CN101291891B - 将气态烷烃转化为烯烃和液态烃的方法 - Google Patents

将气态烷烃转化为烯烃和液态烃的方法 Download PDF

Info

Publication number
CN101291891B
CN101291891B CN2006800390646A CN200680039064A CN101291891B CN 101291891 B CN101291891 B CN 101291891B CN 2006800390646 A CN2006800390646 A CN 2006800390646A CN 200680039064 A CN200680039064 A CN 200680039064A CN 101291891 B CN101291891 B CN 101291891B
Authority
CN
China
Prior art keywords
bromide
metal
reactor
bromine
hydrogen bromide
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
CN2006800390646A
Other languages
English (en)
Other versions
CN101291891A (zh
Inventor
J·J·威库里斯
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.)
Marathon GTF Technology Ltd
Original Assignee
Marathon GTF Technology Ltd
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 Marathon GTF Technology Ltd filed Critical Marathon GTF Technology Ltd
Publication of CN101291891A publication Critical patent/CN101291891A/zh
Application granted granted Critical
Publication of CN101291891B publication Critical patent/CN101291891B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/02—Non-metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/09—Bromine; Hydrogen bromide
    • C01B7/093—Hydrogen bromide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/09—Bromine; Hydrogen bromide
    • C01B7/096—Bromine
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B9/00—General methods of preparing halides
    • C01B9/04—Bromides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • 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
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y

Abstract

将气态烷烃转化为烯烃和液态烃的方法，其中，将含有烷烃的气态进料与干燥的溴蒸气反应而生成烷基溴化物和氢溴酸蒸气。然后，在从约250℃至约500℃的温度下，将烷基溴化物和氢溴酸的混合物在合成的晶态铝硅酸盐催化剂(例如X或Y型沸石)上反应，从而生成烯烃、较高分子量的烃和氢溴酸蒸气。公开了从较高分子量的烃中除去氢溴酸蒸气以及从用于该方法的氢溴酸产生溴的各种方法。

