CN101389735B - 柴油的氧化萃取脱硫 - Google Patents

柴油的氧化萃取脱硫 Download PDF

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CN101389735B
CN101389735B CN200680041722.5A CN200680041722A CN101389735B CN 101389735 B CN101389735 B CN 101389735B CN 200680041722 A CN200680041722 A CN 200680041722A CN 101389735 B CN101389735 B CN 101389735B
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oxidation
sulphur
diesel oil
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G·D·马蒂尼
F·M·阿尔-沙拉尼
B·O·达布西
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Saudi Arabian Oil Co
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Abstract

通过在催化剂存在下进行氧化然后进行液液逆流萃取，实现了柴油燃料的含硫成分的降低。

Description

柴油的氧化萃取脱硫
发明背景 
本发明涉及柴油燃料中含硫化合物的脱除，更进一步说，通过氧化和萃取步骤的结合进行含硫化合物的脱除。 
先有技术 
从原油中脱除硫化合物在过去是相当重要的，由于环境的因素现在变得更加重要。有机材料燃烧的气体排出物如煤，几乎总是含有硫化合物，硫的脱除过程集中于脱除硫化氢，因为它被认为是一种严重的危害健康的因素，而且它是腐蚀性的，特别是在有水存在的情况下。随着不断强调避免或减少将硫排到大气中，研究方向已转向从气体中脱除其他硫化合物。 
从原料中脱除硫化合物，特别是化学结合的硫如有机硫化合物，是非常有用的既能满足环境的要求还可以避免潜在的催化剂失活及设备腐蚀。 
通常烃类产品中含有多种以化学结合硫的方式存在的硫化合物，如无机结合的硫和有机结合的硫，例如有机硫化合物。 
烃类中有机硫化合物的存在无疑是由于在制备和处理烃类产品的传统过程中将有机硫化合物引入到氢流中引起的。 
如前所述，如果化学结合的硫，如有机硫化合物，没有从烃类中脱除，在所得到的烃类产品中，包括天然气，烷烃，烯烃，芳烃，特别是汽油，柴油或其他燃料，有机硫化合物的存在会引起设备和机械部件的腐蚀，以及其他的有害作用，特别是在有水存在下。 
柴油和其他油品的氧化脱硫研究已进行了上百年，下面表格中总结了从1941年到1976年授权的关于氧化脱硫的专利。 
表1 
  专利号   发明人   申请人 题目
  2,253,308  Aug.19，1941   Rosen，Raphael   Standard  Catalytic Desulfurization of Hydrocarbons
  2,697,682  Dec.21，1954   Porter，Fredrich   Anglo-Iranian  Oil Catalytic Desulfurization of Petroleum Hydrocarbons
  2,671,049  March 2，1954   Brown，Russell   Standard Oil Odor Improvement of Petroleum Oils
  2,834,717  May 13，1958   Shiah，Chyn   Process of Desulfurizing Hydrocarbons with a BoronFluoride
  3,284,342  Nov.8，1966   Nathan，  Wilfred   British  Petroleum Desulfurization of Hydrocarbon Materials
