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

柴油的氧化萃取脱硫 Download PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
oxidation
sulphur
diesel oil
described technology
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN200680041722.5A
Other languages
English (en)
Other versions
CN101389735A (zh
Inventor
G·D·马蒂尼
F·M·阿尔-沙拉尼
B·O·达布西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saudi Arabian Oil Co
Original Assignee
Saudi Arabian Oil Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Saudi Arabian Oil Co filed Critical Saudi Arabian Oil Co
Publication of CN101389735A publication Critical patent/CN101389735A/zh
Application granted granted Critical
Publication of CN101389735B publication Critical patent/CN101389735B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/20—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
    • C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/44—Solvents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

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。
CN200680041722.5A 2005-09-08 2006-07-28 柴油的氧化萃取脱硫 Expired - Fee Related CN101389735B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11/222,729 US7744749B2 (en) 2005-09-08 2005-09-08 Diesel oil desulfurization by oxidation and extraction
US11/222,729 2005-09-08
PCT/US2006/029574 WO2007030229A2 (en) 2005-09-08 2006-07-28 Diesel oil desulfurization by oxidation and extraction

Publications (2)

Publication Number Publication Date
CN101389735A CN101389735A (zh) 2009-03-18
CN101389735B true CN101389735B (zh) 2013-07-31

Family

ID=37829075

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200680041722.5A Expired - Fee Related CN101389735B (zh) 2005-09-08 2006-07-28 柴油的氧化萃取脱硫

Country Status (7)

Country Link
US (1) US7744749B2 (zh)
EP (1) EP1941005A4 (zh)
CN (1) CN101389735B (zh)
BR (1) BRPI0617004A2 (zh)
EA (1) EA016125B1 (zh)
NO (1) NO20081119L (zh)
WO (1) WO2007030229A2 (zh)