Description

将气态烷烃转化为烯烃和液态烃的方法
与相关专利申请的参照 
本申请是2005年4月8日提交、标题为“将气态烷烃转化为液态烃的方法”的共同未决的美国专利申请系列号11/101,886的部分继续申请，而美国专利申请系列号11/101,886又是2004年4月16日提交、标题为“将气态烷烃转化为液态烃的方法”的共同未决的美国专利申请系列号10/826,885的部分继续申请。 
发明背景 
发明领域
本发明涉及将较低分子量的气态烷烃转化为适用作化学品(例如润滑剂和燃料添加剂)生产中的单体和中间体的烯烃，以及较高分子量的烃的方法，更具体地说，涉及这样的方法，其中，将含较低分子量烷烃的气体与干燥的溴蒸气反应而生成烷基溴化物和氢溴酸，它们又在晶态铝硅酸盐催化剂上反应而生成烯烃和较高分子量的烃。 
相关技术的描述 
全世界已经发现了大量主要由甲烷和其它轻质烷烃构成的天然气。发现天然气的地区中很多是远离居住区的，而居住区有重要的气体管道设施或对天然气的市场需求。由于天然气的低密度，通过管道以气体形式或者作为容器中的压缩气体输送它是昂贵的。因此，对于可呈存在的气体形式运输天然气的距离有实际的和经济上的限制。天然气的低温液化(LNG)常用来更经济地远距离输送天然气。但是，该LNG方法昂贵，并且只有少数国家装备了有限的再气化设施以进口LNG。 
见于天然气的甲烷的另一个用途是作为生产甲醇的方法中的进料。工业上这样生产甲醇，即，在高温下(约1000℃)将甲烷转化为合成气(CO和H2)，随后在高压下(约100大气压)合成。有几类从甲烷生产合成气(CO和H2)的方法。其中有蒸汽-甲烷转化(SMR)、部分氧化(POX)、自热转化(ATR)、气体加热的转化(GHR)及其各种组合。SMR和GHR在高压和高温下操作，通常超过600℃，并且需要含有填充昂贵的重整催化剂的特殊耐热和耐腐蚀合金管的昂贵的炉或反应器。POX和ATR方法在高压和甚至更高温度下操作，通常超过1000℃。由于没有可在这些温度下工作的已知的实用金属或合金，需要复杂和贵重的耐火材料衬里的反应器和高压废热锅炉来骤冷&冷却合成气流出物。再者，这些高压操作需要相当大的资本费用和大量能源来压缩氧气或空气。所以，由于涉及的高温和压力，合成气技术成本高，产生高成本的甲醇产品，这就限制它的更高价值的应用，例如作为化工原料和溶剂。此外，合成气的生产在热力学和化学上是低效的，产生大为过量的废热和不需要的二氧化碳，这易于降低整个生产的转化效率。还可应用费-托气-液(GTL)技术将合成气转化为重质液态烃，但是该方法的投资费用甚至更高。在每种情况下，合成气的生产占到这些甲烷转化方法的资本费用的大部分。 
人们提出了关于常规生产合成气作为生产甲醇或合成液态烃的途径的很多备选方法。然而，迄今这些备选方法由于各种原因都没有达到工业规模。一些以前的备选的现有技术方法，例如授予Miller的美国专利号5,243,098或5,334,777启示了，将低级烷烃(例如甲烷)，与金属卤化物反应而生成金属卤化物(metalous halide)和氢卤酸，它们又被氧化镁还原而生成相应的醇。但是，应用氯作为优选的卤素将甲烷卤化导致生成单甲基卤(CH3Cl)的差选择性，生成不需要的副产物例如CH2Cl2和CHCl3，它们难于转化或者要求苛刻地限制单程转化率从而要求很高的循环率。 
其它现有技术方法提出甲烷的催化氯化或溴化作为生产合成气(CO和H2)的备选方法。为了改善生产甲醇的整体方法中甲烷卤化步 骤的选择性，授予Miller的美国专利号5,998,679启示了通过金属溴化物的热分解产生的溴的应用，即，用来在过量的烷烃存在下将烷烃溴化，这导致至单卤代中间体例如甲基溴的改善的选择性。为了避免利用移动的固体的流化床的缺点，该方法利用金属氯化物水合物和金属溴化物的循环液体混合物。授予Grosso的美国专利号6,462,243B1、US 6,472,572 B1和US 6,525,230中描述的方法也都能通过应用溴化反应达到至单卤代中间体的更高的选择性。通过在移动的固体的循环床中与金属氧化物反应，将生成的烷基溴化物中间体例如甲基溴进一步转化为相应的醇和醚。美国专利号6,525,230的另一个实施方案通过利用分四步循环操作的包含金属氧化物/金属溴化物的固定床的分段反应器避免了移动床的缺点。这些方法往往还产生大量的甲醚(DME)和任何醇。虽然DME是有前景的柴油机燃料替代物，但是迄今为止，目前还没有DME的实际市场，所以将需要额外的昂贵的催化法转化步骤将DME转化为当前市场化产品。还提出了其它方法，它们无需生产合成气，例如授予Olah的美国专利号4,655,893和4,467,130，其中，应用超强酸催化剂通过催化缩合将甲烷催化缩合成汽油沸程的烃。但是，这些早期的备选方法中没有一种形成了工业过程。 
已知可以在各种形式的晶态铝硅酸盐(也称为沸石)上将取代的烷烃，特别是甲醇，转化为烯烃和汽油沸程的烃。在甲醇转化为汽油(MTG)的方法中，应用择形沸石催化剂ZSM-5将甲醇转化为汽油。于是可应用常规技术将煤或甲烷气转化为甲醇，随后转化为汽油。但是，由于甲醇生产的高成本，在现有的或预计的汽油价格下，认为MTG法在经济上不可行。所以，需要将见于天然气的甲烷和其它烷烃转化为烯烃和较高分子量的烃的经济方法，由于它们的更高密度和价值，运输它们就更经济，从而显著地有助于开发遥远的天然气贮量。还需要转化天然气中存在的烷烃的方法，该方法成本降低，操作安全而简单。 
发明概述 
为了实现前述和其它目标，而且按照本发明的目的，如本文体现的和概述的，本发明的一个特征在于将气态烷烃转化为烯烃的方法。将具有较低分子量烷烃的气态进料与溴蒸气反应而生成烷基溴化物和氢溴酸。然后，在合成的晶态铝硅酸盐催化剂存在下且在足以生成烯烃和氢溴酸蒸气的温度下，使所述烷基溴化物和氢溴酸反应。
本发明的另一个特征在于，提供了将较低分子量的气态烷烃转化为烯烃的方法，它包括，将含有较低分子量烷烃的气态进料与溴蒸气反应而生成烷基溴化物和氢溴酸。然后，在合成的晶态铝硅酸盐催化剂存在下，使所述烷基溴化物和氢溴酸反应而生成烯烃和氢溴酸。该方法还包含将氢溴酸转化为溴。 
本发明的又一个特征在于，提供了将气态烷烃转化为烯烃的方法。将具有较低分子量烷烃的气态进料与溴蒸气反应而生成烷基溴化物和氢溴酸。在合成的晶态铝硅酸盐催化剂存在下且在足以生成烯烃和氢溴酸蒸气的温度下，使所述烷基溴化物与氢溴酸反应。通过将所述氢溴酸蒸气与金属氧化物反应生成金属溴化物和水蒸汽，而从所述烯烃中除去氢溴酸蒸气。 
附图简述 
并入本说明书并且构成本说明书的一部分的附图阐释了本发明的实施方案，并且与描述一起解释本发明的原理。 
在图中： 
图1是本发明方法的简化方块流程图； 
图2是本发明方法的一个实施方案的示意图； 
图3是本发明方法的另一个实施方案的示意图； 
图4A是本发明方法的又一个实施方案的示意图； 
图4B是图4A中阐释的本发明方法实施方案的示意图，它描绘了在氧化阶段用氧气代替空气时可应用的备选操作方案； 
图5A是图4A中阐释的本发明方法实施方案的示意图，其中通过金属氧化物床的流动被改变了方向； 
图5B是图5A中阐释的本发明方法实施方案的示意图，它描绘了在氧化阶段用氧气代替空气时可应用的备选操作方案； 
图6A是本发明方法的另一个实施方案的示意图； 
图6B是图6A中阐释的本发明方法实施方案的示意图，它描绘了在氧化阶段用氧气代替空气时可应用的备选操作方案； 
图7是本发明方法的另一个实施方案的示意图； 
图8是图7中阐释的本发明方法实施方案的示意图，其中通过金属氧化物床的流动被改变了方向；以及 
图9是本发明方法的另一个实施方案的示意图。 
对优选实施方案的详细描述 
如本说明书中应用的术语“较低分子量的烷烃”表示甲烷、乙烷、丙烷、丁烷、戊烷或其混合物。还如本说明书中应用的术语“烷基溴化物”表示一、二和三溴代的烷烃。还有，如图2和3中阐释的本发明方法的实施方案的管道11和111中的原料气各自优选是天然气，可处理它以除去硫化合物和二氧化碳。在任何情况下，重要的是要注意，在本发明方法的原料气中可以允许少量的二氧化碳，例如少于约2mol％。 
图1中显示了总体上描绘本发明方法的方块流程图，而本发明方法的具体的实施方案阐释于图2和3中。参照图2，经由管线、管道或导管62输送或传送由原料气加循环气流的混合物构成的、压力在约1巴至约30巴范围内、含有较低分子量烷烃的气流，与经由管线25和泵24输送的干燥溴液体混合后被送到热交换器26，其中将液溴蒸发。较低分子量的烷烃和干燥溴蒸气的混合物被进料入反应器30。优选地，导入反应器30的混合物中较低分子量烷烃与干燥溴蒸气的摩尔比超过2.5∶1。反应器30具有一个入口预热器区28，它将所述混合物加热到约250℃至约400℃范围内的反应引发温度。 
在第一反应器30内，在约250℃至约600℃范围内的较低温度下，以及在约1巴至约30巴范围内的压力下，较低分子量的烷烃与干燥溴 蒸气发生放热反应而产生气态烷基溴化物和氢溴酸蒸气。由于溴化反应的放热性质，操作温度范围的上限大于将进料混合物被加热至的反应引发温度范围的上限。就甲烷来说，根据下列一般反应，发生甲基溴的形成： 
CH4(g)+Br2(g)→CH3Br(g)+HBr(g) 
以对于甲基溴的相当高程度的选择性发生该反应。例如，就甲烷的溴化来说，约4.5∶1的甲烷对溴的比率增大了对一卤化甲基溴化物的选择性。在溴化反应中还生成少量二溴甲烷和三溴甲烷。更高级烷烃例如乙烷、丙烷和丁烷，也容易被溴化，产生单和多溴代的物质例如乙基溴化物、丙基溴化物和丁基溴化物。如果应用显著小于约2.5∶1的烷烃对溴的比率，就出现对甲基溴的更低选择性，观察到不希望的碳黑的显著形成。此外，进料入第一反应器30的干燥溴蒸气基本上是无水的。申请人已经发现，从第一反应器30中的溴化步骤除去基本上全部水蒸汽，大体上排除了不需要的二氧化碳的生成，于是提高了烷烃溴化生成烷基溴化物的选择性，并且消除了从烷烃生成二氧化碳时产生的大量废热。 
经由管线31从第一反应器抽出含有烷基溴化物和氢溴酸的流出物，并且在流到第二反应器34以前，在热交换器32中部分地冷却到约150℃至约450℃范围内的温度。在第二反应器34中，在从约250℃至约500℃的温度范围，以及在约1巴至20巴范围内的压力下，在晶态铝硅酸盐催化剂(优选是沸石催化剂，而最优选是X型或Y型沸石催化剂)的固定床33上使烷基溴化物进行放热反应。优选的沸石是10X或Y型沸石，不过对于技术人员而言显而易见的是，在本发明的方法中可应用通过改变铝硅比而合成的、具有不同孔径和酸度的其它沸石。虽然优选应用呈质子形式、钠形式或者混合的质子/钠形式的沸石催化剂，所述沸石还可通过离子交换来修饰，即，用其它碱金属阳离子，例如Li、K或Cs，用碱土金属阳离子，例如Mg、Ca、Sr或Ba， 或者用过渡金属阳离子，例如Ni、Mn、V、W，或者变成氢形式。这些不同的备选阳离子具有转变反应选择性的效果。对于技术人员而言显而易见的是，在第二反应器34中可应用通过改变铝硅比而合成的、具有不同孔径和酸度的其它沸石催化剂。在该反应器中，使烷基溴化物反应而产生烯烃和各种较高分子量的烃的混合物，以及额外的氢溴酸蒸气。 
在确定生成烯烃和各种较高分子量烃的反应的选择性时，第二反应器34的操作温度是一个重要参数。优选在约250℃至500℃范围内的温度下操作第二反应器34。第二反应器内高于约450℃的温度导致轻质烃例如不需要的甲烷的产率提高，还有焦炭的沉积，而更低温度则提高乙烯、丙烯、丁烯和更重分子量烃产品的产率。还应注意，在更低温度范围内，相对于甲基氯或其它取代的甲基化合物例如甲醇来说，甲基溴似乎活性更大。值得注意的是，就烷基溴化物在优选的10X沸石催化剂上的反应来说，还发生环化反应，致使C7+馏分含有大量取代的芳烃。在接近400℃的升高的温度下，甲基溴转化率提高到90％或更大，但是向C5+产品的选择性降低，而向轻质产品、特别是烯烃的选择性提高。在高于550℃的温度下，出现甲基溴至甲烷和碳质、焦炭的高转化率。在约300℃和450℃之间的优选的操作温度范围内，作为反应的副产物，在操作中随时间将在催化剂上积聚更少量的焦炭，引起在数小时至数百小时范围内催化剂活性的下降，这取决于反应条件和原料气的组成。认为与甲烷的生成相关的、高于约400℃的更高反应温度，有利于烷基溴化物的热裂化以及碳或焦炭的形成，于是增大催化剂灭活的速率。反之，在所述范围下限、特别是低于约300℃的温度，也可能由于重质产品从催化剂解吸速率减小而有助于结焦。所以，在第二反应器34内约250℃至约500℃范围内，但是优选在约300℃至约450℃范围内的操作温度，解决了所需烯烃和C5+产品的提高的选择性以及更低的由于碳形成导致灭活的速率与更高的单程转化率之间的矛盾，这使需要的催化剂的量、循环速率和设备尺寸最小化。 
可以定期地将催化剂就地再生，即，使反应器34与常规工艺流隔离，在从约1巴至约5巴范围内的压力下，在约400℃至约650℃范围内的升高温度下，经由管线70用惰性气体吹扫，从而在实际可行的范围内除去催化剂上吸附的未反应的物质，然后通过在约1巴至约5巴范围内的压力下，在约400℃至约650℃范围内的升高温度下，经由管线70往反应器34中添加空气或惰性气体稀释的氧，将沉积的碳氧化为CO2。在再生过程中经由管线75从反应器34中排出二氧化碳和残余的空气或惰性气体。