  3,341,448  Sept.12，1967   Ford，John   British  Petroleum Desulfurization of Hydrocarbons Oxidative HydroTreatments
  3,565,793  Feb.23，1971   Herbstman，  Sheldon   Texaco，Inc. Desulfurization With a Catalytic Oxidation Step
  3,595,778  July 27，1971   Srnetana，  Richard   Texaco，Inc. Desulfurization Process Including an Oxidation Step
  3,719,589  March 6，1973   Herbstman，  Sheldon   Texaco，Inc. Asphalt Separation in De-Sulfurization with an OxidativeStep
  3,816,301  June 11，1974   Sorgenti，  Harold   Atlantic  Richfield Process for the Desulfurization of Hydrocarbons
  3,945,914  Mar.23，1976   Yoo，Jim   Atlantic  Richfield Process of Sulfur Reduction of an Oxidized Hydrocarbon
Paris-Marcano获得了两篇用硝酸和过氧化氢进行石油氧化脱硫的专利USP5,017,280和5,087,350。Petrostar公司的Gore获得了两篇氧化脱硫的专利US 6,274,785和6,160,193。Cabrerra获得了一篇转让给UOP公司的复合氧化脱硫专利6,171,478。Unipure公司的Rappas获得了两篇用过甲酸进行氧化脱硫的专利USP6,402,940和6,406,616。Unipure公司的Ohsohl获得了两篇原油脱硫的专利5,985,137和5,948,242。 
Jeanblanc获得了一篇辐射辅助的氧化脱硫专利WO/001 5734。含硫的碳材料通过与一种含有氧化剂和富氧溶剂如乙醚的混合物在碱性条件下反应实现脱硫，最优反应温度从室温到约121℃，反应压力约1～2个大气压。射线的使用推动了脱硫反应的进行，所述射线如X-射线，红外线，可见微波，或紫外射线，α、β或γ射线，由放射性材料发射出的其他原子射线或超声等，反应产物是一种脱硫的碳材料和单独的硫化合物，其中脱硫的碳材料中的硫含量低于1％。 
Cal Tech公司的Yen获得了一篇超声波辅助的氧化脱硫专利USP6,402,939。Gunnerman获得了几篇使用超声波辅助的专利USP6,500,219和6,652,592。Stowe在专利USP 5,547,563中公开了一种用超声波辅助的烃油的氧化脱硫过程。 
Cullen在转让给Petrosonics公司的4篇近期的美国专利申请中公开了氧化脱硫，活性脱硫，超声波脱硫技术：申请号10/411,796，2003年4月11日申请，Sulfone Removal Process；申请号10/429,369，2003年5月5日申请，Process For Generating and RemovingSulfoxides from Fossil Fuel；申请号10/431,666，2003年5月8日申请，Treatment of Crude Oil Fractions，Fossil Fuels&Products Thereof with Sonic Energy；申请号10/644,255，2003年8月20日申请，Treatment of Crude Oil Fractions，Fossil Fuels&Products Thereof。 
Collins在美国专利5,847,120和6,054,580中公开了一种长效的以Fe的四酰氨基大环配体复合物为均相氧化催化剂的催化过氧化反应。这种复合物提供了一种稳定的、长效的氧化反应催化剂或催化剂触媒。 