Families Citing this family (69)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8715489B2 (en) * 2005-09-08 2014-05-06 Saudi Arabian Oil Company Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
US7744749B2 (en) 2005-09-08 2010-06-29 Saudi Arabian Oil Company Diesel oil desulfurization by oxidation and extraction
EP2001802B1 (en) * 2006-03-03 2021-06-09 Saudi Arabian Oil Company Catalytic process for deep oxidative desulfurization of liquid transportation fuels
US8936719B2 (en) * 2006-03-22 2015-01-20 Ultraclean Fuel Pty Ltd. Process for removing sulphur from liquid hydrocarbons
US7634686B2 (en) 2006-07-24 2009-12-15 Marvell World Trade Ltd. File server for redundant array of independent disks (RAID) system
CA2685850C (en) 2007-05-03 2016-06-28 Auterra, Inc. Product containing monomer and polymers of titanyls and methods for making same
CN101173179B (zh) * 2007-10-24 2010-09-29 中国科学院大连化学物理研究所 一种柴油氧化蒸馏超深度脱硫的催化剂及脱硫方法
SG189702A1 (en) * 2008-03-26 2013-05-31 Auterra Inc Sulfoxidation catalysts and methods and systems of using same
US9061273B2 (en) 2008-03-26 2015-06-23 Auterra, Inc. Sulfoxidation catalysts and methods and systems of using same
US8298404B2 (en) * 2010-09-22 2012-10-30 Auterra, Inc. Reaction system and products therefrom
US8764973B2 (en) 2008-03-26 2014-07-01 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US9206359B2 (en) 2008-03-26 2015-12-08 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US8894843B2 (en) 2008-03-26 2014-11-25 Auterra, Inc. Methods for upgrading of contaminated hydrocarbon streams
US20100122937A1 (en) * 2008-11-20 2010-05-20 John Aibangbee Osaheni Method and system for removing impurities from hydrocarbon oils via lewis acid complexation
US20100264067A1 (en) * 2009-04-16 2010-10-21 General Electric Company Method for removing impurities from hydrocarbon oils
EP2478070A4 (en) * 2009-09-16 2014-07-16 Envion Inc DECOMPOSITION OF PLASTIC WASTE
US20110073526A1 (en) * 2009-09-30 2011-03-31 General Electric Company Method for Desulfurization of Hydrocarbon Oils
US20110220550A1 (en) * 2010-03-15 2011-09-15 Abdennour Bourane Mild hydrodesulfurization integrating targeted oxidative desulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US9296960B2 (en) 2010-03-15 2016-03-29 Saudi Arabian Oil Company Targeted desulfurization process and apparatus integrating oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US8658027B2 (en) 2010-03-29 2014-02-25 Saudi Arabian Oil Company Integrated hydrotreating and oxidative desulfurization process
US10087377B2 (en) * 2010-09-07 2018-10-02 Saudi Arabian Oil Company Oxidative desulfurization of oil fractions and sulfone management using an FCC
US10035960B2 (en) 2010-09-07 2018-07-31 Saudi Arabian Oil Company Process for oxidative desulfurization and sulfone management by gasification
US10093871B2 (en) 2010-09-07 2018-10-09 Saudi Arabian Oil Company Desulfurization and sulfone removal using a coker
