CN101657527A - 除去中间馏分燃料中硫的组合物和方法 - Google Patents

除去中间馏分燃料中硫的组合物和方法 Download PDF

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CN101657527A
CN101657527A CN200780050903A CN200780050903A CN101657527A CN 101657527 A CN101657527 A CN 101657527A CN 200780050903 A CN200780050903 A CN 200780050903A CN 200780050903 A CN200780050903 A CN 200780050903A CN 101657527 A CN101657527 A CN 101657527A
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CN101657527B (zh
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K·蔡
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Abstract

一种用于除去中间馏分石油烃燃料中硫的组合物和方法。所述组合物包含氧化铝成分和碳成分。所述组合物的存在量可有效吸附燃料中的硫化合物。氧化铝成分和碳成分优选共同构成复合材料。所述组合物还可包含硫成分，优选金属硫化物或硫氧化物。所述组合物还可进一步包含至少一种具有元素周期表VI族或VIII族金属的化合物。

Description

除去中间馏分燃料中硫的组合物和方法
发明技术背景
本发明涉及一种除去中间馏分燃料中硫的组合物和方法。
发明背景
在石油工业中，轻质瓦斯油，特别是中间馏分石油燃料，常含有含硫物质。使用这些受污染燃料的发动机和车辆可产生氮氧化物、硫氧化物和颗粒物质的排放。近些年来，政府管制对这些潜在有害排放的允许标准已经越来越严格。
已经提出各种方法来降低这些轻质瓦斯油中的硫水平。但是，之前提出的这些方法都有缺点。例如提议在催化反应器中对燃料进行加氢脱硫，从而催化剂可以除去燃料中的噻吩、苯并噻吩和二苯并噻吩硫化合物。然而，通过催化剂对石油燃料流进行有效的加氢脱硫，通常需要在低流速且高温、高压、高耗氢条件下使用两个或多个串联的反应器。这些苛刻的操作条件，对于克服难熔硫和氮化合物对抗加氢脱硫的强烈抑制是必须的。
也提议使用各种有机和无机吸附剂来有效吸附除去硫化合物。之前提议的吸附剂例子包括硅土、氧化铝、沸石、活性碳、基于活性碳的纤维材料和用过的加氢脱硫催化剂。然而，这些吸附剂的体积吸附容量通常过低，而硫化合物穿透进入燃料产品的速度通常过快。另外，无机吸附剂通常需要进行高温再生处理，这对于稳定和连续操作来讲并不现实，而且吸附再生周期过于频繁，这使得有效操作变得困难。此外，这些吸附剂通常昂贵且易于磨损。因吸附剂颗粒之间的磨损而产生的细小颗粒会引起堵塞和高压降，这可能会缩短吸附工艺的运行周期。
使用环境温度下具有高度选择性和经热处理具有高体积吸附容量的组合物和方法，来除去中间馏分石油燃料中的硫化合物，这将是有益的。使用具有高磨损强度和较长吸附床使用期限的组合物和方法，来除去中间馏分石油燃料中的硫化合物，也是有益的。使用可以用普通溶剂进行再生，且再次使用前无需特殊活化处理的组合物和方法，来除去中间馏分石油燃料中的硫化合物，也是有益的。
发明概述
本发明提供了有利的用于除去中间馏分石油烃燃料中硫的组合物和方法。在本发明的实施方式中，所提供的组合物包含氧化铝成分和碳成分。所述氧化铝成分和碳成分优选共同构成复合材料。所述复合材料还可以包含硫成分。所述碳成分可以是非活性碳。所述组合物的存在量优选能够吸附燃料中的硫化合物。所述复合材料优选部分被煅烧，而且可以包含5％至50％材料重量的硫和碳。所述组合物优选在低于600℃的温度下部分燃烧，使得在煅烧过程中碳成分不会100％从复合材料中烧尽。复合材料可用于充分减少石油烃燃料流中存在的硫化合物，以生产沸点为50℃至650℃，更优选200℃至400℃的脱硫流。组合物中的硫成分优选为金属硫化物或硫氧化物。本发明复合材料的表面积优选为100-250m2/g，由N2吸附法测量。所述组合物还可以进一步包含至少一种金属化合物，优选铬、钼、钨、铀、硒、碲、钋、铁、钴、镍、锌、铜、钌、磷、硼、铑、钯、锇、铱和铂中的一种或多种。
还提供了用于除去中间馏分石油烃燃料中硫的方法。在本发明的实施方式中，所述方法包括以下步骤，部分煅烧含氧化铝成分和碳成分的复合材料，以改善复合材料的吸附性能，并使烃燃料与复合材料在吸附反应器中接触。反应器中复合材料的存在量优选能够吸附石油烃燃料中的硫化合物。在优选的实施方式中，反应器含0.5kg至1.5kg的复合材料/每升反应器体积。本发明实施方式中，所述复合材料还可以包含硫成分。