Kocal在转让给UOP公司的2001年8月21日授权的美国专利6,277,271中公开了一种烃油的脱硫过程。这是一个烃油脱硫的过程，其中烃油和含有氧化的硫化合物的循环物流在加氢脱硫反应区与加氢脱硫催化剂相接触，使硫含量降低到相对较低的水平，然后将从加氢脱硫反应区得到的烃类与氧化剂相接触，将其中残留的低硫化合物转化成氧化的硫化合物。将残留的氧化剂分解后，将得到的含有氧化的硫化合物的烃油进行分离制备得到含有氧化的硫化合物的部分和含有低含量氧化的硫化合物的烃油。至少有部分氧化的硫化合物可以再循环到加氢脱硫反应区。 
在转让给UOP的另一篇专利，2002年4月9日授权的美国专利6,368,495中Kocal公开了在空气中使用过氧化氢与非均相过渡金属催化剂从液态烃中脱除含硫化合物的过程。这个过程特别强调了几种石油馏分中噻吩和噻吩衍生物的脱除，所说石油馏分包括汽油、柴油和煤油。该过程的第一步是将液态烃置于氧化条件下，将至少几种噻吩类化合物氧化成砜。然后，砜可被催化分解成烃类(如羟基联苯)和挥发性的硫化合物(如SO2)。烃类分解产物保留在处理后的液体中可作为有用的调和组分，而挥发性的硫化合物通过熟知技术如闪蒸或蒸馏技术很容易从处理后的液体中分离出来。 
Cabrera在2001年1月9日授权的美国专利6,174,178中公开 了一种烃油的脱硫过程。在该脱硫过程中烃油在加氢脱硫反应区与加氢脱硫催化剂相接触，使硫含量降低到相对较低的水平，然后将从脱硫反应区得到的烃类与氧化剂相接触，将其中残留的低硫化合物转化成氧化的硫化合物。将残留的氧化剂分解后，将得到的含有氧化的硫化合物的烃油进行分离制备得到含有氧化的硫化合物的部分和含有低含量氧化的硫化合物的烃油。 
Shum在1988年9月20日授权的美国专利4,772,731中公开了用二烯基甘醇酸酯二氧化钼组合物催化的烯烃环氧化反应。新型的二烯基甘醇酸酯二氧化钼组合物的制备是通过三氧化钼与特定的二烯基甘醇化合物在一定高温下反应脱水得到的，该组合物特别适宜作为催化剂与有机过氧化物反应用于烯类化合物的环氧化反应。 
Shum在1998年7月14日授权的美国专利5,780,655中公开了一种用烷基磷酸铵稳定的过氧化钨酸盐化合物为催化剂的环氧化反应过程。在均一液相反应体系中用过氧化氢作氧化剂烯烃可以选择性的转化为环氧化物，其中特性的液相主要是由有机溶剂组成的。该反应可由一种磷稳定的过氧化钨酸盐物种组成的化合物来催化，其中钨∶磷原子比为2∶1。该专利涉及了在均一液相中使用过氧化氢和一种以盐或酸形式存在的催化剂将烯烃转化为环氧化物的方法，其中的催化剂是由对应于(R4N)2PW2O13(OH)的物种组成的。 
Venturello在美国专利5,274,140中公开了一种按照两相反应体系(如既含有水相又含有有机相的两相反应体系)，通过与过氧化氢反应进行烯烃环氧化反应的过程。催化剂体系由第一组分和第二组分组成，第一组分选自元素W，Mo，V或其衍生物中的至少一种，第二组分选自P和As的衍生物中的至少一种。催化剂组分的原子比介于12到0.1之间，优选介于1.5到0.25之间。 
Venturello在美国专利4,562,276和4,595,671中公开了烯类化合物的环氧化反应催化剂，既可用于均相水溶液也可用于非均相体系。对应于分子式Q3XW4O24-2n的催化剂，其中Q代表阴离子盐中的阳离子，X是P或As，n＝0，1或2。当X为P时，W与P的原子比必须是4。这类组合物在反应物始终处于均一有机相中的环氧化反应中的使用还未见报道。 
Bonsignore在美国专利5,324,849中公开了一系列基于钨和二磷酸的化合物，其含有活性氧原子和由鎓盐衍生出的阳离子基团。这类化合物可在既含有机相又含水相的两相反应体系中催化烯烃氧化反应。此化合物含有2个磷原子和5个钨原子，其W:P原子比为5：2。
然而，在前述专利中描述的两相反应体系有很多缺点限制了其在大规模商业应用中的使用。相转移剂的使用显著提高了操作费用，传质问题也会经常遇到，特别是对相对易挥发的烯烃如丙烯，另外还有一些与操作两相反应器和相分离器相关的机械困难。因此需要开发能在均相环氧化反应过程中提供高选择性的活性催化剂。 
发明概要
本发明所述过程是指在催化剂和共催化剂存在下，用一种含水氧化试剂，对全馏程、加氢处理的柴油进行脱硫，再通过溶剂萃取选择性地脱除氧化的化合物。在上述步骤后可选择性地进行溶剂汽提及回收，最后为精制步骤。 
图例简要说明 
附图是本发明所述过程的示意图。 
发明内容
发明内容 