US9574142B2 (en) 2010-09-07 2017-02-21 Saudi Arabian Oil Company Process for oxidative desulfurization and sulfone management by gasification
US10081770B2 (en) * 2010-09-07 2018-09-25 Saudi Arabian Oil Company Process for oxidative desulfurization and sulfone disposal using solvent deasphalting
US9598647B2 (en) 2010-09-07 2017-03-21 Saudi Arabian Oil Company Process for oxidative desulfurization and sulfone disposal using solvent deasphalting
US10093870B2 (en) 2010-09-07 2018-10-09 Saudi Arabian Oil Company Desulfurization and sulfone removal using a coker
US10093872B2 (en) * 2010-09-07 2018-10-09 Saudi Arabian Oil Company Oxidative desulfurization of oil fractions and sulfone management using an FCC
US9574144B2 (en) 2010-09-07 2017-02-21 Saudi Arabian Oil Company Process for oxidative desulfurization and denitrogenation using a fluid catalytic cracking (FCC) unit
US9574143B2 (en) 2010-09-07 2017-02-21 Saudi Arabian Oil Company Desulfurization and sulfone removal using a coker
US9828557B2 (en) 2010-09-22 2017-11-28 Auterra, Inc. Reaction system, methods and products therefrom
US9296956B2 (en) 2010-10-28 2016-03-29 Chevron U.S.A. Inc. Method for reducing mercaptans in hydrocarbons
US8741127B2 (en) 2010-12-14 2014-06-03 Saudi Arabian Oil Company Integrated desulfurization and denitrification process including mild hydrotreating and oxidation of aromatic-rich hydrotreated products
JP6026428B2 (ja) * 2010-12-15 2016-11-16 サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ 気体酸化剤を用いた炭化水素供給原料の脱硫方法
US8741128B2 (en) 2010-12-15 2014-06-03 Saudi Arabian Oil Company Integrated desulfurization and denitrification process including mild hydrotreating of aromatic-lean fraction and oxidation of aromatic-rich fraction
EP2737014B1 (en) 2011-07-29 2021-02-17 Saudi Arabian Oil Company Process for in-situ electrochemical oxidative generation and conversion of organosulfur compounds
JP6114285B2 (ja) * 2011-09-27 2017-04-12 サウジ アラビアン オイル カンパニー 酸化脱硫反応生成物の選択的液−液抽出
KR101336266B1 (ko) * 2011-12-21 2013-12-05 에스케이이노베이션 주식회사 황산화물 함유 고비점 유분으로부터 황산화물을 분리 제거하는 방법
US8906227B2 (en) 2012-02-02 2014-12-09 Suadi Arabian Oil Company Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds
US20120138449A1 (en) * 2012-02-12 2012-06-07 King Abdulaziz City for Science and Technology (KACST) Method of removing sulfur from crude oil and diesel using ionizing radiation
WO2014052951A1 (en) * 2012-09-28 2014-04-03 Saudi Arabian Oil Company Process for reducing the sulfur content from oxidized sulfur-containing hydrocarbons
US8920635B2 (en) 2013-01-14 2014-12-30 Saudi Arabian Oil Company Targeted desulfurization process and apparatus integrating gas phase oxidative desulfurization and hydrodesulfurization to produce diesel fuel having an ultra-low level of organosulfur compounds
US11440815B2 (en) 2013-02-22 2022-09-13 Anschutz Exploration Corporation Method and system for removing hydrogen sulfide from sour oil and sour water
US9364773B2 (en) 2013-02-22 2016-06-14 Anschutz Exploration Corporation Method and system for removing hydrogen sulfide from sour oil and sour water