附图简述
为了对本发明特征、优势和目标及其它显而易见的内容有更详尽的理解，以上简要概述的本发明的更具体的描述，可以参考用附图阐述的实施方式，其构成本说明书的一部分。然而，需要指出的是，附图仅例证了本发明的优选实施方式，因此不应认为其限制本发明的范围，因为其可以得到其它同等有效的实施方式。
图1是本发明实施方式的方法的简化侧视图。
发明详述
本发明组合物优选使用碳-氧化铝复合材料作为吸附剂的基材。所述碳成分可以是相对小的碳粒子，类似于例如碳黑或“焦炭”。所述碳成分也可以是非活性碳。所述组合物能够在工业吸附工艺中除去中间馏分石油烃燃料中的部分或全部硫。所述组合物可用于获得前述工业工艺中较长的贯穿时间(breakthrough times)。相比现有技术所用的含高表面积活性碳材料的组合物，所述组合物还对包含于部分氢化处理的轻质瓦斯油中的硫化合物有更高的体积吸附容量。
本发明的组合物可以包含5％至50％吸附剂重量的硫和碳。优选地，碳和氧化铝是所述组合物中的两种主要物质。所述组合物还可包含硫和/或一种或多种周期表中的VI族或VIII族金属。所述硫优选以金属硫化物或硫氧化物的形式存在。现发现金属化合物和/或硫的存在对吸附可产生有益影响。
所述组合物可以在环境温度下除去中间馏分石油烃燃料中的部分或全部硫。给料中包含的含硫物质吸附在复合材料上，并被保留在复合材料上。
在本发明的实施方式中，本文所公开的组合物可以除去沸点50℃至650℃，且优选200℃至400℃的石油给料流中的硫。操作压力取决于进入反应器的复合材料的堆积密度、给料的流速和温度。通常，操作压力小于100巴，优选50巴。所述组合物对于整个烃含量范围都是可行的，而且可以用于汽油、煤油和柴油应用。
对碳-氧化铝复合材料进行煅烧或类似热处理，对于增加体积吸附容量也是有益的。在含氧的气体氛围下对复合材料进行热处理的优选温度为200℃至800℃。煅烧过程是通过将复合材料放在具有流动的含氧气体，特别是大气压下的空气的过程加热器中进行。以一定速度升高加热器的温度至指定温度，然后在指定温度下保持一段时间，接着冷却至室温。煅烧步骤增加氧化铝-碳复合材料的吸附活性。煅烧步骤还增加复合材料的表面积。氧化铝-碳复合材料上的碳物质优选已被碳化，且不需要碳化步骤，所述碳化步骤有时在约1000℃的温度下进行，以除去挥发性物质，并在惰性气体或含氧气体条件下使芳烃聚合。
本发明组合物的磨损强度高于活性碳。与脆弱的活性碳相比，本文所公开的组合物具有更长的吸附床使用周期。通常，活性碳由烃物质经碳化和活化而制得。进行碳化以除去挥发性物质，并在制备活性碳的惰性气体环境下经热处理使芳烃聚合。碳化物质可在惰性气体或含氧气体流(例如约700至1000℃的流和空气)下经热处理被活化。活性碳物质具有多孔结构和高的表面积。
相比之下，本发明的碳成分不需要碳化和活化步骤。本发明的吸附剂是具有低比表面积碳的用过的加氢处理催化剂。通常，通过吸附芳烃并耦合或聚合已吸附的烃，使固体碳沉积在催化剂的表面上。用过的加氢处理催化剂上存在的固体碳，类似于活性碳和碳黑，只是比表面积很低，这导致改良的硫除去性能。
本发明组合物特别可用于获得含硫量低的柴油燃料。所述组合物对于除去轻质瓦斯油中的硫化合物，比具有高表面积的活性碳更加有效。在本发明的实施方式中，所述组合物可以是之前已用于加氢处理一种或多种石油流的用过的催化剂。在本发明的实施方式中，复合材料是包含例如约10％重量的碳、5％重量的硫、14％重量的Mo和余量氧化铝的用过的加氢处理催化剂。
图1阐明了依照本发明实施方式的吸附方法。该方法使用两个或多个吸附单元，包括在吸附和再生阶段之间以循环方式运行的第一吸附单元20和第二吸附单元30。所述第一和第二吸附单元20、30各自包含碳-氧化铝复合材料，其吸附硫以生产低硫烃流。还可以使用一个或多个含碳-氧化铝复合材料的备用单元(未显示)。所述第一和第二吸附单元20、30可以是固定床类型、扩张床类型或类似类型。操作温度为0至100℃，优选10至40℃，操作压力为1巴至100巴，优选10至50巴。
在本发明的实施方式中，经给料流15将石油烃给料引入第一加氢处理单元10。给料流15通常包含1至2％重量的硫、尽管其可含有多达3％重量的硫。给料包含的部分含硫物质通过高压氢存在下的借助催化剂的加氢脱硫反应被除去。通过该反应，所述含硫物质转化为硫化氢。
石油烃燃料流经流25从加氢处理单元10中出来，并被引到吸附单元20中，其在气体产物和氢被适当装置除去之后发挥作用。燃料流与碳-氧化铝复合材料在单元20中接触，并优选充分除去燃料流中的硫。含硫物质在吸附操作期间保留在复合材料上，然后在再生操作期间被溶剂从复合材料除去。