经由管线35从第二反应器34中抽出包含烯烃、较高分子量的烃和氢溴酸的流出物，在交换器36中冷却到0℃至约100℃范围内的温度，并且与管线12内的来自烃汽提塔47的蒸气流出物合并，所述蒸气流出物含有原料气和通过与烃汽提塔47中的原料气接触而汽提出的残余烃。将合并的蒸气混合物转入涤气器38并且与浓缩的部分氧化金属溴化物盐的水溶液接触，该溶液包含通过泵42经由管线41被输送到涤气器38的金属氢氧化物和/或金属氧化物和/或金属氧-溴化物。所述溴化物盐的优选的金属是Fe(III)、Cu(II)或Zn(II)，或其混合物，因为这些金属不太昂贵并且在约120℃至约180℃范围内的较低温度下容易氧化，允许使用玻璃内衬的或含氟聚合物内衬的设备；不过在本发明的方法中还可应用Co(II)、Ni(II)、Mn(II)、V(II)、Cr(II)或形成可氧化的溴化物盐的其它过渡金属。备选地，可应用也形成可氧化的溴化物盐的碱土金属，例如Ca(II)或Mg(II)。可撇取在涤气器38内冷凝的任何液态烃，在管线37中抽出并加到管线54中的离开产品回收单元52的液态烃中。将氢溴酸溶于水溶液并被金属氢氧化物和/或金属氧化物和/或金属氧-溴化物中和，生成金属溴化物盐的溶液和水，经由管线44将它从涤气器38除去。 
经由管线39将作为流出物从涤气器38取出的含有烯烃和较高分子量的烃的残余蒸气相运送到脱水器50，经由管线53从蒸气流脱除基本上所有的水。然后经由管线53从脱水器50除去水。进一步经由管线51将包含烯烃和较高分子量烃的干燥蒸气流通入产品回收单元52，由管线54作为液体产品回收烯烃和C5+汽油沸程烃馏分。在本发明的方法中可以使用对于技术人员而言显而易见的任何常规脱水和液体回收的方法，如用于加工天然气或炼油厂气流以及用于回收烯烃的方法，例如固体床干燥剂吸附后接着冷冻冷凝，深冷膨胀，或者循环吸收油或其它溶剂。然后将来自产品回收单元52的残余蒸气流出物分离为可用作工业用燃料的吹扫气流57以及经压缩机58压缩的再循环残余蒸气。从压缩机58排出的再循环残余蒸气被分为两部分。经由管线62输送等于原料气摩尔体积的至少2.5倍的第一部分，并且与通过泵24传送的干燥液溴合并，在交换器26内加热将溴蒸发后进料入第一反应器30。经由管线63将第二部分从管线62抽出并且通过控制阀60调节流速，即，调节后的流速足以稀释导入反应器34的烷基溴浓度和吸收反应热以致反应器34保持在选定的操作温度，优选在约300℃至约450℃范围内，以便使转化率对选择性最大化并且使由于碳沉积引起的催化剂灭活速率最小化。所以，由再循环的蒸气流出物提供的稀释作用，除了调节第二反应器34中的温度以外，还可使第一反应器30中的溴化选择性受到控制。 
经由管线44将从涤气器38脱除的含金属溴化物盐的水溶液通入烃汽提塔47，其中，通过与经由管线11输入的入流原料气接触而从水相汽提残余的溶解的烃。经由管线65从烃汽提塔47输送汽提的水溶液，在热交换器46内冷却到约0℃至约70℃范围内的温度，随后通入吸收器48，其中，从管线67中的放空物流中回收残余溴。经由管线49将从涤气器48流出的水溶液输送到热交换器40供预热到约100℃至约600℃范围内，而最优选约120℃至约180℃范围内的温度，再流入第三反应器16。通过鼓风机或压缩机13经由管线10以约常压至约5巴范围内的压力将氧气或空气运送到溴汽提塔14而从水中汽提残余的溴，水是经由管线64从汽提塔14脱除的，与来自脱水器50的水流53合并后形成管线56中的废水流，将它从工艺中除去。经由管线15将离开溴汽提塔14的氧气或空气送入反应器16，它在约常压至约5巴范围内的压力和在约100℃至约600℃范围内，但是最优选在约120℃至约180℃范围内的温度下操作，以便氧化金属溴化物盐的水溶液 而生成单质溴与金属氢氧化物和/或金属氧化物和/或金属氧-溴化物。如上所述，虽然可应用Co(II)、Ni(II)、Mn(II)、V(II)、Cr(II)或形成可氧化的溴化物盐的其它过渡金属，但是溴化物盐的优选的金属是Fe(III)、Cu(II)或Zn(II)，或其混合物，因为这些金属不太昂贵并且容易在约120℃至约180℃范围内的较低温度下被氧化，允许使用玻璃内衬的或含氟聚合物内衬的设备。备选地，可应用也形成可氧化的溴化物盐的碱土金属例如Ca(II)或Mg(II)。 
氢溴酸与这样生成的金属氢氧化物和/或金属氧化物和/或金属氧-溴化物反应，再次生成金属溴化物盐和水。反应器16中的热交换器18提供热量以蒸发水和溴。所以，总反应导致在第一反应器30和第二反应器34中产生的氢溴酸的净氧化，生成单质溴和液相中的蒸汽，由在催化循环中操作的金属溴化物/金属氧化物或金属氢氧化物催化。在所述金属溴化物是Fe(III)Br3的情况下，认为反应是： 
1)Fe(+3a)+6Br(-a)+3H(+a)+3/2O2(g)＝3Br2(g)+Fe(OH)3 
2)3HBr(g)+H2O＝3H(+a)+3Br(-a)+H2O 
3)3H(+a)+3Br(-a)+Fe(OH)3＝Fe(+3a)+3Br(-a)+3H2O 
在冷凝器20内，在约0℃至约70℃范围内的温度和在约常压至约5巴范围内的压力下，冷却作为蒸汽经由管线19从第三反应器16的出口离开的单质溴和水和任何残余的氧或氮(如果将空气用作氧化剂)，从而冷凝溴和水再通入三相分离器22。在三相分离器22中，由于液态水对溴具有有限的溶解度，相当于约3重量％，所以冷凝的任何额外的溴都形成单独的、较密的液溴相。但是，液溴相具有对水显著更低的溶解度，相当于小于0.1％。所以，可轻易通过下列方式获得基本上干燥的溴蒸气，即，将液溴和水冷凝，通过简单的物理分离滗去水，随后将液溴再蒸发。 
经过泵24将管线25中的液溴从三相分离器22泵至足以与蒸气流62混合的压力。于是在该工艺中回收和再循环溴。残余的氧或氮和没有冷凝的任何残余溴蒸气从三相分离器22排出后经由管线23通入溴涤气器48，其中，通过溶解入金属溴化物水溶液流65中还原的金属 溴化物和通过与其反应而回收残余的溴。经由管线27从分离器22除去水并且导入汽提塔14。 
在本发明另一个实施方案中，参照图3，经由管线、管道或导管162输送或传送由原料气加循环气流的混合物构成的、压力在约1巴至约30巴范围内、含有较低分子量烷烃的气流，与经由泵124输送的干燥溴液体混合后被送到热交换器126，其中，液溴被蒸发。较低分子量的烷烃和干燥溴蒸气的混合物被进料入反应器130。优选地，导入反应器130的混合物中较低分子量烷烃与干燥溴蒸气的摩尔比大于2.5∶1。反应器130具有一个入口预热器区128，它将所述混合物加热到约250℃至约400℃范围内的反应引发温度。在第一反应器130内，在约250℃至约600℃范围内的较低温度下，以及在约1巴至约30巴范围内的压力下，将较低分子量的烷烃与干燥溴蒸气反应而产生气态烷基溴化物和氢溴酸蒸气。由于溴化反应的放热性质，操作温度范围的上限大于进料混合物被加热到的反应引发温度范围的上限。就甲烷来说，根据下列一般反应，发生甲基溴的形成： 
CH4(g)+Br2(g)→CH3Br(g)+HBr(g) 
以对于甲基溴的显著高程度的选择性发生该反应。例如，当溴与摩尔过量的甲烷以4.5∶1的甲烷与溴的比率反应时，出现了对于一卤化的甲基溴化物的高选择性。在溴化反应中还生成少量二溴甲烷和三溴甲烷。更高级烷烃例如乙烷、丙烷和丁烷，也容易被溴化，产生单和多溴代的物质例如乙基溴化物、丙基溴化物和丁基溴化物。如果应用显著小于2.5∶1的烷烃与溴的比率，就大致出现对甲基溴的显著更低的选择性，观察到不希望的碳黑的显著形成。此外，进料入第一反应器130的干燥溴蒸气基本上是无水的。申请人已经发现，从第一反应器130中的溴化步骤除去基本上全部水蒸汽大体上排除了不需要的二氧化碳的生成，于是提高了烷烃溴化生成烷基溴化物的选择性，并且消除从烷烃生成二氧化碳时产生的大量废热。 
经由管线131从第一反应器130抽出含有烷基溴化物和氢溴酸的流出物，并且在流到第二反应器134以前，在热交换器132中部分地冷却到约150℃至450℃范围内的温度。在第二反应器134中，在从约250℃至约500℃范围内的温度下，以及在约1巴至30巴范围内的压力下，在晶态铝硅酸盐催化剂(优选是沸石催化剂、而最优选是X型或Y型沸石催化剂)的固定床133上使烷基溴化物进行放热反应。优选的沸石是10X或Y型沸石，不过对于技术人员而言显而易见的是，在本发明的方法中可应用通过改变铝硅比而合成的、具有不同孔径和酸度的其它沸石。虽然优选应用呈质子形式、钠形式或者混合的质子/钠形式的沸石催化剂，例如Li、K或Cs，用碱土金属阳离子，例如Mg、Ca、Sr或Ba，或者用过渡金属阳离子，例如Ni、Mn、V、W，或者变成氢形式。这些不同的备选阳离子具有转变反应选择性的效果。对于技术人员而言显而易见的是，在第二反应器134中可应用通过改变铝硅比而合成的、具有不同孔径和酸度的其它沸石催化剂。在该反应器中，将烷基溴化物反应而产生烯烃和较高分子量的烃的混合物，以及额外的氢溴酸蒸气。 
在确定生成烯烃和各种较高分子量液态烃的反应的选择性时，第二反应器134的操作温度是一个重要的参数。优选在约250℃至500℃范围内，但是更优选在约300℃至450℃范围内的温度下操作第二反应器134。第二反应器内高于约450℃的温度导致轻质烃例如不需要的甲烷的产率增大，还产生碳质焦炭，而更低温度则提高烯烃例如乙烯、丙烯和丁烯和更重分子量烃产品的产率。值得注意的是，就在优选的10X沸石催化剂上反应的烷基溴化物来说，还发生环化反应，致使产生的C7+馏分包含大量取代的芳烃。在接近400℃的升高的温度下，甲基溴转化率提高到90％或更大，但是对C5+产品的选择性降低，而对轻质产品、特别是烯烃的选择性提高。在高于550℃的温度下，发生甲基溴几乎完全转化为甲烷和焦炭。在约300℃至450℃的优选的操作温度范围内，作为反应的副产物，在操作中随时间将在催化剂上积聚少量的碳，引起在数百小时范围内催化剂活性的下降，这取决于反应 条件和原料气的组成。观察到，高于约400℃的较高反应温度有利于烷基溴化物热裂化而形成碳，于是提高催化剂灭活的速率。反之，在所述温度范围下限、特别是低于约300℃下操作也可能促进结焦，可能由于烃产品解吸速率的降低。所以，在第二反应器134内约250℃至500℃、但是更优选在约300℃至450℃范围内的操作温度，解决了所需烯烃和C5+产品的提高的选择性以及更低的由于碳形成引起灭活的速率与更高的单程转化率之间的矛盾，这使所需要的催化剂的量、循环速率和设备尺寸最小化。 
可以定期地将催化剂就地再生，即，使反应器134与正常工艺流隔离，在约1巴至约5巴范围内的压力下，在400℃至650℃范围内的升高的温度下，经由管线170用惰性气体吹扫，从而在实际可行的范围内除去催化剂上吸附的未反应的物质，然后通过在约1巴至约5巴范围内的压力下，在400℃至650℃范围内的升高的温度下，经由管线170往反应器134中添加空气或惰性气体稀释的氧，将沉积的碳氧化为CO2。在再生过程中经由管线175从反应器134中排出二氧化碳和残余的空气或惰性气体。 
经由管线135从第二反应器134中抽出包含烯烃、更高分子量的烃和氢溴酸的流出物，在交换器136中冷却到约0℃至约100℃范围内的温度，并且与管线112内来自烃汽提塔147的蒸气流出物合并。然后将该混合物通到涤气器138并且与通过任何合适的装置例如泵143经由管线164输送到涤气器138并且在热交换器155内冷却到约0℃至约50℃范围内的温度的汽提的、再循环的水接触。可撇取在涤气器138内冷凝的任何液态烃产品并且作为物流137抽出后加到液态烃产品154中。将氢溴酸溶于涤气器138中水溶液中，经由管线144将它从涤气器138脱除，再通入烃汽提塔147，其中，溶于水溶液的残余的烃通过与原料气111接触而被汽提出来。来自烃汽提塔147的汽提的水相流出物在热交换器146内被冷却到约0℃至约50℃范围内的温度，然后经由管线165将它通入吸收器148，其中，从放空物流167回收残余的溴。 
从涤气器138作为流出物脱除包含烯烃和更高分子量烃的残余蒸气相，经由管线139将其送入脱水器150，从气流中脱除基本上所有的水。然后经由管线153从脱水器150除去水分。进一步经由管线151将包含烯烃和更高分子量的烃的干燥气流通入产品回收单元152，作为管线154中的液体产品回收烯烃和C5+汽油沸程烃馏分。在本发明的实施中可应用技术人员已知的任何常规脱水和液体回收的方法，如用于加工天然气或炼油厂气流以及用于回收烯烃的方法，例如固体床干燥剂吸附后接着例如冷冻冷凝，深冷膨胀，或者循环吸收油或其它溶剂。然后将来自产品回收单元152的残余蒸气流出物分离为可用作工艺用燃料的吹扫气流157以及经压缩机158压缩的再循环残余蒸气。从压缩机158排出的再循环残余蒸气被分为两部分。经由管线162输送等于原料气体积的至少2.5倍的第一部分，与管线125中传送的液溴合并，通入热交换器126内，其中，将液溴蒸发后进料入第一反应器130。经由管线163将第二部分从管线162抽出并且通过控制阀160调节流速，即，调节后的流速足以稀释导入反应器134的烷基溴浓度和吸收反应热以致反应器134被保持在选定的操作温度，优选在约300℃至约450℃范围内，以便使转化率对选择性最大化并且使由于碳沉积引起的催化剂灭活的速率最小化。所以，除了调节第二反应器134中的温度之外，由再循环的蒸汽流出物提供的稀释还可使第一反应器130中溴化的选择性受到控制。 