如附图所示，将储罐10中的加氢柴油输入反应器柱12中，在此处其处于连续氧化反应条件下，与从储罐14输入到反应器柱12顶部的水溶性氧化剂和复合催化剂进行反应。水溶性氧化剂可以是过氧化氢、次氯酸钠或过硫酸钠，由复合催化剂催化得到。随后再用水和极性溶剂的混合物对柴油进行连续的液-液萃取。 
该过程用于沸程为240℃到360℃的全馏程加氢柴油的脱硫。该过程包括在逆流罐或湍流罐反应器中，在有催化剂和共催化剂也可作为相转移剂的存在下，用过氧化氢水溶液对柴油进行处理。这个过程实现了加氢柴油中硫物种的氧化，使总硫以重量计达到较满意的1000ppm的水平。存在的硫物种氧化成相应的亚砜、砜、sultines、磺酸内酯、磺酸酯、亚磺酸酯，甚至氧化成二氧化硫和三氧化硫、亚硫酸酯和硫酸酯。 
使用的催化剂可以选自许多均相或非均相氧化催化剂，包括四酰氨基大环铁复合物、四烷基铵多氧金属化物、二甘醇酸酯二氧化钼、过渡金属四苯基卟啉、过渡金属乙酰丙酮化物、钼酸铋、氨基二甘醇酸酯二氧化钼、四烷基铵金属硫代四苯基卟啉、钨钼膦酸盐以及其他一些物质。还可包括多氧金属化物的季铵盐、单一金属氧化物。还可包括四辛基磷钨酸铵、过氧化钨钼膦酸盐、磷钼酸、氨基二异丙醇二氧化钼、三膦酰基-聚过氧化钨酸盐、铋钼酸、磺基酞菁钠钴过氧化物。 
由于传质问题反应速度慢，共催化剂的使用就是通过有利于热动力学的方法来加强和促进反应的进行。共催化剂可以是阴离子、阳离子和非离子的，优选阳离子相转移剂。本发明中每个实施例中所使用的共催化剂均是季铵盐。 
这些盐类不必在反应前预先合成，可以通过先加入过渡金属盐或酸，再加入到相同的溶剂体系中，如水溶性过氧化物体系，来原位合成相转移剂如季铵盐卤化物。典型的相转移剂有甲基三辛基溴化铵、十六烷基三甲基溴化铵、四丁基氯化铵、十四烷基氯化吡啶鎓和十四烷基溴化吡啶鎓。 
氧化反应发生在逆流反应器12中，反应器可以是静态的、湍流的，搅拌的、靠摆动或转盘搅拌，反应温度为50-150℃，优选70-110℃。氧化反应后的反应残液，其中含有残留的催化剂、过剩或残留的氧化剂，被循环到氧化剂-催化剂储罐14中，再加入补充的催化剂和氧化剂。 
催化剂的浓度以重量计约为氧化剂的0.001%～1.00%，优选0.01%～0.10%。氧化剂的浓度按重量计可在1%～100%范围内变化，通常介于10%～50%，对于水相中的过氧化氢按重量计优选15%～30%。氧化剂可根据化学类型、氧化电势、效率、稳定性和可溶性发生变化，该领域技术人员可较容易的确定氧化剂的有效浓度。可用于本发明过程的氧化剂包括过氧化氢、次氯酸钠、过氧化二硫酸或过氧化单硫酸钠或钾、叔丁基过氧化氢、高氯酸、硝酸、硫酸、过甲酸以及它们的混合物。 
 所述过程的第二步是通过馏出液与柱16中的选择性萃取溶剂相接触来脱除氧化的化合物。正如文献报道的氧化脱硫过程(ODS)，通常会使用用水溶性极性溶剂进行的液-液萃取技术，所述水溶性极性溶剂如二甲基亚砜、二甲基甲酰胺、甲醇和乙腈。二甲基亚砜和二甲基甲酰胺对砜具有较高的萃取能力，但其沸点高，与砜的沸点接近，因此通过蒸馏再生后不能在后续的萃取中重复使用。甲醇和乙腈可作为优选的萃取溶剂，因它们具有相对较低的沸点，极易通过蒸馏的方法从砜和其他氧化的硫化合物中分离出来。当甲醇和乙腈与轻油接触时，有大量的芳烃伴随砜被萃取出来，然而水的加入会抑制芳烃的萃取。极性溶剂包括那些具有高希尔德布兰德可溶性参数δ的溶剂；δ值高于22的液体可成功用于这些化合物的萃取。极性液体的范例及其希尔德布兰德值列于下表中。 
表2几种有用的极性溶剂的希尔德布兰德值 
  溶剂   希尔德布兰德  值   溶剂   希尔德布兰德  值
  丙酮   19.7   二甲基亚砜   26.4
  乙二醇二丁醚   20.2   正丁醇   28.7
  二硫化碳   20.5   乙腈   30.0
  吡啶   21.7   甲醇   29.7
  乙二醇一乙醚   21.9   丙二醇   30.7
  二甲基甲酰胺   24.7   乙二醇   34.9
  丙醇   24.9   丙三醇   36.2
  乙醇   26.2   水   48.0
然而对于本领域技术人员显而易见的是，仅从极性考虑不足以确定有效的萃取溶剂。例如，甲醇的极性高，但其密度0.79g/cc几乎和一种典型的轻油的密度一样，导致分离更加困难。需要考虑的其他性能还包括沸点、凝固点、黏度及表面张力等。二甲基亚砜所表现出的这些性能使其成为一个很好的溶剂，用来萃取液态轻油中氧化的硫、氮化合物，但遗憾的是其本身含有较大比例的硫。含有氮、磷和硫的杂原子溶剂必须是易挥发的，以保证能从柴油中被汽提出来。基于乙腈和甲醇所具有的极性、挥发性和低成本，使它们成为本发明所述过程中的优选溶剂。 