US9708196B2 (en) 2013-02-22 2017-07-18 Anschutz Exploration Corporation Method and system for removing hydrogen sulfide from sour oil and sour water
CA2843041C (en) 2013-02-22 2017-06-13 Anschutz Exploration Corporation Method and system for removing hydrogen sulfide from sour oil and sour water
JP6389832B2 (ja) * 2013-03-15 2018-09-12 ウルトラクリーン フューエル ピーティーワイ リミテッド 炭化水素から硫黄化合物を除去する処理方法
US9441169B2 (en) 2013-03-15 2016-09-13 Ultraclean Fuel Pty Ltd Process for removing sulphur compounds from hydrocarbons
DE102013205302A1 (de) * 2013-03-26 2014-10-16 BSH Bosch und Siemens Hausgeräte GmbH Hausgerät mit einer katalytisch wirksamen Oberfläche sowie Verfahren zu seinem Betrieb
CN105934494B (zh) * 2013-10-07 2019-06-18 氟石科技公司 使用溶剂回收元素硫的构造、系统和方法
US10307706B2 (en) 2014-04-25 2019-06-04 Ada Carbon Solutions, Llc Sorbent compositions for use in a wet scrubber unit
RU2584697C1 (ru) * 2015-02-03 2016-05-20 Александр Иванович Пойманов Способ очистки дизельного топлива от соединений серы
WO2016154529A1 (en) 2015-03-26 2016-09-29 Auterra, Inc. Adsorbents and methods of use
US10522860B2 (en) * 2015-06-09 2019-12-31 Honeywell International Inc. Systems for hybrid fuel cell power generation
WO2017011242A1 (en) 2015-07-15 2017-01-19 Uop Llc Oxidation catalyst and processes for using same
CN105289472A (zh) * 2015-11-19 2016-02-03 兰州坤仑环保科技有限公司 一种蜂窝状凹凸棒陶粒柴油脱硫剂
CN105396548A (zh) * 2015-11-19 2016-03-16 兰州坤仑环保科技有限公司 一种酸活化和热改性凹凸棒汽油脱硫剂
US10450516B2 (en) 2016-03-08 2019-10-22 Auterra, Inc. Catalytic caustic desulfonylation
CN106367100B (zh) * 2016-09-05 2017-12-22 山东大学 一种利用纳米碳材料和空气氧一步氧化吸附脱硫的方法
CN106753517B (zh) * 2017-02-08 2018-10-19 浙江理工大学 一种燃油氧化脱硫的方法
KR20190115084A (ko) * 2017-02-20 2019-10-10 사우디 아라비안 오일 컴퍼니 코커를 사용한 탈황 및 설폰 제거
AU2017413746B2 (en) * 2017-05-08 2023-05-11 Solvay Sa Process for removing sulfur compounds from a liquid composition
US10564142B2 (en) 2017-09-29 2020-02-18 Saudi Arabian Oil Company Quantifying organic and inorganic sulfur components
CN108277043B (zh) * 2018-02-26 2019-12-03 烟台大学 一种柴油脱硫的方法
CN108998060B (zh) * 2018-08-23 2021-06-08 中石化（洛阳）科技有限公司 一种低硫焦炭生产新工艺
RU2708629C1 (ru) * 2019-05-30 2019-12-10 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ, НИ ТГУ) Способ обессеривания тяжелого нефтепродукта с применением микроволнового излучения
RU2711756C1 (ru) * 2019-06-27 2020-01-21 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) Способ каталитического крекинга вакуумного газойля
KR20240004920A (ko) * 2021-05-06 2024-01-11 킹 압둘라 유니버시티 오브 사이언스 앤드 테크놀로지 초음파로 유도된 공동현상을 사용하여 중유 탈황을 위한 방법
CN113621439B (zh) * 2021-10-11 2022-01-07 苏州丰倍生物科技有限公司 脂肪酸甲酯的纯化方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277271B1 (en) * 1998-07-15 2001-08-21 Uop Llc Process for the desulfurization of a hydrocarbonaceoous oil
US6402938B1 (en) * 2000-05-23 2002-06-11 Marathon Ashland Petroleum Llc Vaporization of used motor oil with non-hydrogenating recycle vapor
CN1534082A (zh) * 2003-03-28 2004-10-06 中国科学院大连化学物理研究所 一种超低硫柴油的制备方法