通过鼓风机或压缩机113以约常压至约5巴范围内的压力将氧气、富含氧气的空气或空气110送入溴汽提塔114而从水中汽提残余的溴，水是经由管线164从汽提塔114脱除的，它被分为两部分。经由管线164将汽提的水的第一部分再循环，在热交换器155内冷却到约20℃至约50℃范围内的温度，并且保持在足以通过任何合适的装置例如泵143进入涤气器138的压力。选定再循环的部分水，以致经由管线144从涤气器138脱除的氢溴酸溶液流出物的浓度在从约10重量％至约50重量％氢溴酸的范围内，但是更优选在约30重量％至约48重量％的范围内，从而将必须在交换器141和预热器119内蒸发的水的量减到最小，以及使生成的酸上方的HBr蒸汽压减到最小。从管线164和经由管线156的操作从汽提塔114除去第二部分水。 
经由管线149输送含于来自涤气器148的水溶液流出物中的溶解的氢溴酸，与管线115中离开溴汽提塔114的氧气、富含氧气的空气或空气合并。让合并后的水溶液流出物和氧气、富含氧气的空气或空气进入热交换器141的第一侧和流过预热器119，其中，将混合物预热到约100℃至约600℃范围内，而最优选约120℃至约180℃范围内的温度，随后送入装有金属溴化物盐或金属氧化物的第三反应器117。所述溴化物盐或金属氧化物的优选的金属是Fe(III)，Cu(II)或Zn(II)，不过还可应用Co(II)、Ni(II)、Mn(II)、V(II)、Cr(II)或形成可氧化的溴化物盐的其它过渡金属。备选地，可应用也形成可氧化的溴化物盐的碱土金属，例如Ca(II)或Mg(II)。氧化反应器117中的金属溴化物盐可作为浓缩的水溶液应用，或者优选地，可将该浓缩的水性盐溶液吸收入多孔的、高表面积的、耐酸的惰性载体例如硅胶。更优选地，将10至20重量％范围内的氧化物形式的金属沉积在惰性载体上，例如具有50至200m2/g范围内的比表面积的氧化铝上。氧化反应器117在约常压至约5巴范围内的压力和在约100℃至约600℃范围内，但最优选约120℃至约180℃范围内的温度下操作；此处，金属溴化物被氧所氧化，生成单质溴和金属氢氧化物，金属氧化物或金属氧-溴化物物质，或者在负载的金属溴化物盐的情况下生成几种金属氧化物，或者在更高温度和更低压力下操作时生成金属氧化物，此时，水可能主要以蒸气形式存在。在任一情况下，氢溴酸与金属氢氧化物、金属氧-溴化物或金属氧化物反应而被中和，再生金属溴化物盐和生成水。所以，总的反应导致在第一反应器130和第二反应器134中产生的氢溴酸的净氧化而生成单质溴和蒸汽，由催化循环中操作的金属溴化物/金属氢氧化物或金属氧化物催化。当所述金属溴化物是水溶液中的Fe(III)Br2，并且在水可能呈液态存在的压力和温度范围内操作时，认为反应是： 
1)Fe(+3a)+6Br(-a)+3H(+a)+3/2O2(g)＝3Br2(g)+Fe(OH)3
2)3HBr(g)+H2O＝3H(+a)+3Br(-a)+H2O 
3)3H(+a)+3Br(-a)+Fe(OH)3＝Fe(+3a)+3Br(-a)+3H2O 
当所述金属溴化物是负载在惰性载体上的Cu(II)Br2，并且在水可能主要以蒸气形式存在的更高温度和更低压力条件下操作时，认为反应是： 
1)2Cu(II)Br2＝2Cu(I)Br+Br2(g) 
2)2Cu(I)Br+O2(g)＝Br2(g)+2Cu(II)O 
3)2HBr(g)+Cu(II)O＝Cu(II)Br2+H2O(g) 
以蒸气形式离开第三反应器117的出口的单质溴和水和任何残余的氧气或氮气(如果空气或富含氧气的空气用作氧化剂)，经由管线127输送并在交换器141的第二侧和冷凝器120中被冷却到约0℃至约70℃范围内的温度，其中，溴和水被冷凝后进入三相分离器122。在三相分离器122内，由于液态水对溴具有有限的溶解度，相当于约3重量％，所以任何冷凝的另外的溴都形成单独的、较密的溴相。但是，液溴相具有对水显著更低的溶解度，相当于小于0.1％。所以，可容易通过下列方法获得基本上干燥的溴蒸气，即，将液溴和水冷凝，通过简单的物理分离滗去水，随后将液溴再蒸发。重要的是在导致HBr几乎完全反应的条件下操作，从而避免冷凝的液溴和水中较大量残余的HBr，因为HBr增大溴在水相中的混溶性，以及在足够高的浓度下，导致单一的三元液相。 
经由泵124将液溴从三相分离器122泵送到足以与蒸气流162混合的压力。于是在该工艺中回收和再循环溴。残余的空气、富含氧的空气或氧气和任何没有冷凝的溴蒸气从三相分离器122出来后经由管线123通入溴涤气器148，其中，通过溶于经由管线165传送到涤气器148的氢溴酸溶液流中而回收残余的溴。经由管线129从三相分离器122除去水并且通入汽提塔114。 
所以，根据前述本发明的所有实施方案，在催化循环中操作金属溴化物/金属氢氧化物、金属氧-溴化物或金属氧化物，可使溴在该工艺中被轻易地再循环。在约100℃至约600℃范围内，而最优选在约120℃至约180℃范围内的温度下，金属溴化物容易被水相或蒸气相中的氧气、富含氧的空气或空气氧化，生成单质溴蒸气和金属氢氧化物、金属氧-溴化物或金属氧化物。在低于约180℃的温度下操作是有利的，于是能利用低成本、耐腐蚀的氟聚合物内衬的设备。通过与金属氢氧化物或金属氧化物的反应中和氢溴酸，生成水蒸气和金属溴化物。 
单质溴蒸气和水蒸气被冷凝后容易通过简单的物理分离呈液相分离，生成基本上干燥的溴。不存在显著量的水就允许烷烃的选择性溴化而不产生CO2，以及后续烷基溴化物的高效和选择性的反应生成主要是C2至C4烯烃和更重的产品，它的C5+馏分包含大量支化的烷烃和取代的芳烃。使来自溴化反应和随后在反应器134内的反应的副产物氢溴酸蒸气轻易溶于水相而被金属溴化物的氧化生成的金属氢氧化物或金属氧化物中和。 
根据图4A中阐释的本发明方法的另一个实施方案，按照与前述关于图2和3描述的相应阶段基本上相似的方式操作烷基溴化反应和烷基溴化物转化阶段。更具体地说，分别经由管线、管道或导管262和211输送或传送由原料气加循环气流的混合物组成的、压力在约1巴至约30巴范围内、含有更低分子量烷烃的气流，并且与管线225内的干燥溴液体混合。经由泵224输送形成的混合物，通入热交换器226，其中，液溴被蒸发。更低分子量的烷烃和干燥溴蒸气的混合物被进料入反应器230。优选地，导入反应器230的混合物中更低分子量烷烃与干燥溴蒸气的摩尔比大于2.5∶1。反应器230具有一个入口预热器区228，它将所述混合物加热到250℃至400℃范围内的反应引发温度。在第一反应器230内，在约250℃至约600℃范围内的较低温度下，以及在约1巴至约30巴范围内的压力下，更低分子量的烷烃与干燥溴蒸气发生放热反应而产生气态烷基溴化物和氢溴酸蒸气。由于溴化反应的放热性质，操作温度范围的上限大于进料混合物被加热到的反应引发温度范围的上限。就甲烷来说，根据下列一般反应，发生甲基溴的形成： 
CH4(g)+Br2(g)→CH3Br(g)+HBr(g) 
以对于甲基溴的显著高程度的选择性发生该反应。例如，当溴与摩尔过量的甲烷以4.5∶1的甲烷与溴的比率反应时，出现了对于一卤化甲基溴化合物的高选择性。在溴化反应中还生成少量二溴甲烷和三溴甲烷。更高级烷烃例如乙烷、丙烷和丁烷，也容易被溴化，产生单和多溴代的物质例如乙基溴化物、丙基溴化物和丁基溴化物。如果应用显著小于2.5∶1的烷烃与溴的比率，就出现对甲基溴的显著更低的选择性，观察到显著形成不希望的碳黑。此外，进料入第一反应器230的干燥溴蒸气基本上是无水的。申请人已经发现，从第一反应器230中的溴化步骤除去基本上所有水蒸气大体上排除了不需要的二氧化碳的生成，于是提高了烷烃溴化生成烷基溴化物的选择性，并且消除了从烷烃生成二氧化碳时产生的大量废热。 
经由管线231从第一反应器230抽出包含烷基溴化物和氢溴酸的流出物，并且在流到第二反应器234以前，在热交换器232中部分地冷却到约150℃至450℃范围内的温度。在第二反应器234中，在从约250℃至约500℃范围内的温度下，以及在约1巴至30巴范围内的压力下，在晶态铝硅酸盐催化剂(优选是沸石催化剂，而最优选是X型或Y型沸石催化剂)的固定床233上使烷基溴化物进行放热反应。优选的沸石是10X或Y型沸石，不过对于技术人员显而易见的是，在本发明的方法中可应用通过改变铝硅比而合成的、具有不同孔径和酸度的其它沸石。虽然优选应用呈质子形式、钠形式或者混合的质子/钠形式的沸石催化剂，所述沸石还可通过离子交换来修饰，即，用其它碱金属阳离子，例如Li，K或Cs，用碱土金属阳离子，例如Mg，Ca，Sr或Ba，或者用过渡金属阳离子，例如Ni、Mn、V、W，来交换，或者变成氢形式。这些不同的备选阳离子具有转变反应选择性的效果。对于技术人员显而易见的是，在第二反应器234中可应用通过改变铝硅比而合成的、具有不同孔径和酸度的其它沸石催化剂。在该反应器中，使烷基溴化物反应而产生烯烃和各种更高分子量的烃与另外的氢溴酸蒸气的混合物。 
在确定生成烯烃和各种更高分子量的液态烃的反应选的择性时，第二反应器234的操作温度是一个重要参数。优选在约250℃至约500℃范围内，但是更优选在约300℃至约450℃范围内的温度下操作第二反应器234。第二反应器内高于约450℃的温度导致轻质烃例如不需要的甲烷的产率提高，还产生碳质焦炭，而更低温度则提高烯烃和更重分子量烃产品的产率。值得注意的是，就在优选的10X沸石催化剂上反应的烷基溴化物来说，还发生环化反应，致使产生的C7+馏分包含大量取代的芳烃。在接近400℃的升高的温度下，甲基溴转化率提高到90％或更大，但是对C5+产品的选择性降低，而对轻质产品、特别是烯烃的选择性提高。在高于550℃的温度下，发生甲基溴几乎全部转化为甲烷和焦炭。在约300℃至450℃的优选的操作温度范围内，作为反应的副产物，在操作中随时间将在催化剂上积聚少量的碳，引起在数百小时范围内催化剂活性的下降，这取决于反应条件和原料气的组成。观察到，高于约400℃的更高反应温度有利于烷基溴化物热裂化而形成碳，于是增大催化剂灭活的速率。反之，在所述温度范围下限、特别是低于约300℃的温度下操作也可能促进结焦，可能由于烃产品解吸的速率减小。所以，在第二反应器234内约250℃至500℃、但是更优选在约300℃至450℃范围内的操作温度，解决了向所需烯烃和C5+产品的提高的选择性以及更低的由于碳形成引起的灭活的速率与更高的单程转化率之间的矛盾，这使需要的催化剂的量、循环速率和设备尺寸最小化。 
可以定期地将催化剂就地再生，即，通过使反应器234与正常工艺流隔离，在约1巴至约5巴范围内的压力下，在约400℃至约650℃范围内的升高的温度下，经由管线270用惰性气体吹扫，从而在实际可行的范围内除去催化剂上吸附的未反应的物质，然后通过在约1巴至约5巴范围内的压力下，在约400℃至约650℃范围内的升高的温度下，经由管线270往反应器234中添加空气或惰性气体稀释的氧，将沉积的碳氧化为CO2。在再生过程中经由管线275从反应器234中排出二氧化碳和残余的空气或惰性气体。 
经由管线235从第二反应器234中抽出包含烯烃、更高分子量烃和氢溴酸的流出物，在交换器236中冷却到约100℃至约600℃范围内的温度。如图4A中所述，经由管线235和241输送冷却的流出物，阀238位于开启位置而阀239和243处于关闭位置，导入包含固相金属氧化物的床298的容器或反应器240。所述金属氧化物的金属选自镁(Mg)、钙(Ca)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Sn)或锡(Sn)。选择金属时考虑它的物理性质和热力学性质相对于所需操作温度的影响，还考虑可能的环境和健康的影响与成本。优选地，将镁、铜和铁用作所述金属，而镁是最优选的。这些金属具有不但生成氧化物，还生成溴化物盐的性质，在小于约500℃的温度范围内的反应是可逆的。优选将固体金属氧化物固定在合适的耐磨载体上，例如合成的无定形二氧化硅，例如Davison Catalysts ofColumbia，Maryland生产的Davicat Grade 57。或者更优选地，具有约50至200m2/g的比表面积的氧化铝载体。在反应器240中，氢溴酸与金属氧化物在低于约600℃，优选在约100℃和约500℃之间的温度下按照下列通式反应，其中，M表示所述金属： 
               2HBr+MO→MBr2+H2O 
该反应产生的水蒸汽与烯烃和高分子量的烃一起在管线244、218和216中经开启的阀219输送到热交换器220中，其中，将混合物冷却到约0℃至约70℃范围内的温度。冷却后的混合物被运送到脱水器250，从气流中脱除基本上全部水分。然后经由管线253从脱水器250除去水分。进一步经由管线251将包含烯烃和更高分子量的烃的干燥气流通入产品回收单元252，作为管线254中的液体产品回收烯烃和C5+馏分。在本发明的实施中可应用对于技术人员而言显而易见的任何常规脱水和液体回收的方法，如用于加工天然气或炼油厂气流以及用于回收烯烃的方法，例如固体床干燥剂吸附后接着例如冷冻冷凝，深冷膨胀，或者循环吸收油或其它溶剂。然后将来自产品回收单元252的残余蒸气流出物分离为可用作工艺用燃料的吹扫气流257以及经压缩机258压缩的再循环残余蒸气。从压缩机258排出的再循环残余蒸 气被分为两部分。经由管线262输送等于原料气体积的至少1.5倍的第一部分，与液溴和经由管线225传送的进料气合并，通入热交换器226内，其中，按照前述方法将液溴蒸发后进料入第一反应器230。经由管线263将第二部分从管线262抽出并且通过控制阀260调节流速，即，调节后的流速足以稀释导入反应器234的烷基溴浓度和吸收反应热以致反应器234保持在选定的操作温度，优选在约300℃至约450℃范围内，以便使转化率对选择性最大化并且使由于碳沉积引起的催化剂灭活的速率最小化。所以，除了调节第二反应器234中的温度以外，由再循环的蒸气流出物提供的稀释还可使第一反应器230中溴化的选择性受到控制。 