在第二阶段或第二步中，在逆流萃取器16中对氧化的硫化合物进行萃取，从柴油中脱除氧化的硫化合物，萃取器16可为Karr、Scheibel或其他构造的逆流或湍流罐萃取器。萃取相由水溶液组成，该水溶液是在极性有机溶剂中含有10％～30％水的水溶液，极性有机溶剂包括乙腈、甲醇或其他溶剂。因此所述溶剂必须具有足够的极性才能对萃取过程中的极性化合物具有选择性。 
在所述过程的第三阶段，用汽提塔柱脱除柴油中的痕量溶剂，溶剂回收后送至溶剂回收分馏器20。 
在所述过程的第四阶段，在汽提塔回收闪蒸器(没有列出)中回收萃取富集的溶剂。从闪蒸器出来的残渣被排到一个砜的储罐中作为石化中间体出售，或添加到燃料油或原油中。 
在所述过程的第五阶段，柴油通过吸附剂精制塔来脱除柴油中最后的痕量硫，至硫含量低于10ppm。为此许多吸附剂都是可用的，包括活性炭、硅胶、氧化铝和其他无机吸附剂。在本发明的一优选实施例中，使用了一种新型吸附剂，由极性高分子组成，但其表面上涂覆了惰性的高比表面积的载体，如硅胶、氧化铝和活性炭等。这些高分子包括聚砜、聚丙烯腈、聚苯乙烯、聚对苯二甲酸酯、聚氨酯和其他一些对氧化的硫化合物具有亲合性的高分子。使用涂覆有载体的高分子的优点是吸附和脱附过程迅速可逆，吸附剂易回收，塔柱经适宜的溶剂萃取后易再生和干燥。 
实施例1-7 
对于实施例中公开的催化剂的制备和氧化反应，下述文献给各实施例提供了相应的指导。 
1.Venturello，Carlo，et al.，US Patent 4,562,276，Peroxide Composition Based on Tungstenand Phosphorus or Arsenic and Processes and Uses Relative Thereto，December 31，1985. 
2.Bonsignore，Stefanio，et al，US Patent 5,324,849 Class of Peroxy Compounds Based onTungsten and Diphoshonic Acids and Process for Obtaining Them，June 28，1994. 
3.Te，Mure，et al，Oxidation Reactivities of Dibenzothiophenes in Polyoxyrnetalate/H2O2and Formic Acid/H2O2 Systems，Applied Catalysis A：General 219(2001)267-280. 
4.Shum，Wilfred，et al，Production of Molybdenum Dioxo DialkyleneglycolateCompositions for Epoxidation of Olefins，US Patent 4,607,113，August 19，1986. 
5.Campos-Martin，J.M.，et al，Highly Efficient Deep Desulfurization of Fuels by ChemicalOxidation，Green Chemistry，2004，6，556-562. 
6.Hu，Changwen，Catalysis by Heteropoly Compounds XXII.Reactions of Esters andEsterifications Catalyzed by Heteropolyacids in a Homogeneous Liquid Phase，Journal ofCatalysis 143，437-448(1993). 
7.Bressan，Mario，et al，Oxidation of Dibenzothiophene by Hydrogen Peroxide orMonopersulfate and Metal-Sulfophthalocyanine Catalysts，New Journal of Chemistry，2003，27，989-993. 