Family Cites Families (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US14911A (en) * 1856-05-20 Improvement in artificial decoloring compounds
US178121A (en) * 1876-05-30 Improvement in gas-engines
US178122A (en) * 1876-05-30 Improvement in thill-couplings
US35306A (en) * 1862-05-20 Improvement in combined cultivator and seeding-machine
US29997A (en) * 1860-09-11 Machine foe
US2253308A (en) 1937-05-05 1941-08-19 Standard Catalytic Co Desulphurization of hydrocarbons
US2697682A (en) 1949-05-23 1954-12-21 Anglo Iranian Oil Co Ltd Catalytic desulfurization of petroleum hydrocarbons
US2593761A (en) 1950-02-21 1952-04-22 Universal Oil Prod Co Reducing the mercaptan content of petroleum distillates with a hydroperoxide
US2671049A (en) 1951-06-30 1954-03-02 Standard Oil Co Odor improvement of petroleum oils
US2834717A (en) 1956-03-07 1958-05-13 Shiah Chyn Duog Process of desulfurizing hydrocarbons with a boron fluoride coordination compound followed by hydrofining with a hydrogen donor
BE610625A (zh) 1960-11-22
BE625074A (zh) 1961-11-24
US3595778A (en) 1968-12-16 1971-07-27 Texaco Inc Desulfurization process including an oxidation step with ozone and a vanadium catalyst
US3565793A (en) 1968-12-27 1971-02-23 Texaco Inc Desulfurization with a catalytic oxidation step
US3719589A (en) 1971-03-05 1973-03-06 Texaco Inc Asphalt separation in desulfurization with an oxidation step
US3816301A (en) 1972-06-30 1974-06-11 Atlantic Richfield Co Process for the desulfurization of hydrocarbons
US3945914A (en) 1974-08-23 1976-03-23 Atlantic Richfield Company Process for "sulfur reduction of an oxidized hydrocarbon by forming a metal-sulfur-containing compound"
US4088569A (en) * 1976-02-24 1978-05-09 Uop Inc. Mercaptan oxidation in a liquid hydrocarbon with a metal phthalocyanine catalyst
US5274140A (en) 1979-07-19 1993-12-28 Instituto Guido Donegani, S.P.A. Process for catalytically epoxidizing olefin with hydrogen peroxide
IT1205277B (it) 1982-11-10 1989-03-15 Montedison Spa Nuovo composizioni perossidiche a base di tungsteno e fosforo o arsenico
US4772731A (en) 1984-11-05 1988-09-20 Arco Chemical Company Epoxidation of olefins with molybdenum dioxo dialkyleneglycolate compositions
US4607113A (en) 1984-11-05 1986-08-19 Atlantic Richfield Company Production of molybdenum dioxo dialkyleneglycolate compositions for epoxidation of olefins
IT1186782B (it) 1985-10-18 1987-12-16 Montedison Spa Processo per la preparazione di fenilpropanoni
US5017280A (en) 1990-05-08 1991-05-21 Laboratorios Paris, C.A. Process for recovering metals and for removing sulfur from materials containing them by means of an oxidative extraction
US5087350A (en) 1990-05-08 1992-02-11 Laboratorios Paris, C.A. Process for recovering metals and for removing sulfur from materials containing them by means of an oxidative extraction
US5310479A (en) 1991-12-04 1994-05-10 Mobil Oil Corporation Process for reducing the sulfur content of a crude
IT1252669B (it) 1991-12-23 1995-06-21 Donegani Guido Ist Classe di composti perossidici a base di tungsteno e acidi difosfonici e procedimento per il loro ottenimento
IT1256601B (it) * 1992-10-16 1995-12-12 Eniricerche Spa Composizioni supportate a base di tungsteno o molibdeno,procedimento per il loro ottenimento e proprieta' come catalizzatori eterogenei di ossidazione
US5547563A (en) 1993-10-14 1996-08-20 Stowe; Lawrence R. Method of conversion of heavy hydrocarbon feedstocks
US6503471B1 (en) 1995-08-29 2003-01-07 Korea Institute Of Science & Technology Process for malodorous gas treatment
US6054580A (en) 1996-07-22 2000-04-25 Carnegie Mellon University Long-lived homogenous amide containing macrocyclic compounds
US5847120A (en) 1996-07-22 1998-12-08 Carnegie Mellon University Long-lived homogenous oxidation catalysts
US5780655A (en) 1997-05-05 1998-07-14 Arco Chemical Technology, L.P. Epoxidation process using a phosphate-stabilized peroxotungstate compound as catalyst
US5948242A (en) 1997-10-15 1999-09-07 Unipure Corporation Process for upgrading heavy crude oil production
US6160193A (en) 1997-11-20 2000-12-12 Gore; Walter Method of desulfurization of hydrocarbons
US5985137A (en) 1998-02-26 1999-11-16 Unipure Corporation Process to upgrade crude oils by destruction of naphthenic acids, removal of sulfur and removal of salts
US5961820A (en) 1998-05-27 1999-10-05 Ds2 Tech, Inc. Desulfurization process utilizing an oxidizing agent, carbonyl compound, and hydroxide
US6171478B1 (en) 1998-07-15 2001-01-09 Uop Llc Process for the desulfurization of a hydrocarbonaceous oil