通过鼓风机或压缩机213以约常压至约10巴范围内的压力将氧气、富含氧气的空气或空气210运送到与经由管线214、管线215和阀249输送的溴结合，通过热交换器215，其中，将氧气、富含氧气的空气或空气预热到约100℃至约500℃范围内的温度，输送到包含固相金属溴化物的床299的第二容器或反应器246。氧与所述金属溴化物按照下列一般反应进行反应，其中，M表示所述金属： 
                MBr2+1/2O2→MO+Br2
按照该方式，生成了干燥的、基本不含HBr的溴蒸气，于是不需后续的水或氢溴酸与液溴的分离。反应器246在低于600℃，而更优选在约300℃和约500℃之间操作。经由管线247、阀248和管线242将生成的溴蒸气从反应器246输送到热交换器或冷凝器221，其中，将溴冷凝成液体。经由管线242将液溴输送到分离器222，其中，经由管线225脱除液溴后通过任何合适的装置，例如通过泵224经由管线225输送到热交换器226和第一反应器230。经由管线227从分离器222将残余的空气或未反应的氧气输送到溴涤气装置223，例如文丘里涤气系统，它包含由技术人员选定的合适的溶剂或合适的固态吸附介质，其中，捕集残余的溴。通过加热或其它合适的方法将捕集的溴从涤气用溶剂或吸附剂中脱附，于是经由管线212将回收的溴输送到管线225。经由管线229排出洗涤过的空气或氧气。按这种方式，从本发明的系统除去氮气和任何其它基本上无活性的组分，于是不允许进入该操作工艺的含烃部分；还避免将溴损失到周围的环境中。
按照该实施方案通过化学反应而不是通过简单的物理溶解性除去HBr的一个优点是，在更高操作温度下基本上完全地消除HBr至低含量。另一个显著的优点是从脱除的溴中除去水，于是不需分离溴和水相，并且不需从水相汽提残余的溴。 
可按循环方式操作反应器240和246。如图4A中所示，阀238和219以开启方式操作使氢溴酸能从第二反应器234中抽出的流出物中除去，而阀248和249以开启方式操作使空气或富含氧的空气或氧气流过反应器246以氧化含于其中的固态金属溴化物。一旦发生反应器240和246中的金属氧化物和金属溴化物分别被显著转化，就关闭这些阀。此时，反应器246中的床299是基本固态的金属溴化物的床，而反应器240中的床298是基本固态的金属氧化物。如图5A中所示，然后开启阀245和243使氧气、富含氧的空气或空气流过反应器240以氧化含于其中的固态金属溴化物，而开启阀239和217使包含烯烃、更高分子量烃和从第二反应器234中抽出的氢溴酸的流出物经由管线237导入反应器246。按这种方式操作反应器直到发生反应器246和240中的金属氧化物和金属溴化物分别显著转化，随后通过如前述那样开启和关闭阀将反应器循环返回图4A中所示的示意流程。 
当氧用作氧化气体经由管线210输送到被用来氧化含于其中的固态金属溴化物的反应器时，可修饰图4A和5A中阐释的本发明方法的实施方案以致经由管线242和225将从反应器246(图4B)或240(图5B)产生的溴蒸气直接输送到第一反应器230。由于氧是反应性的，所以不会在系统中聚集，于是不需将溴蒸气冷凝成液体来除去非反应性的组分，例如氮气。在图4B和5B中没有阐释压缩机213，因为基本上所有商品化氧源，例如商品化空气分离器，将在要求的压力下对管线210提供氧气。如果不这样，对于技术人员而言显而易见的是，可应用压缩机213达到这样的压力。 
在图6A中阐释的本发明的实施方案中，将分别含于反应器240和246中的固态金属氧化物颗粒和固态金属溴化物颗粒的床流化后按下述方式连接以提供所述床的连续操作而不需提供设备，例如阀，来改变各反应器往来的流向。根据该实施方案，经由管线235从第二反应器234抽出包含烯烃、更高分子量的烃和氢溴酸的流出物，在交换器236中冷却到约100℃至约500℃范围内的温度，再导入包含固态金属氧化物颗粒的床298的反应器240的底部。随着氢溴酸与金属氧化物按前文图4A所述方式那样反应，该导入的流体的流动引起床298中的颗粒在反应器240内向上移动。在床298的顶部或附近，经溢流装置或旋风分离器或固体/气体分离的其它常规装置抽出由于固态金属氧化物与氢溴酸在反应器240内基本上完全的反应而包含耐磨载体上的基本上固态的金属溴化物的颗粒，在重力作用下流下管线259并且被导向反应器246中的固态金属溴化物颗粒的床299底部或底部附近。在图6A中阐释的实施方案中，通过鼓风机或压缩机213以约常压至约10巴范围内的压力运送氧气、富含氧气的空气或空气210，经由管线214输送通过热交换器215，其中，将氧气、富含氧气的空气或空气预热到约100℃至约500℃范围内的温度，再导入第二容器或反应器246中的固相金属溴化物的床299下方。氧与金属氧化物按前文图4A所述方式那样反应而生成干燥的、基本上不含HBr的溴蒸气。随着氧与金属溴化物反应，这种导入的气体的流动引起床299中的颗粒在反应器246内向上移动。在床298的顶部或附近，经溢流装置或旋风分离器或固体/气体分离的其它常规装置抽出由于固态金属溴化物与氧气在反应器246内基本上完全的反应而包含耐磨载体上的基本上固态的金属氧化物的颗粒，在重力作用下流下管线264并且被导向反应器240中的固态金属氧化物颗粒的床298底部或底部附近。这样，可连续操作反应器240和246而不用改变操作参数。 
在图6B中阐释的实施方案中，氧气被用作氧化气体并且经由管线210输送到反应器246。因此，修饰图6A中阐释的本发明方法的实施方案，以致经由管线242和225将从反应器246产生的溴蒸气直接输送到第一反应器230。由于氧气是有活性的，所以不会在系统中聚集， 于是不需将溴蒸气冷凝成液体来除去非反应性的组分，例如氮气。在图6B中没有阐释压缩机213，因为基本上所有的商品化氧源，例如商品化空气分离器，将在要求的压力下对管线210提供氧气。如果不这样，对于技术人员而言显而易见的是，可应用压缩机213达到这样的压力。 
按照图7中阐释的本发明方法的另一个实施方案，按照与关于图4A中详述的那些相应的阶段基本相似的方式操作烷基溴化和烷基溴化物转化阶段，不同点如下所述。经由管线247、阀248以及管线242和阀300将从反应器246释放的残余空气或氧气和溴蒸气输送到热交换器或冷凝器221，其中，将含溴气体冷却到约30℃至约300℃范围内的温度。然后经由管线242将含溴蒸气输送到包含呈还原价态的固相金属溴化物的床322的容器或反应器320。呈还原价态的金属溴化物的金属选自铜(Cu)、铁(Fe)或钼(Mo)。金属的选择考虑到与所需操作温度相关的物理和热力学性质的影响，以及可能的环境和健康影响和成本。优选地，将铜或铁用作所述金属，而铜是最优选的。优选将固体金属溴化物固定在合适的耐磨载体上，例如合成的无定形二氧化硅，例如Davison Catalysts of Columbia，Maryland生产的DavicatGrade 57。更优选地，所述金属以约10至20wt％的范围以氧化物形式沉积于比表面积在约50至200m2/g范围内的氧化铝载体上。在反应器320中，溴蒸气与优选保持在合适的耐磨载体上的固相金属溴化物，在低于约300℃，优选在约30℃和约200℃之间的温度下，按照下列通式反应，其中，M2表示所述金属 
                 2M2Brn+Br2→2M2Brn+1
按该方式，将溴作为第二金属溴化物，即2M2Brn+1贮存在反应器320中，而经由管线324、阀326和管线318将产生的包含残余空气或氧气的蒸气从反应器320排出。 
包含更低分子量烷烃、由原料气(管线211)和再循环气流的混合物构成的气流经由管线262、热交换器352(其中将所述气流预热到约150℃至约600℃范围内的温度)、阀304和管线302输送或运送到包含呈氧化价态的固相金属溴化物的床312的第二容器或反应器310。所述呈氧化价态的金属溴化物的金属选自铜(Cu)、铁(Fe)或钼(Mo)。金属的选择考虑到与所需操作温度相关的物理和热力学性质的影响，以及可能的环境和健康影响和成本。优选地，将铜或铁用作所述金属，而铜是最优选的。优选将呈氧化态的固体金属溴化物固定在合适的耐磨载体上，例如合成的无定形二氧化硅，例如Davison Catalysts ofColumbia，Maryland生产的Davicat Grade 57。更优选地，所述金属呈氧化态以约10至20重量％的范围沉积于比表面积约50至200m2/g的氧化铝载体上。所述气流的温度从约150℃至约600℃，而优选从约200℃至约450℃。在第二反应器310中，所述气流的温度使呈氧化价态的固相金属溴化物按照下列通式发生热分解，生成单质溴蒸气和呈还原态的固体金属溴化物，其中，M2表示所述金属：
2M2Brn+1→2M2Brn+Br2
在被导入烷基溴化反应器230以前，经由管线314、315、阀317、管线330、热交换器226输送产生的溴蒸气与包含更低分子量烷烃的气流。 
反应器310和320可呈循环方式操作。如图7中所示，阀304呈开启方式工作，让包含更低分子量烷烃的气流被输送到第二反应器310，而阀317呈开启方式工作，让该气流与在反应器310中产生的溴蒸气被输送到烷基溴化反应器230。同样，阀306呈开启方式工作，让溴蒸气经由管道307从反应器246输送到反应器320，而阀326呈开启方式工作，让残余空气或氧气从反应器320放出。一旦发生还原的金属溴化物和氧化的金属溴化物分别在反应器320和310中被显著转化为相应的氧化态和还原态，这些阀就如图8中所示那样关闭。此时，反应器320中的床322基本是呈氧化态的金属溴化物的床，而反应器310中的床312基本是呈还原态的金属溴化物的床。如图8中所示，关闭阀304、317、306和326，然后开启阀308和332，让含有更低分子量烷烃的气流经由管线262、热交换器352(其中将气流加热到约150℃至约600℃范围内)、阀308和管线309输送或传送到反应 器320，从而将呈氧化价态的固相金属溴化物热分解，生成单质溴蒸气和呈还原态的固态金属溴化物。还开启阀332让产生的溴蒸气在导人烷基溴化反应器230以前，与含有更低分子量烷烃的气流一起经由管线324和330和热交换器226输送。此外，开启阀300让从反应器246放出的溴蒸气经由管线242通过交换器221输送到反应器310，其中，呈还原价态的固相金属溴化物与溴反应而有效地将溴作为金属溴化物贮存。另外，开启阀316，让生成的基本上不含溴的气体经由管线314和318放出。按这种方式操作反应器直到发生分别在反应器310和320中的还原的金属溴化物和氧化的金属溴化物的床被显著转化为相应的氧化态和还原态，然后通过如前述那样开启和关闭阀将反应器循环返回图7中示意的流程。 
在图9中阐释的本发明的实施方案中，流化分别含于反应器310和320中的床312和322，再按照下述方式连接以提供床的连续操作而不需提供设备，例如阀，来改变往来各反应器的流向。按照该实施方案，将经由管线242从反应器246抽出的含溴气体在交换器370和372内冷却到约30℃至约300℃范围内的温度，再导入装有呈流化状态的移动的固体床322的反应器320的底部。按前文关于图7中所述的方式，随着溴蒸气与进入床322的底部的还原态金属溴化物反应，导入的这种流体的流动引起床322中的颗粒在反应器320内向上移动。在床322的顶部或附近，经溢流装置或旋风分离器或固体/气体分离的其它常规装置抽出由于还原的金属溴化物与溴蒸气在反应器320内基本上完全的反应而包含耐磨载体上的基本上氧化的金属溴化物的颗粒，在重力作用下流下管线359并且被导向反应器310中的床312底部或底部附近。所得到的完全不含溴的气体经由管线350放出。在图9中阐释的实施方案中，经由管线262和热交换器352(其中，将气流加热到约150℃至约600℃范围内的温度)输送或传送含有更低分子量烷烃、由原料气(管线211)和再循环气流的混合物组成的气流，并且导入反应器310。加热后的气流将进入床312底部或底部附近的、呈氧化价态的固相金属溴化物热分解，生成单质溴蒸气和呈还原态的固 体金属溴化物。随着呈氧化态的金属溴化物被热分解，该导入的气体的流动引起床312中的颗粒在反应器310内向上移动。在床312的顶部或顶部附近，经溢流装置或旋风分离器或固体/气体分离的其它常规装置抽出由于反应器310内基本上完全的热分解反应而包含耐磨载体上的基本还原的固态金属溴化物的颗粒，在重力作用下流下管线364并且被导向反应器310中颗粒的床322底部或底部附近。所得到的溴蒸气与含更低分子量的烷烃的气流一起经由管线354和热交换器355输送并且导入烷基溴化反应器230。这样，反应器310和320可连续操作而不改变操作参数。 
本发明的方法比传统方法更廉价，因为它在约1巴至约30巴范围内的低压力和关于气相约20℃至约600℃，以及优选关于液相约20℃至约180℃范围内的较低温度下操作。这些操作条件允许应用较简单设计的更廉价设备，即，关于气相从容易获得的金属合金或玻璃内衬的设备构成，以及关于液相使用聚合物内衬的或玻璃内衬的容器、管道和泵。本发明的方法还更加高效，因为操作所需的能量更少并且将作为不需要的副产物的过量二氧化碳的产生减到最少。本发明的方法能直接生产在液化石油气(LPG)中含有不同分子量的组分的混合的烃产品、烯烃和具有较大芳烃含量的发动机汽油燃料，于是显著提高汽油沸程燃料组分的辛烷值。 
虽然描述和示出了本发明的前文优选的实施方案，但是应懂得，可对其进行改变和修饰，例如那些启示的和其它，并且改变和修饰的方案都属于本发明的范围。 