实施例1四辛基磷钨酸铵 
Carlo Venturello催化剂{(C8H17)4N}3PW4O24分子量2550.99) 
A.Venturello催化剂的制备：称取3.30g(10mmol)钨酸钠置于250ml烧杯中，加入7ml浓度为30％的过氧化氢水溶液，在25℃下搅拌至无色；将1.0ml浓度为85％的磷酸加入到该溶液中，再用水将其稀释到50ml；搅拌下再将2.5g溶于二氯甲烷的四辛基氯化铵(Aldrich)滴加到上述溶液中，滴加时间在2分钟以上；继续搅拌15分钟后，将有机相分离、过滤，并在室温下挥发过夜，得到3.5g无色浆液。 
B.阿拉伯轻瓦斯油的氧化：将100ml全馏程(FR)加氢(HT)阿拉伯轻瓦斯油(ALGO)，含有总硫910ppm，在搅拌电炉上搅拌加热至85℃；然后加入50ml浓度为15％的过氧化氢水溶液和50mg在上述A.Venturello催化剂的制备中描述的催化剂三(十六烷基三甲基)磷钨酸铵(Venturello催化剂)；反应15分钟后，冷却并将反应物倒入250ml的分液漏斗中，放掉处于下层的过氧化物水相。油相样品用气相色谱-美国Sievers公司的硫化学发光检测器(GC-SCD)进行分析，并与初始的全馏程加氢阿拉伯轻瓦斯油样品进行对比。色谱结果明显显示出两样品具有相同数量的硫存在，但色谱中硫的峰位置向后移 动，表明有砜生成。硫分析显示氧化的样品含有880ppm的硫，允许分析误差的存在，表明没有硫被脱除。 
C.氧化油的分批萃取：将100ml在上述B.阿拉伯轻瓦斯油的氧化中得到的油样，用50ml浓度为10％的乙腈水溶液萃取两次，第二次萃取后，得到98ml油样，经总硫分析显示含有60ppm的硫，油样经GC-SCD分析发现初始的和氧化的硫的峰几乎都被脱除了。将两次萃取液混合，挥发过夜成干油样，然后再用色质联用(GCMS)和GC-SCD进行分析。GC-SCD分析结果表明有烷基苯并噻吩二氧化物和烷基二苯并噻吩二氧化物的存在，它们通常存在于氧化油中。GCMS结果表明有甲基、二甲基、三甲基和四甲基苯并噻吩砜和二苯并噻吩砜的存在。 
D.氧化油的逆流萃取：将100ml全馏程(FR)加氢(HT)阿拉伯轻瓦斯油(ALGO)，含有总硫910ppm，按照上述B.阿拉伯轻瓦斯油的氧化所述进行氧化处理，但不进行萃取。将100ml氧化油样，其中含有以砜形式存在的近900ppm的硫，转移到直径2.5cm高75cm的玻璃逆流萃取装置中，该装置中装有直径3mm的玻璃珠约50cm高。用HitachiL2000实验泵以10ml/min的速度将150ml乙腈/水混合物，体积比为90∶10，从下向上通过玻璃装置和氧化油。经混合的极性溶剂逆流萃取后，从萃取装置中收集油样，用GC-SCD进行分析并测定总硫。结果表明在萃取的油样中没有发现硫的峰，且总硫的分析结果显示硫含量为25ppm。 
E.用固相吸附介质精制萃取的氧化油：将100ml全馏程(FR)加氢(HT)阿拉伯轻瓦斯油(ALGO)，含有总硫910ppm，按照上述B和C过程进行氧化和萃取处理。将氧化萃取后的油样通过一直径2.5cm高50cm的玻璃色谱柱，色谱柱中含有10g微孔氰基键合的固相萃取介质。经过色谱柱的流体用GC-SCD进行分析，没有检测到硫的峰，Antek总硫分析结果表明含硫8ppm。 
F.用氧化铝精制氧化萃取油：将100ml在上述D.氧化油的逆流萃取中得到的氧化萃取油样通过一直径2.5cm高50cm的玻璃色谱柱，色谱柱中含有10gDavidson氧化铝。经过色谱柱的流体用GC-SCD进行分析，没有检测到硫的峰，Antek总硫分析结果表明含硫5ppm。 
实施例2.钨钼膦酸盐 
Stefanio Bonsignore催化剂MO2W7O30·2N(CH2PO)3(分子量2217.75) 