US5958224A (en) 1998-08-14 1999-09-28 Exxon Research And Engineering Co Process for deep desulfurization using combined hydrotreating-oxidation
EA003072B1 (ru) 1998-09-16 2002-12-26 Джеймс К. Жанблан Способ десульфурации
FR2793256B1 (fr) 1999-05-05 2001-07-27 Total Raffinage Distrib Procede d'obtention de produits petroliers a faible taux de soufre par desulfuration d'extraits
US6368495B1 (en) 1999-06-07 2002-04-09 Uop Llc Removal of sulfur-containing compounds from liquid hydrocarbon streams
EA004903B1 (ru) 1999-12-13 2004-08-26 Дс2 Тек, Инк. Способ десульфурации нефтяных дистиллятов
EP1252253A2 (en) 1999-12-13 2002-10-30 DS2 Tech, Inc. Process for the demercaptanization of petroleum distillates
FR2802939B1 (fr) 1999-12-28 2005-01-21 Elf Antar France Procede de desulfuration des derives du thiophene contenus dans les carburants
US6596914B2 (en) 2000-08-01 2003-07-22 Walter Gore Method of desulfurization and dearomatization of petroleum liquids by oxidation and solvent extraction
US6402940B1 (en) 2000-09-01 2002-06-11 Unipure Corporation Process for removing low amounts of organic sulfur from hydrocarbon fuels
US6402939B1 (en) * 2000-09-28 2002-06-11 Sulphco, Inc. Oxidative desulfurization of fossil fuels with ultrasound
ES2179753B1 (es) 2000-10-11 2005-02-16 Universidad Politecnica De Valencia Proceso y catalizadores para la eliminacion de compuestos de azufre de la fraccion gasolina.
US6881325B2 (en) * 2001-02-08 2005-04-19 Bp Corporation North America Inc. Preparation of components for transportation fuels
US20020148754A1 (en) 2001-02-08 2002-10-17 Gong William H. Integrated preparation of blending components for refinery transportation fuels
US6827845B2 (en) 2001-02-08 2004-12-07 Bp Corporation North America Inc. Preparation of components for refinery blending of transportation fuels
FR2821350B1 (fr) 2001-02-26 2004-12-10 Solvay Procede de desulfuration d'un melange d'hydrocarbures
US6500219B1 (en) 2001-03-19 2002-12-31 Sulphco, Inc. Continuous process for oxidative desulfurization of fossil fuels with ultrasound and products thereof
ES2183710B1 (es) 2001-04-12 2004-01-16 Univ Valencia Politecnica Proceso y catalizadores para la eliminacion de compuestos de azufre de la fraccion diesel.
ATE290999T1 (de) * 2001-05-04 2005-04-15 Johnson Matthey Plc Verfahren zur herstellung von ammoniak
US7081196B2 (en) 2001-05-10 2006-07-25 Mark Cullen Treatment of crude oil fractions, fossil fuels, and products thereof with sonic energy
US7871512B2 (en) 2001-05-10 2011-01-18 Petrosonics, Llc Treatment of crude oil fractions, fossil fuels, and products thereof
US6544409B2 (en) 2001-05-16 2003-04-08 Petroleo Brasileiro S.A. - Petrobras Process for the catalytic oxidation of sulfur, nitrogen and unsaturated compounds from hydrocarbon streams
US20030051988A1 (en) 2001-05-22 2003-03-20 Gunnerman Rudolf W. Treatment of crude oil fractions, fossil fuels, and products thereof with ultrasound
US6673236B2 (en) 2001-08-29 2004-01-06 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Method for the production of hydrocarbon fuels with ultra-low sulfur content
US20040007501A1 (en) 2002-07-08 2004-01-15 Sughrue Edward L. Hydrocarbon desulfurization with pre-oxidation of organosulfur compounds
US6827844B2 (en) 2002-10-23 2004-12-07 Sulphco, Inc. Ultrasound-assisted desulfurization of fossil fuels in the presence of dialkyl ethers
US7153414B2 (en) 2002-12-10 2006-12-26 Petroleo Brasileiro S.A.-Petrobras Process for the upgrading of raw hydrocarbon streams
ATE404652T1 (de) 2002-12-17 2008-08-15 Shell Int Research Verfahren zur selektiven katalytischen oxidation von schwefelverbindungen
US7252756B2 (en) 2002-12-18 2007-08-07 Bp Corporation North America Inc. Preparation of components for refinery blending of transportation fuels
US6652992B1 (en) 2002-12-20 2003-11-25 Sulphco, Inc. Corrosion resistant ultrasonic horn
US7270742B2 (en) 2003-03-13 2007-09-18 Lyondell Chemical Technology, L.P. Organosulfur oxidation process
US20040178121A1 (en) 2003-03-13 2004-09-16 Leyshon David W. Organosulfur oxidation process
US20040200759A1 (en) 2003-04-11 2004-10-14 Mark Cullen Sulfone removal process
US20040222131A1 (en) 2003-05-05 2004-11-11 Mark Cullen Process for generating and removing sulfoxides from fossil fuel
US7314545B2 (en) * 2004-01-09 2008-01-01 Lyondell Chemical Technology, L.P. Desulfurization process
US7744749B2 (en) 2005-09-08 2010-06-29 Saudi Arabian Oil Company Diesel oil desulfurization by oxidation and extraction