Claims (27)

1.一种将较低分子量气态烷烃转化为烯烃的方法，它包含：
将具有较低分子量烷烃的气态进料与溴蒸气在第一反应器中反应而生成烷基溴化物和氢溴酸；和
在所述氢溴酸和由合成的晶态铝硅酸盐催化剂组成的催化剂的存在下且在足以生成烯烃和另外的氢溴酸的温度下，使所述烷基溴化物在第二反应器中反应；以及
在容器中，从所述烯烃中除去所述氢溴酸和所述另外的氢溴酸，其中，所述较低分子量气态烷烃为甲烷、乙烷、丙烷、丁烷、戊烷或其混合物。
2.权利要求1的方法，其中，所述溴蒸气是大体上干燥的，从而避免了在生成所述烷基溴化物的同时还生成显著量的二氧化碳。
3.权利要求1的方法，其中，所述气态进料是天然气。
4.权利要求3的方法，其中，在与所述溴蒸气反应以前处理所述天然气以从中除去几乎全部二氧化碳和硫化合物。
5.权利要求1的方法，其中，所述温度是从250℃至500℃。
6.权利要求5的方法，其中，所述温度是从300℃至450℃。
7.权利要求1的方法，其中，所述晶态铝硅酸盐催化剂是沸石催化剂。
8.权利要求7的方法，其中，所述沸石催化剂是X或Y型沸石催化剂。
9.权利要求8的方法，其中，所述沸石催化剂是10X沸石催化剂。
10.权利要求1的方法，它进一步包含：
在容器中，通过与水溶液的中和反应从所述烯烃中除去所述氢溴酸和所述另外的氢溴酸，所述水溶液包含通过氧化含有金属溴化物盐的水溶液而获得的反应产物，所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
11.权利要求1的方法，其中，所述溴蒸气是通过氧化金属溴化物盐的水溶液产生的，所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
12.权利要求1的方法，它进一步包含：
将所述烯烃脱水。
13.权利要求1的方法，它进一步包含：
将从所述氢溴酸和所述另外的氢溴酸转化的所述溴再循环到所述与所述气态进料反应的步骤，所述溴以蒸气形式被再循环。
14.权利要求1的方法，它进一步包含：
在容器中，通过将所述氢溴酸和所述另外的氢溴酸与金属氧化物反应生成金属溴化物和蒸汽而从所述烯烃除去所述氢溴酸和所述另外的氢溴酸。
15.权利要求14的方法，其中，所述金属氧化物的所述金属是镁、钙、钒、铬、锰、铁、钴、镍、铜、锌或锡。
16.权利要求14的方法，其中，所述金属氧化物被负载在固态载体上。
17.权利要求14的方法，其中，所述金属氧化物含于所述容器内的床中。
18.权利要求14的方法，它进一步包含：
使所述金属溴化物与含氧气体反应而获得金属氧化物和溴蒸气。
19.权利要求18的方法，其中，在使所述具有较低分子量烷烃的气态进料反应的步骤中应用在使所述金属溴化物与含氧气体反应的步骤中产生的所述溴蒸气。
20.权利要求18的方法，它进一步包含：
使在使所述金属溴化物与含氧气体反应的步骤中产生的所述溴蒸气与还原的金属溴化物反应而生成第二金属溴化物。
21.权利要求20的方法，它进一步包含：
加热所述第二金属溴化物，从而使所述第二金属溴化物热分解成所述溴蒸气和所述还原的金属溴化物。
22.权利要求21的方法，其中，在使所述具有较低分子量烷烃的气态进料反应的步骤中应用通过所述第二金属溴化物的热分解而产生的所述溴蒸气。
23.权利要求21的方法，其中所述加热步骤包含使所述第二金属溴化物与所述气态进料接触，在使所述具有较低分子量烷烃的气态进料反应的步骤中应用通过所述第二金属溴化物的热分解而产生的所述溴蒸气。
24.权利要求1的方法，其中所述除去步骤包括将所述氢溴酸、所述另外的氢溴酸和所述烯烃在所述容器中与水接触以从所述烯烃中除去所述氢溴酸和所述另外的氢溴酸。
25.权利要求24的方法，其中通过将金属溴化物盐的水溶液氧化产生所述的溴，所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
26.权利要求24的方法，其中所述接触步骤包括通过溶解于所述水中从所述烯烃中除去所述氢溴酸和所述另外的氢溴酸形成氢溴酸溶液，通过与包含金属氢氧化物的水溶液反应而将所述氢溴酸溶液中和，所述金属氢氧化物通过用氧氧化金属溴化物盐的水溶液而获得，所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
27.权利要求24的方法，其中所述氢溴酸和所述另外的氢溴酸溶解于所述水中形成氢溴酸溶液，所述方法进一步包括：
将所述氢溴酸溶液蒸发并将所述蒸发的氢溴酸溶液与金属氧化物反应，所述金属氧化物通过将金属溴化物盐氧化而获得，所述金属溴化物盐容纳在多孔载体上，所述金属溴化物盐的金属选自Cu、Zn、Fe、Co、Ni、Mn、Ca或Mg。
CN2006800390646A 2005-10-19 2006-09-13 将气态烷烃转化为烯烃和液态烃的方法 Expired - Fee Related CN101291891B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11/254,438 2005-10-19
US11/254,438 US20060100469A1 (en) 2004-04-16 2005-10-19 Process for converting gaseous alkanes to olefins and liquid hydrocarbons
PCT/US2006/035788 WO2007046986A2 (en) 2005-10-19 2006-09-13 Process for converting gaseous alkanes to olefins and liquid hydrocarbons