当吸附单元20处于使用中时，优选吸附单元30正在进行再生。在本发明的实施方式中，通过用普通烃溶剂洗涤，然后在低于100℃下干燥，可使吸附剂再生至全吸附容量。在优选的实施方式中，所述烃溶剂是甲苯或二甲苯。再生之后的活化吸附剂不需要任何特殊的预处理。优选使用溶剂回收单元50来贮藏用过的再生剂，并将含硫物质与溶剂分离。最后，通过溶剂再生单元50将含硫物质与溶剂分离，并经线路45送回至加氢处理单元10。在本发明的实施方式中，从给料中除去的含硫物质是噻吩、烷基化噻吩、苯并噻吩、烷基化苯并噻吩、二苯并噻吩和烷基化二苯并噻吩。
从吸附单元20出来的烃燃料，优选经流35被转运到第二阶段加氢处理单元40。流35的硫含量降低，有利于经催化剂的加氢脱硫，因为作为加氢脱硫强抑制剂的硫化氢，较少地在加氢处理中产生。此外，除去难熔的含硫物质可增加催化剂的活性，因为难熔的含硫物质也是加氢脱硫的强抑制剂。此外，具有较低硫含量的给料经加氢处理以生产含硫量更少的烃流。在本发明的实施方式中，从第二阶段加氢处理单元20出来的燃料流，优选包含0至10ppm的硫。
在本发明的实施方式中，吸附过程可以同时使用多个吸附单元，因此在任一时间可不止一个单元以吸附或再生模式运行。另外，在用于图1所示的吸附单元之前，碳-氧化铝复合材料可以优选进行煅烧或者其它类似的热处理。
以下系列实施例表明，与代表性现有技术方法相比，本发明组合物和方法降低部分加氢处理后的轻质瓦斯油中硫水平的有效性。虽然其中某些实施例是为了详细阐明本发明的实施方式，但是他们绝对不是要限制本发明的范围。
实施例1(现有技术方法)：吸附试验之前，将0.84克含灰量为0.65％重量的活性碳在110℃下干燥24小时。活性碳是由木材、煤及其它含碳原料经碳化(在氮气下加热至约1000℃)而制成。因此，活性碳包含一些矿物质。矿物质的含量可经燃烧活性碳来测定。将干燥的活性碳装填入50毫米长且8毫米直径的不锈钢管中。经HPLC泵以0.5ml/min的速度将部分加氢处理过的含1,122ppm重量硫的轻质瓦斯油加入管内。不同取样间隔的流出物的总硫含量，如表1第2列所示。
实施例2(本发明实施方式)：已用于加氢处理瓦斯油的基于氧化铝的吸附剂，含有非活性碳和硫共26.6％重量，碳和氧化铝成分为碳-氧化铝复合材料形式，将其在600℃空气下煅烧2小时，然后在110℃下干燥24小时，再进行吸附试验。将2.07克干燥的吸附剂装填入50毫米长且8毫米直径的不锈钢管中。经HPLC泵以0.5ml/min的速度将部分加氢处理过的含1,122ppm重量硫的轻质瓦斯油加入管内。不同取样间隔流出物的总硫含量，如表1第3列所示。
实施例3(本发明实施方式)：已用于加氢处理瓦斯油的基于氧化铝的吸附剂，含有非活性碳和硫共26.6％重量，碳和氧化铝为碳-氧化铝复合材料形式，将其在350℃空气下煅烧2小时，然后在110℃下干燥24小时，再进行吸附试验。将2.13克干燥的吸附剂装填入50毫米长且8毫米直径的不锈钢管中。经HPLC泵以0.5ml/min的速度将部分加氢处理过的含1,122ppm重量硫的轻质瓦斯油加入管内。不同取样间隔流出物的总硫含量，如表1第4列所示。
实施例4(本发明实施方式)：已用于加氢处理瓦斯油的基于氧化铝的吸附剂，含有非活性碳和硫共26.6％重量，碳和氧化铝为碳-氧化铝复合材料形式，将其在250℃空气下煅烧2小时，然后在110℃下干燥24小时，再进行吸附试验。将2.55克干燥的吸附剂装填入50毫米长且8毫米直径的不锈钢管中。经HPLC泵以0.5ml/min的速度将部分加氢处理过的含1,122ppm重量硫的轻质瓦斯油加入管内。不同取样间隔流出物的总硫含量，如表1第5列所示。
表1
部分加氢处理后的轻质瓦斯油中的硫ppm
  加入给料后的取样时间  实施例1(ppm重量硫)  实施例2(ppm重量硫)  实施例3(ppm重量硫)  实施例4(ppm重量硫)
  0分钟至5分钟   331   324   193   153
  5分钟至10分钟   579   577   461   534
  15分钟至20分钟   778   617   624   666
  25分钟至30分钟   832   648   680   792
  35分钟至40分钟   846   687   752   841
硫成分的贯穿图(breakthrough pattern)取决于以下因素：所用吸附剂的类型和吸附剂的表面性质等。例如，实施例2中吸附剂的含碳量明显少于实施例3和4中吸附剂的含碳量，因此整体表面性质及由此得到的贯穿图(breakthrough pattern)会明显不同。
通常，由于活性碳的表面积极高，其除去瓦斯油中硫的吸附容量比氧化铝大很多。与活性碳相比，本发明的碳-氧化铝复合材料显示更强的吸附除去硫化合物的能力。本发明复合材料的表面积以N2吸附法测量，优选为100至250m2/g。相比之下，实施例1中活性碳的比表面积以N2吸附法测量，为1,440m2/g。
与活性碳的性能相比，本发明复合材料的改良性能表明，在这种特定应用中碳与氧化铝之间有很强的协同和有益的相互作用。
尽管本发明仅以其某些形式进行了说明或描述，但是本领域技术人员应该明白，本发明并不受限于此，而是可以进行各种改变而不脱离本发明的范围。

