气。含氧分子的气体和进料可单独供应至反应区域或作为混合物供应至反应区域。可向反应区域分段供应含分子的气体，以避免出现局域氧过剩引起的热点。
为了将烃类化合物被氧化成碳氧化物以及二硫化碳被氧化成二氧化碳和二氧化硫减到最小，优选将氧分子以低于化学计量量供应至反应区域，即供应至反应区域的氧分子的数目少于供应至反应区域的烃类和硫化氢中氢原子数目的25％。供应至反应区域的氧分子的量优选不少于化学计量量的5％，更优选不少于化学计量量的10％，甚至更优选不少于化学计量量的30％。
在本发明的方法中，通常将进料和含氧分子的气体连续供应至反应区域。如果进料是气态，则可将进料单独或与含氧分子的气体一起供应至反应区域。如果在所应用的反应条件下烃类化合物是固态，则优选通过将进料与反应区域将要填充的液态硫相进行预混而将进料供应至反应区域。当在所应用的反应条件下烃类化合物是液态时，也可按照这种方法进行处理。优选地，以与供应至反应区域的含氧分子的气体并流或逆流的方式，将液态进料连续供应至反应区域。
该方法可在任意适用于气-液接触的反应器结构中进行，通常通过将气态反应物鼓泡通过填充有液体硫的反应器进行。为了防止形成气栓，反应器可含有固体接触器，例如规整填料或滤网。
当存在元素硫的净消耗时，可将液态补充硫物流连续供应至反应区域。替代地，将反应区域中的元素硫定期更新。
当在所应用的反应条件下烃类化合物是气态时，烃类化合物与液体硫的初始接触时间优选为0.1-200秒。应该意识到最佳接触时间随着烃类化合物的折光特性而增大。因此，在所应用的反应条件下是固态的烃类化合物通常比在所应用的反应条件下是液态的化合物需要更长的接触时间，和液态化合物通常比气态化合物需要更长的接触时间。
本发明的方法在300-750℃、优选400-700℃、更优选400-650℃的温度下进行。
反应物在足以维持液态元素硫相的压力下互相反应。因此，压力主要取决于反应温度。优选地，压力为3-200巴(绝压)，更优选5-100巴(绝压)，甚至更优选5-30巴(绝压)。
本发明的方法的优点是不需要催化剂。优选地，烃类化合物在不存在催化剂的条件下与硫进行反应。
本发明的方法的优点是在所应用的反应条件下，氧分子与硫化氢选择性进行反应，即不会氧化大量的烃类化合物或二硫化碳。
在本发明的方法中形成了主要包含二硫化碳和蒸汽的气相。在优选的实施方案中，使用了不足化学计量量的氧分子，气相还包含硫化氢。通常，气相还包含少量的硫化羰、二氧化碳、二氧化硫和元素硫。当使用气态烃类化合物时，气相通常还包含未转化的烃类化合物。
优选地，本发明的方法另外包括从反应区域采出含二硫化碳和蒸汽的气相，和冷凝至少部分所述气相以获得含二硫化碳的液态物流。
如果反应区域的流出物是混合的液态和气态流出物，例如可能是当将液态进料与含氧分子的气体以并流方式供应至反应区域时的情况，则首先在气-液分离器中分离流出物的气相和液相。
可将采出的气相冷凝以获得含二硫化碳的液态物流。优选地，将气相进行顺序部分冷凝步骤以获得含有更高二硫化碳浓度的液态物流。为了获得具有所需组成的含二硫化碳的液态物流，也可使用除冷凝步骤以外的纯化步骤。
优选地，首先将从反应区域采出的气相在超大气压力下冷却至元素硫冷凝同时二硫化碳和其它组分保留在贫硫气相中的温度。随后可将冷凝的硫再循环至反应区域。可将贫硫气相进行冷凝以获得含二硫化碳的液态物流。优选地，从贫硫气相选择性冷凝水以获得贫蒸汽气相。随后将贫蒸汽气相冷凝以获得含二硫化碳的液相。
应该意识到含二硫化碳的液态物流的所需组成决定了所需的冷凝和/或纯化步骤。对于二硫化碳的常规用途例如二硫化碳用作生产人造丝的原料或用作溶剂，需要高纯度的二硫化碳。如果液态物流用于强化油采收，即将液态物流注入油储层以提高从该储层的油产量，则液态二硫化碳物流可包含大量的其它组分例如硫化氢、硫化羰、碳氧化物、硫氧化物、烃类化合物和水。
本发明的方法中形成的含二硫化碳的液态物流特别适用于强化油采收，因为所述液态物流通常包含在该应用中无需移除的二硫化碳之外的组分。因此，本发明的方法优选另外包括将含二硫化碳的液态物流注入油储层中以强化油采收。在将含二硫化碳的液态物流注入油储层中之前，可将含二硫化碳的液态物流与其它液态组分或物流进行混合。
通常，可通过本发明的方法获得的含二硫化碳的液态物流还包含溶解于二硫化碳中的硫化氢和硫化羰。以二硫化碳的含量计，硫化氢的典型浓度为0.05-50wt％，硫化羰的典型浓度为0.01-15wt％。因此，本发明另外提供可通过本发明的方法获得的含二硫化碳、硫化氢和硫化羰的液态物流用于强化油采收的用途。
具体实施方式
本发明的方法将通过以下非限定实施例进一步进行说明。
实施例1
在石英反应器管中(内径12mm，长度40mm)中装入一定量的粉末元素硫。用氮气流将反应器的压力升高到10巴(绝压)，和将反应器加热至高于400℃的反应温度。在反应温度下，用高度为15cm的液态硫柱(相当于1.7×10-2升硫)填充反应器管。将含烃(甲烷或乙烷)和氧气的气体混合物供应至反应器的底部。在反应器的顶部，采出气态流出物。通过气相色谱分析气态流出物的组成。进行了6次不同的实验。在对比实验1和4中，不向反应器供应氧气。实施例2、3、5和6是本发明的实验。
在表1中，给出了实验1-6的反应条件和结果。
在这些实施例中使用的实验室规模的反应器装置中，无法将氧气分段供应至反应器。因此，将供应至反应器的氧气的量保持在较低的水平以最小化接近反应器入口的烃和二硫化碳的氧化。如果在可以于反应器中不同阶段下供应氧气的反应器中进行实验，则可以供应更大量、但仍然低于化学计量量的氧气。