Publications (2)

Publication Number Publication Date
CN101291891A CN101291891A (zh) 2008-10-22
CN101291891B true CN101291891B (zh) 2013-03-27

Family

ID=37962979

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2006800390646A Expired - Fee Related CN101291891B (zh) 2005-10-19 2006-09-13 将气态烷烃转化为烯烃和液态烃的方法

Country Status (21)

Country Link
US (2) US20060100469A1 (zh)
EP (1) EP1945598A4 (zh)
JP (1) JP5396082B2 (zh)
KR (1) KR101363300B1 (zh)
CN (1) CN101291891B (zh)
AP (1) AP2008004417A0 (zh)
AR (1) AR058123A1 (zh)
AU (1) AU2006302939B2 (zh)
BR (1) BRPI0617707A2 (zh)
CA (1) CA2625459C (zh)
EA (1) EA022696B1 (zh)
EC (1) ECSP088361A (zh)
EG (1) EG26651A (zh)
MY (1) MY151088A (zh)
NO (1) NO20082252L (zh)
NZ (1) NZ567480A (zh)
PE (1) PE20070737A1 (zh)
TN (1) TNSN08176A1 (zh)
UA (1) UA105476C2 (zh)
WO (1) WO2007046986A2 (zh)
ZA (1) ZA200803330B (zh)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7838708B2 (en) 2001-06-20 2010-11-23 Grt, Inc. Hydrocarbon conversion process improvements
US20050171393A1 (en) * 2003-07-15 2005-08-04 Lorkovic Ivan M. Hydrocarbon synthesis
RU2366642C2 (ru) 2003-07-15 2009-09-10 Джи Ар Ти, Инк. Синтез углеводородов
US20080275284A1 (en) 2004-04-16 2008-11-06 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US8642822B2 (en) 2004-04-16 2014-02-04 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor
US7244867B2 (en) 2004-04-16 2007-07-17 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8173851B2 (en) * 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US20060100469A1 (en) 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons
CA2641348C (en) 2006-02-03 2014-12-23 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
KR101335397B1 (ko) * 2006-02-03 2013-12-02 지알티, 인코포레이티드 할로겐으로부터 가벼운 기체를 분리하는 방법
CN101284756A (zh) * 2007-04-13 2008-10-15 微宏科技（湖州）有限公司 碳氢化合物中HBr的净化方法
EA201200888A1 (ru) * 2007-05-14 2013-02-28 Грт, Инк. Способ конверсии углеводородного сырья с электролитическим извлечением галогенов
JP2010528054A (ja) 2007-05-24 2010-08-19 ジーアールティー インコーポレイテッド 可逆的なハロゲン化水素の捕捉及び放出を組み込んだ領域反応器
US20090312586A1 (en) * 2008-06-13 2009-12-17 Marathon Gtf Technology, Ltd. Hydrogenation of multi-brominated alkanes
US8282810B2 (en) * 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
KR101740419B1 (ko) * 2008-07-18 2017-05-26 지알티, 인코포레이티드 천연 가스를 액체 탄화수소로 변환시키는 연속 공정
JP5562245B2 (ja) * 2008-09-17 2014-07-30 旭化成ケミカルズ株式会社 オレフィンの製造方法およびその製造装置
US7812201B2 (en) 2008-10-01 2010-10-12 Targa Resources, Inc. Process and catalyst for converting alkanes
US8367884B2 (en) 2010-03-02 2013-02-05 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8198495B2 (en) 2010-03-02 2012-06-12 Marathon Gtf Technology, Ltd. Processes and systems for the staged synthesis of alkyl bromides
US8815050B2 (en) 2011-03-22 2014-08-26 Marathon Gtf Technology, Ltd. Processes and systems for drying liquid bromine
US8436220B2 (en) 2011-06-10 2013-05-07 Marathon Gtf Technology, Ltd. Processes and systems for demethanization of brominated hydrocarbons
US8829256B2 (en) 2011-06-30 2014-09-09 Gtc Technology Us, Llc Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons
US8802908B2 (en) * 2011-10-21 2014-08-12 Marathon Gtf Technology, Ltd. Processes and systems for separate, parallel methane and higher alkanes' bromination
TW201341609A (zh) * 2011-12-12 2013-10-16 Exxonmobil Upstream Res Co 用於形成碳奈米管之方法及系統
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
WO2016061584A1 (en) * 2014-10-17 2016-04-21 Solutions Labs, Inc. Production of clean hydrocarbon and nitrogen-based fuel
WO2016191122A1 (en) * 2015-05-27 2016-12-01 Sabic Global Technologies B.V. Ion-exchanged zsm-5 zeolite catalyst for conversion of alkyl halide to olefins
DE102016116265A1 (de) * 2016-08-31 2018-03-01 Faurecia Emissions Control Technologies, Germany Gmbh Lotwerkstoff auf Kupferbasis und Verwendung des Lotwerkstoffs
KR102365335B1 (ko) * 2019-12-12 2022-02-18 한국화학연구원 합성가스로부터 가솔린 범위의 액상 탄화수소 혼합물을 제조하는 방법
WO2021198166A1 (en) 2020-03-30 2021-10-07 Total Se Gas to olefins process with coproduction of hydrogen together with heat integration process
WO2021198175A1 (en) 2020-03-30 2021-10-07 Total Se Gas to olefins process with coproduction of hydrogen together with electrified reactional section
EP4126798A1 (en) 2020-03-30 2023-02-08 Totalenergies Onetech Gas to olefins processes with coproduction of hydrogen

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6525230B2 (en) * 2001-04-18 2003-02-25 Grt, Inc. Zone reactor