A.Bonsignore催化剂的制备：称取3.54g钼酸铵(分子量1235.86)和23.10g钨酸钠(分子量329.86)置于250ml烧杯中并加入100ml蒸馏水，溶液中含20毫(克)当量的钼和7O毫(克)当量的钨，剧烈搅拌15分钟直至溶液变澄清无色。取3ml该溶液置于一20ml的管形瓶中，加入1.0ml浓度30％的过氧化氢溶液，混合至变成酒红色，再加入2.00ml30％的(摩尔浓度1.0M)氨基-三亚甲基磷酸(ATMP，分子量299.05)溶液，溶液很快变成绿黄色。 
B.油的氧化与分析：将制备的100ml全馏程加氢直馏柴油置于400ml烧杯中，加入50ml浓度15％的过氧化氢，加热并搅拌，再加入25mg四癸基溴化铵(TDAB)相转移剂，最后将5.0ml制备的过氧化钨钼酸三膦催化剂加入该油-水-过氧化物混合物中，继续加温至80℃并在80-100℃下保持40分钟。 
将氧化的混合物冷却并转移至250ml分液漏斗中，分离并放掉处于下部的水层，并将油层转移到200ml的聚乙烯瓶中。油样经GC-SCD分析，所有硫的峰都向色谱中砜的区域移动，表观转化率为100％。 
实施例3.十二烷基磷钼酸 
Mere Te催化剂磷钼酸H3PO4Mo12O36·XH2O(分子量1825.25) 
A.催化剂的制备：称取2g钼酸(Fisher，含MoO389.1％)置于400ml烧杯中并加入40ml蒸馏水，加入0.25g片状氢氧化钠并搅拌至全部溶解，再加入2g对钼酸铵(NH4)6Mo7O24·4H2O并与加入的0.5g片状氢氧化钠搅拌10分钟至全部溶解。在连续搅拌下加入5.0ml浓度85％的磷酸，然后再加入3.0ml浓硝酸，溶液呈暗黄色。 
B.油的氧化与分析：将100ml加氢柴油置于400ml烧杯中，加入50ml浓度15％的过氧化氢，在样品加热过程中在搅拌下再加入2ml上述的催化剂溶液，最后加入50mg十六烷基氯化吡啶鎓(Aldrich)，将溶液加热至80℃并在80-100℃剧烈搅拌下保持30分钟。将样品冷却并转移至250ml分液漏斗中，分离并放掉处于下部的水层，将油层转移到200ml的聚乙烯瓶中并用GC-SCD分析。约20％硫的峰的保留时间后移，表明苯并噻吩和二苯并噻吩被氧化成相应的砜。 
实施例4.氨基二异丙醇二氧化钼 
Wilfred Shum催化剂MoO2NH(CHCH3CH2O)2(分子量763.03) 
A.催化剂制备：称取17.7g对钼酸铵(NH4)6Mo7O24·4H2O(分子量1235.86)置于400ml烧杯中并加入125ml蒸馏水，搅拌下加入40ml浓度40％的二异丙醇胺(工业级)水溶液，搅拌下升温至135℃并恒温8小时，此过程中需向溶液中缓慢通入空气。 
B.油的氧化与分析：将100ml加氢柴油置于400ml烧杯中，加入50ml浓度15％的过氧化氢，在样品加热过程中在搅拌下再加入2ml上述的催化剂溶液，最后加入50mg四辛基溴化铵，将溶液加热至80℃并在80-100℃剧烈搅拌下保持30分钟。将样品冷却并转移至250ml分液漏斗中，分离并放掉处于下部的水层。将油层转移到200ml的聚乙烯瓶中并用GC-SCD分析，约10％硫的峰的保留时间后移，表明苯并噻吩和二苯并噻吩被氧化成相应的砜。 
实施例5.三膦酰基-聚过氧化钨酸盐 
J.M.Campos-Martin催化剂N(CH2PO)3(WO5)9(分子量2571.54) 
A.催化剂制备：将3.0g钨酸钠溶于10ml浓度30％的过氧化氢中生成亮黄色溶液，再加入3ml浓度30％的氨基三亚甲基磷酸溶液(N(CH2PO3H2)3)，溶液立即变成无色，再用蒸馏水将溶液稀释至30ml。 
B.油的氧化与分析：将100ml加氢柴油置于400ml烧杯中，加入50ml浓度15％的过氧化氢，在样品加热过程中在搅拌下再加入2ml上述的催化剂溶液，最后加入50mg十六烷基三甲基溴化铵，将溶液加热至80℃并在80-100℃剧烈搅拌下保持30分钟。将样品冷却并转移至250ml分液漏斗中，分离并放掉处于下部的水层。将油层转移到200ml的聚乙烯瓶中并用GC-SCD分析，约90％硫的峰的保留时间后移，表明苯并噻吩和二苯并噻吩被氧化成相应的砜。 
实施例6.铋钼酸 
Changwen Hu H5BiMo12O40·4H2O(分子量2077.34) 