实施例2
如实施例1中所述进行了3次不同的实验(实验7-9)。在实验7-9中，供应至反应器管的进料气体混合物包含硫化氢。在表2中，给出了反应条件和结果。
Claims (10)
1.一种制备二硫化碳的方法，该方法包括：将含氧分子的气体和含烃类化合物的进料供应至含液态元素硫相的反应区域，在300-750℃的温度下于液态硫相中使烃类化合物与元素硫进行反应以形成二硫化碳和硫化氢，和将至少部分所形成的硫化氢氧化成元素硫和水。
2.权利要求1的方法，其中所述烃类化合物在不存在催化剂的条件下与元素硫进行反应。
3.权利要求1或2的方法，其中所述进料包含硫化氢。
4.前述权利要求任一项的方法，其中所述烃类化合物是在反应条件下为气态的化合物。
5.前述权利要求任一项的方法，其中所述烃类化合物是烃，优选饱和或不饱和脂族烃，更优选含有至多20个碳原子的脂族烃，更优选含有至多4个碳原子的饱和脂族烃。
6.前述权利要求任一项的方法，其中供应至反应区域的氧分子的数目少于供应至反应区域的烃类化合物和硫化氢中氢原子数目的25％。
7.前述权利要求任一项的方法，其中反应区域中的温度是400-700℃，优选400-650℃。
8.前述权利要求任一项的方法，其中反应区域中的压力为3-200巴(绝压)，优选5-100巴(绝压)，更优选5-30巴(绝压)。
9.前述权利要求任一项的方法，另外包括从反应区域采出含二硫化碳和蒸汽的气相，和将至少部分所述气相冷凝以获得含二硫化碳的液态物流，优选另外包括将含二硫化碳的液态物流注入油储层中以强化油采收。
10.可通过权利要求9的方法获得的含二硫化碳、硫化氢和硫化羰的液态物流用于强化油采收的用途。
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2007
- 2007-05-14 CN CN2007800175521A patent/CN101443268B/zh not_active Expired - Fee Related
- 2007-05-14 WO PCT/EP2007/054613 patent/WO2007131977A1/en active Application Filing
- 2007-05-14 EA EA200802328A patent/EA014709B1/ru not_active IP Right Cessation
- 2007-05-14 CA CA2652002A patent/CA2652002C/en not_active Expired - Fee Related
- 2007-05-14 US US12/300,748 patent/US8722006B2/en not_active Expired - Fee Related
- 2007-05-14 MX MX2008014476A patent/MX2008014476A/es unknown
- 2007-05-14 AU AU2007251609A patent/AU2007251609A1/en not_active Abandoned
- 2007-05-14 EP EP07729065A patent/EP2021278A1/en not_active Withdrawn
- 2007-05-14 BR BRPI0711264-5A patent/BRPI0711264A2/pt not_active IP Right Cessation
-
2008
- 2008-12-15 NO NO20085245A patent/NO20085245L/no not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695672A (zh) * | 2010-01-07 | 2012-09-26 | 国际壳牌研究有限公司 | 制备硫化物的方法 |
| CN114906849A (zh) * | 2022-06-23 | 2022-08-16 | 上海德迈世欧科技有限公司 | 制备硫化氢和二硫化碳的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20085245L (no) | 2008-12-15 |
| EA014709B1 (ru) | 2011-02-28 |
| WO2007131977A1 (en) | 2007-11-22 |
| BRPI0711264A2 (pt) | 2011-08-30 |
| CA2652002A1 (en) | 2007-11-22 |
| US8722006B2 (en) | 2014-05-13 |
| CN101443268B (zh) | 2012-06-06 |
| AU2007251609A1 (en) | 2007-11-22 |
| EP2021278A1 (en) | 2009-02-11 |
| CA2652002C (en) | 2015-01-06 |
| EA200802328A1 (ru) | 2009-04-28 |
| MX2008014476A (es) | 2008-11-26 |
| US20090226358A1 (en) | 2009-09-10 |
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