Claims (15)

1.一种用于除去石油烃中硫的组合物，所述组合物包含含有氧化铝成分和碳成分的煅烧复合材料，所述组合物的存在量可吸附中间馏分石油烃燃料中的硫化合物。
2.权利要求1的组合物，其中所述碳成分是非活性碳。
3.权利要求1的组合物，其还包含硫成分。
4.权利要求3的组合物，其中所述硫成分选自金属硫化物和硫氧化物。
5.权利要求1的组合物，其中所述复合材料包含占组合物5％至50％重量的碳和硫。
6.权利要求1的组合物，其还包含选自铬、钼、钨、铀、硫、硒、碲、钋、铁、钴、镍、锌、铜、钌、磷、硼、铑、钯、锇、铱和铂的金属化合物。
7.权利要求1的组合物，其中所述复合材料可充分减少石油烃中存在的硫化合物，以生产沸点为50℃至650℃的石油烃流。
8.权利要求1的组合物，其中所述复合材料可充分减少石油烃中存在的硫化合物，以生产沸点为200℃至400℃的石油烃流。
9.权利要求1的组合物，其中所述复合材料在250℃至600℃的温度下进行煅烧。
10.权利要求1的组合物，其中所述复合材料的N2吸附法测量的表面积优选为100至250m2/g。
11.一种除去中间馏分石油烃燃料中硫的方法，所述方法包括以下步骤：
煅烧包含氧化铝成分和碳成分的复合材料；和
使烃燃料与所述复合材料在吸附反应器中接触，反应器中复合材料的存在量可吸附石油烃燃料中的硫化合物。
12.权利要求11的方法，其还包括以下步骤：在使烃燃料与复合材料在反应器中接触之前干燥复合材料。
13.权利要求11的方法，其中所述碳成分是非活性碳。
14.权利要求11的方法，其中所述复合材料在250℃至600℃的温度下进行煅烧。
15.权利要求11的方法，其中所述复合材料的N2吸附法测量的表面积优选为100至250m2/g。
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US8426336B2 (en) 2013-04-23
WO2008069880A3 (en) 2009-06-25
US20130079222A1 (en) 2013-03-28
CN101657527B (zh) 2013-08-21
EP2102313A2 (en) 2009-09-23
US7842181B2 (en) 2010-11-30
BRPI0720143B1 (pt) 2017-03-21
US20080135454A1 (en) 2008-06-12

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