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6277271B1 (en) * 1998-07-15 2001-08-21 Uop Llc Process for the desulfurization of a hydrocarbonaceoous oil
US6402938B1 (en) * 2000-05-23 2002-06-11 Marathon Ashland Petroleum Llc Vaporization of used motor oil with non-hydrogenating recycle vapor
CN1534082A (zh) * 2003-03-28 2004-10-06 中国科学院大连化学物理研究所 一种超低硫柴油的制备方法

Also Published As

Publication number Publication date
EP1941005A2 (en) 2008-07-09
US20070051667A1 (en) 2007-03-08
WO2007030229A3 (en) 2008-06-26
CN101389735A (zh) 2009-03-18
EA200800771A1 (ru) 2008-10-30
BRPI0617004A2 (pt) 2011-07-05
WO2007030229A2 (en) 2007-03-15
EP1941005A4 (en) 2013-06-19
US7744749B2 (en) 2010-06-29
EA016125B1 (ru) 2012-02-28
NO20081119L (no) 2008-05-22

Similar Documents

Publication Publication Date Title
CN101389735B (zh) 柴油的氧化萃取脱硫
Bhutto et al. Oxidative desulfurization of fuel oils using ionic liquids: A review
US9499751B2 (en) Process for oxidative conversion of organosulfur compounds in liquid hydrocarbon mixtures
EP2001802B1 (en) Catalytic process for deep oxidative desulfurization of liquid transportation fuels
Srivastava An evaluation of desulfurization technologies for sulfur removal from liquid fuels
CN100432190C (zh) 烃油的脱硫方法
Gao et al. Deep desulfurization from fuel oil via selective oxidation using an amphiphilic peroxotungsten catalyst assembled in emulsion droplets
Jiang et al. Oxidative desulfurization of fuel oils
CN101611119B (zh) 石油的氧化脱硫和脱氮
US7758745B2 (en) Diesel desulfurization method
US20090242459A1 (en) Oxidative desulfurization of fuel oil
CN1331987C (zh) 石油油品氧化脱硫的方法
Gooneh-Farahani et al. A review of advanced methods for ultra-deep desulfurization under mild conditions and the absence of hydrogen
Mirshafiee et al. Current status and future prospects of oxidative desulfurization of naphtha: a review
CN101544907A (zh) 燃料油的氧化脱硫
WO2015065668A1 (en) Methods for treating hydrocarbon streams containing mercaptan compounds
Luis Garcia-Gutierrez et al. R & D in oxidative desulfurization of fuels technologies: From chemistry to patents
JP3564533B2 (ja) 燃料油の酸化脱硫方法
Kowsari Recent advances in the science and technology of desulfurization of diesel fuel using ionic liquids
US11517889B2 (en) Catalytic carbon fiber contactor
CN102732289B (zh) 一种基于甲基三氧化铼耦合离子液体的fcc汽油氧化脱硫方法
Cheng Ultra clean fuels via modified UAOD process with room temperature ionic liquid (RTIL) & solid catalyst polishing
Jiang Deep Eutectic Solvents Extraction of Dibenzothiophene in Model Diesel
Bhutto et al. Desulphurization of fuel oils using ionic liquids
Haddadi et al. Zinc Substituted Keggin Type Polyoxometalate as an Effective Catalyst for the Oxidative Desulfurization of Dibenzothiophene by Hydrogen Peroxide as Oxidant

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20130731

Termination date: 20210728

CF01 Termination of patent right due to non-payment of annual fee