A.催化剂制备：在250ml烧杯中将2.0g硝酸铋溶于50ml蒸馏水中，将浓硝酸滴加到该溶液中直至完全溶解，称取25.0g对钼酸铵 (NH4)6Mo7O24·4H2O置于400ml烧杯中，在剧烈搅拌下将其溶于150ml蒸馏水中，混合后立即产生白色沉淀，并于50℃陈化6小时，产物经过滤、洗涤后，干燥过夜。将所得样品研成粉末混匀后于450℃焙烧12小时。 
B.油的氧化与分析：将100ml加氢柴油置于400ml烧杯中，加入50ml浓度15％的过氧化氢，在样品加热过程中在搅拌下再加入100mg催化剂，最后加入50mg四辛基溴化铵，将溶液加热至80℃并在80-100℃剧烈搅拌下保持30分钟。将样品冷却并转移至250ml分液漏斗中，分离并放掉处于下部的水层。将油层转移到200ml的聚乙烯瓶中并用GC-SCD分析，至少95％硫的峰的保留时间后移，表明苯并噻吩和二苯并噻吩被氧化成相应的砜。 
实施例7.磺基酞菁钠钴过氧化物 
Mario Bressan催化剂Na4C32H12N8S4O12Co(II)O2(分子量1011.64) 
A.催化剂制备：将0.50gUOP商业产品磺基酞菁钴(Merox催化剂)溶于100ml浓度10％的氢氧化钠中，得到含5000ppm原料催化剂溶液。将4.0ml催化剂溶液加入到36ml浓度3.8625％的单过硫酸钾KHSO5(0.25Molar)水溶液中，将催化剂溶液置于一管形瓶中备用。催化剂溶液的最终浓度是含有500ppm的磺基酞菁钴和0.225M的单过硫酸钾。 
B.油的氧化与分析：将100ml加氢柴油置于500ml锥瓶中，并在锥瓶上加一冷凝管，在样品加热过程中在搅拌下再加入40ml催化剂-单过硫酸溶液和60ml乙腈，将混合物加热至83℃并在80-100℃回流并剧烈搅拌下保持3小时，样品在5℃下冷却2小时，分成两相。将锥瓶中的物质转移至250ml分液漏斗中，分离并放掉处于下部的乙腈水溶液层，将油层转移到200ml的聚乙烯瓶中并用GC-SCD分析。约50％的硫的峰从油相中脱除，其他峰的保留时间后移，表明苯并噻吩和二苯并噻吩被氧化成相应的砜。约有半数的硫从油相中脱除并转移到乙腈水相。 

Claims (11)

1.用于降低柴油硫含量的工艺，包括以下步骤：
a.在均相或非均相氧化催化剂存在下，在反应器中将含有硫化合物的柴油燃料与含水氧化剂接触，在50-150℃的温度下反应一段足以对硫化合物进行氧化的时间，所述含水氧化剂选自硫酸、过乙酸、过氧化氢、次氯酸钠、高氯酸、硝酸、过氧化二硫酸或过氧化单硫酸钠和钾、以及它们的混合物，所述氧化催化剂选自过氧化钨钼膦酸盐、磷钼酸、钨钼膦酸盐、氨基二异丙醇二氧化钼、三膦酰基-聚过氧化钨酸盐、铋钼酸和磺基酞菁钠钴过氧化物；
b.通过以水溶性极性溶剂的液-液逆流萃取从柴油燃料中脱除氧化的硫化合物。
2.按照权利要求1所述的工艺，包括以下步骤：
a.从柴油燃料中汽提出溶剂；
b.通过将其通过吸附剂以脱除残余硫化合物来精制柴油燃料。
3.按照权利要求1所述的工艺，其中所述反应器为逆流反应器。
4.按照权利要求1所述的工艺，其中所述反应器为湍流式、搅拌式、振动式或静态反应器。
5.按照权利要求1所述的工艺，其中所述溶剂选自乙腈和甲醇的水溶液。
6.按照权利要求2所述的工艺，其中所述精制受吸附剂床层影响，吸附剂床层由极性有机基团涂覆或结合的载体组成，载体选自氧化硅、氧化铝或活性炭。
7.按照权利要求5所述的工艺，其中所述溶剂中含有10％-30％的水。
8.按照权利要求7所述的工艺，其中所述溶剂含有10％的水。
9.按照权利要求1所述的工艺，其中在所述处理的柴油燃料中的硫浓度被降低到小于10ppm。
10.按照权利要求6所述的工艺，其中所述固体载体涂覆有选自聚砜、聚丙烯腈、聚苯乙烯、聚对苯二甲酸酯和聚氨酯的极性高分子。
11.按照权利要求1所述的工艺，其中所述催化剂为过氧化钨钼膦酸盐。
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