Family Cites Families (754)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3172915A (en) * 1965-03-09 Preparation of oxygenated methane derivatives
GB156122A (en) 1919-12-08 1922-03-30 Otto Traun S Forschungslaborat Process for the manufacture of diolefines and derivatives thereof
GB294100A (en) 1927-07-16 1929-06-27 Curt Epner Improvements in and relating to the production of liquid polymerisation products from gases containing hydrocarbons
GB363009A (en) 1930-09-19 1931-12-17 John Philip Baxter Production of acetylene and vinyl chloride from ethylene dichloride
FR745544A (zh) 1931-11-11 1933-05-12
DE698778C (de) * 1934-11-11 1941-07-10 I G Farbenindustrie Akt Ges Verfahren zur Herstellung von organischen Monochlor- oder Monobromverbindungen
GB474922A (en) 1936-05-14 1937-11-15 Ig Farbenindustrie Ag Process for chlorinating and brominating hydrocarbons
US2246082A (en) * 1939-08-22 1941-06-17 Shell Dev Preparation of alkyl halides
GB536491A (en) 1939-09-28 1941-05-16 Bataafsche Petroleum A process for the production of aromatic hydrocarbons from unsaturated hydrocarbons
GB553950A (en) 1941-09-09 1943-06-11 Du Pont Improvements in or relating to the manufacture of halogenated hydrocarbons
GB586483A (en) 1944-07-05 1947-03-20 Standard Oil Dev Co Process for the conversion of normally gaseous olefins to liquid hydrocarbons
US2488083A (en) * 1946-06-18 1949-11-15 Socony Vacuum Oil Co Inc Manufacture of liquid hydrocarbons
US2677598A (en) * 1953-01-19 1954-05-04 Dow Chemical Co Oxidation of ferrous halides to form ferric halides
GB775590A (en) 1953-11-27 1957-05-29 Standard Oil Co Improvements in or relating to production of ethyl toluenes
US2941014A (en) * 1954-08-06 1960-06-14 Hoechst Ag Manufacture of alkyl chlorination products
GB793214A (en) 1955-02-18 1958-04-09 Bataafsche Petroleum Process for the conversion of hydrocarbons containing acyclic carbon atoms
GB796085A (en) 1955-12-22 1958-06-04 Bataafsche Petroleum Hydrocarbon conversion process
GB796048A (en) 1956-02-06 1958-06-04 Bataafsche Petroleum Conversion of hydrocarbons
DE1037137B (de) 1957-01-25 1958-08-21 Bayer Ag Verfahren zur Herstellung halogenhaltiger, aromatisch-aliphatischer Polyaether
GB883256A (en) 1958-05-02 1961-11-29 Columbia Southern Chem Corp Halogenation process
US3562321A (en) * 1961-10-10 1971-02-09 Sun Oil Co Preparation of oxygenated hydrocarbons
GB950976A (en) 1961-10-13 1964-03-04 British Hydrocarbon Chem Ltd Improvements in and relating to the production of olefines
BE623466A (zh) 1961-10-13
GB991303A (en) 1962-07-26 1965-05-05 British Hydrocarbon Chem Ltd The production of olefines by the dehydrochlorination of alkyl chlorides
US3294846A (en) 1962-10-10 1966-12-27 Dow Chemical Co Process for preparing metaaryloxy phenols
US3246043A (en) * 1962-12-12 1966-04-12 Universal Oil Prod Co Preparation of olefinic hydrocarbons
GB1015033A (en) 1963-01-31 1965-12-31 Shell Int Research Preparation of olefin oxides
NL125428C (zh) 1963-02-27
US4011278A (en) 1963-02-27 1977-03-08 Mobil Oil Corporation Conversion of polar compounds using a zsm-5 zeolite catalyst
US3273964A (en) * 1963-02-28 1966-09-20 Universal Oil Prod Co Process for producing bromine from a mixture of hydrogen bromide and olefinic hydrocarbon
GB1104294A (en) 1963-12-10 1968-02-21 Ralph William King Production of lower alkanols and lower alkyl bromides
US3310380A (en) * 1964-02-13 1967-03-21 Universal Oil Prod Co Bromine recovery
US3923913A (en) 1964-05-12 1975-12-02 Pechiney Saint Gobain Process for obtaining chlorinated derivatives of ethylene
US3254023A (en) * 1964-06-08 1966-05-31 Socony Mobil Oil Co Inc Method of heat balancing in organic catalytic reactions
US3353919A (en) 1964-07-23 1967-11-21 Air Preheater Apparatus for the elimination of odors from noxious gases
BE672377A (zh) 1964-11-24 1966-05-16
US3353916A (en) * 1966-04-25 1967-11-21 Universal Oil Prod Co Quantitative recovery of bromine by two stage catalytic oxidation of hydrogen bromide
DE1618686B1 (de) 1966-04-28 1971-08-26 Marathon Oil Co Tieftemperatur-Verfahren für die Chlorierung oder Bromierung von Kohlenwasserstoffen
US3346340A (en) 1966-08-11 1967-10-10 Universal Oil Prod Co Production of bromine by oxidation of hydrogen bromide
DE1807780B2 (de) 1968-11-08 1976-11-04 Henkel & Cie GmbH, 4000 Düsseldorf Verfahren zur herstellung von aether- und polyaetheralkoholen
DE1618254B1 (de) 1967-06-29 1971-07-08 Kalk Chemische Fabrik Gmbh Verfahren zur Herstellung von Bromverbindungen aus Alkoholen aus Brom
US3496242A (en) 1967-08-30 1970-02-17 Fmc Corp Oxychlorination of mixed hydrocarbons
US3598876A (en) * 1967-11-13 1971-08-10 Universal Oil Prod Co Selective halogenation of hydrocarbons
US3879480A (en) 1967-12-07 1975-04-22 Lummus Co Vinyl chloride process
US3679758A (en) 1968-02-05 1972-07-25 Sun Oil Co Dihalogenation of branched alkanes
GB1253618A (en) 1968-03-28 1971-11-17 Perstorp Ab Process for the production of dry semi-formals
CA920775A (en) 1968-05-13 1973-02-13 Vadekar Mohan Oxidation of hydrogen chloride using molecular sieve catalysts
US3673264A (en) 1968-05-21 1972-06-27 Dow Chemical Co Method of preparing optically active propylene chlorohydrins and propylene oxides
US3920764A (en) 1968-10-23 1975-11-18 Lummus Co Dehydrogenation process
US3657367A (en) 1968-10-31 1972-04-18 Stauffer Chemical Co Oxychlorination of saturated and unsaturated hydrocarbons in the presence of a fluidized catalyst containing lanthanum and didymium
US3670037A (en) 1969-02-19 1972-06-13 Exxon Research Engineering Co Catalyst system
US3883651A (en) 1969-08-08 1975-05-13 Boehringer Sohn Ingelheim Pharmaceutical compositions containing a 2-(aminoalkylamino)-4-amino-thieno{8 3,2-d{9 pyrimidine and method of use
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3705196A (en) 1969-10-31 1972-12-05 Sun Oil Co Synthesis of aliphatic and alicyclic ethers
US3799997A (en) 1971-11-08 1974-03-26 Universal Oil Prod Co Preparation of alkenynes
US3968200A (en) 1972-03-27 1976-07-06 The Lummus Company Reactor effluent quench system
US4172099A (en) 1972-05-30 1979-10-23 Stauffer Chemical Company Process for chlorination of ethylene
GB1395926A (en) 1972-07-27 1975-05-29 Bp Chem Int Ltd Process for the production of isoprene by the chlorination/ dehydrochlorination of 2-methylbutene-2
JPS5231022B2 (zh) 1972-10-06 1977-08-12
US3876715A (en) * 1972-12-01 1975-04-08 Gulf Research Development Co Process for preparing 2,3-dibromo-2-alkylalkanes
IT982662B (it) 1973-03-30 1974-10-21 Montedison Spa Procedimento di bromofluorurazio ne del metano
US4347391A (en) * 1973-06-11 1982-08-31 Stauffer Chemical Company Process for preparing ethylene dichloride
US3865886A (en) 1973-06-20 1975-02-11 Lummus Co Production of allyl chloride
US3894103A (en) 1973-08-09 1975-07-08 Mobil Oil Corp Aromatization reactions
US3894105A (en) * 1973-08-09 1975-07-08 Mobil Oil Corp Production of durene
US3894107A (en) * 1973-08-09 1975-07-08 Mobil Oil Corp Conversion of alcohols, mercaptans, sulfides, halides and/or amines
US3894104A (en) 1973-08-09 1975-07-08 Mobil Oil Corp Aromatization of hetero-atom substituted hydrocarbons
US3879473A (en) 1973-08-14 1975-04-22 Phillips Petroleum Co Preparation of ethers from alcohols and olefins catalyzed by iodine
US3987119A (en) 1973-10-23 1976-10-19 Allied Chemical Corporation Production of vinyl chloride from ethane
US3919336A (en) 1973-10-23 1975-11-11 Allied Chem Method of preparing vinyl chloride from liquid ethylene dichloride
US4092368A (en) 1974-03-13 1978-05-30 General Electric Company Vapor phase transesterification
US4046825A (en) 1974-05-15 1977-09-06 Mobil Oil Corporation Conversion of oxygenated compounds to gasoline
US4117251A (en) 1974-05-15 1978-09-26 Chemische Werke Huls Ag Method for preparing straight chain primary alcohols from 1-bromoalkanes
US4035285A (en) 1974-05-28 1977-07-12 Mobil Oil Corporation Hydrocarbon conversion process
US3965205A (en) 1974-06-10 1976-06-22 Mobil Oil Corporation Conversion of low octane hydrocarbons to high octane gasoline
US4169862A (en) 1974-07-22 1979-10-02 The B. F. Goodrich Company Low temperature catalytic combustion of chlorohydrocarbons
US4058576A (en) 1974-08-09 1977-11-15 Mobil Oil Corporation Conversion of methanol to gasoline components
US4138440A (en) 1974-08-14 1979-02-06 Mobil Oil Corporation Conversion of liquid alcohols and ethers with a fluid mass of ZSM-5 type catalyst
US4044061A (en) 1974-09-23 1977-08-23 Mobil Oil Corporation Preheating methanol effects steady state operation of conversion to gasoline
US3928483A (en) 1974-09-23 1975-12-23 Mobil Oil Corp Production of gasoline hydrocarbons
US3974062A (en) 1974-10-17 1976-08-10 Mobil Oil Corporation Conversion of full range crude oils with low molecular weight carbon-hydrogen fragment contributors over zeolite catalysts
US4071753A (en) 1975-03-31 1978-01-31 Gte Laboratories Incorporated Transducer for converting acoustic energy directly into optical energy
US4049734A (en) 1975-04-08 1977-09-20 Mobil Oil Corporation Conversion of coal to high octane gasoline
US4025575A (en) 1975-04-08 1977-05-24 Mobil Oil Corporation Process for manufacturing olefins
US4025576A (en) 1975-04-08 1977-05-24 Mobil Oil Corporation Process for manufacturing olefins
US4133838A (en) 1975-05-15 1979-01-09 Pearson Research Corp. Process for preparing hydrocarbons from methanol and phosphorus pentoxide
ZA763551B (en) 1975-07-02 1978-01-25 Mobil Oil Corp Manufacture of gasoline
US4039600A (en) 1975-07-02 1977-08-02 Mobil Oil Corporation Conversion of synthesis gas to aromatic hydrocarbons
US4087475A (en) 1975-07-03 1978-05-02 Robert Kenneth Jordan Carbonyl fluorination process
US4052471A (en) 1975-08-06 1977-10-04 Pearsall Chemical Corporation Process for chlorinating C8 to C30 linear hydrocarbons
US3992466A (en) 1975-08-13 1976-11-16 Mobil Oil Corporation Hydrocarbon conversion
US4052472A (en) 1976-01-16 1977-10-04 Mobil Oil Corporation Mordenite conversion of alkanols to penta- and hexamethyl benzenes
US4049573A (en) 1976-02-05 1977-09-20 Mobil Oil Corporation Zeolite catalyst containing oxide of boron or magnesium
US4006169A (en) * 1976-02-26 1977-02-01 Smithkline Corporation Epoxidation of α,β-ethylenic ketones
US4060568A (en) 1976-03-31 1977-11-29 Mobil Oil Corporation Silica-modified zeolite catalyst and conversion therewith
US4072733A (en) 1976-04-02 1978-02-07 Ethyl Corporation Conversion of methanol and dimethyl ether
US4110180A (en) 1976-04-28 1978-08-29 Diamond Shamrock Technologies S.A. Process for electrolysis of bromide containing electrolytes
IT1075503B (it) 1976-05-08 1985-04-22 Basf Ag Processo per la preparazione di glicolesteri
US4025571A (en) 1976-05-12 1977-05-24 Mobil Oil Corporation Manufacture of hydrocarbons
US4025572A (en) 1976-05-12 1977-05-24 Mobil Oil Corporation Manufacture of hydrocarbons
GB1542112A (en) 1976-06-11 1979-03-14 Shell Int Research Process for the preparation of 2-phenylethanol or derivatives thereof
US4143084A (en) 1976-07-19 1979-03-06 Mobil Oil Corporation Di-alkylbenzene isomer mixtures
US4035430A (en) 1976-07-26 1977-07-12 Mobil Oil Corporation Conversion of methanol to gasoline product
CA1089632A (en) 1976-08-20 1980-11-18 Alfred J. Darnell Hydrogen production
US4194990A (en) 1977-02-11 1980-03-25 Allied Chemical Corporation Catalyst and process for the production of chlorofluorinated hydrocarbons
US4380682A (en) 1977-03-30 1983-04-19 Diamond Shamrock Corporation Balanced chlorination process
US4156698A (en) 1977-05-05 1979-05-29 Mobil Oil Corporation Conversion of alcohols or ethers using rare earth crystalline aluminosilicate in an alumina matrix
IT1077342B (it) * 1977-07-18 1985-05-04 Snam Progetti Processo per la produzione di oligomeri da alfaolefine lineari,successiva idrogenazione degli stessi e prodotti saturi cosi' ottenuti
NL7710901A (nl) 1977-10-05 1979-04-09 Esmil B V Stationsstraat 48 Werkwijze voor het gelijktijdig verwerken van gebruikt metaal en/of metaalafval van gehaloge- neerde koolwaterstoffen.
US4300005A (en) 1977-12-02 1981-11-10 Monsanto Co. Preparation of vinyl chloride
US4191618A (en) 1977-12-23 1980-03-04 General Electric Company Production of halogens in an electrolysis cell with catalytic electrodes bonded to an ion transporting membrane and an oxygen depolarized cathode
US4133966A (en) 1977-12-23 1979-01-09 Gulf Research & Development Company Selective formation of ethanol from methanol, hydrogen and carbon monoxide
GB1604081A (en) * 1978-01-20 1981-12-02 Gallaher Ltd Production of catalysts from activated supports
SU694483A1 (ru) 1978-05-22 1979-10-30 Уфимский Нефтяной Институт Способ переработки побочных галоидуглеводородов производства хлористого аллила и металлилхлорида
US4282159A (en) 1978-06-19 1981-08-04 Wisconsin Alumni Research Foundation Preparation of alkylene oxides
DE2832532A1 (de) 1978-07-25 1980-02-07 Hoechst Ag Verfahren zur gewinnung von reinen 2-(perfluoralkyl)-aethanolen aus ihren gemischen mit 2-(perfluoralkyl)-aethylenen und gegebenenfalls 2-(perfluoralkyl)- aethylestern
US4187255A (en) 1978-08-21 1980-02-05 Conoco, Inc. Process for methylating naphthalene
FR2434861A1 (fr) 1978-08-31 1980-03-28 Inst Francais Du Petrole Procede de production d'essence a haut indice d'octane et en particulier d'essence utilisable sans plomb
US4849573A (en) 1978-09-05 1989-07-18 Mobil Oil Corporation Process for manufacturing light olefins
US4300009A (en) 1978-12-28 1981-11-10 Mobil Oil Corporation Conversion of biological material to liquid fuels
JPS55130923A (en) * 1979-03-30 1980-10-11 Mitsubishi Heavy Ind Ltd Condensation of methyl chloride through dehydrochlorination
US4311865A (en) 1979-04-04 1982-01-19 Mobil Oil Corporation Manufacture of hydrocarbons from oxygenates
NL7902886A (nl) 1979-04-12 1980-10-14 Shell Int Research Werkwijze voor de bereiding van een koolwaterstof- mengsel.
US4410714A (en) 1979-05-03 1983-10-18 The Lummus Company Production of epoxy compounds from olefinic compounds
US4496752A (en) * 1979-05-03 1985-01-29 The Lummus Company Production of epoxy compounds from olefinic compounds
US4443620A (en) 1979-05-03 1984-04-17 The Lummus Company Production of epoxy compounds from olefinic compounds
US4272338A (en) 1979-06-06 1981-06-09 Olin Corporation Process for the treatment of anolyte brine
US4371716A (en) 1979-09-04 1983-02-01 Shell Oil Company β-(Sec-alkoxy) ethanol process
US4462814A (en) 1979-11-14 1984-07-31 Koch Process Systems, Inc. Distillative separations of gas mixtures containing methane, carbon dioxide and other components
DE3069081D1 (en) 1979-12-13 1984-10-04 Ici Plc Method of recovering bromine from methyl bromide
US4307261A (en) 1980-02-19 1981-12-22 Vulcan Materials Company Process for separating ferric iron from chlorinated hydrocarbons
US4412086A (en) 1980-02-19 1983-10-25 Vulcan Materials Company Process for separating ferric iron from chlorinated hydrocarbons
US4350511A (en) 1980-03-18 1982-09-21 Koch Process Systems, Inc. Distillative separation of carbon dioxide from light hydrocarbons
EP0039547B1 (en) 1980-05-01 1984-07-18 Imperial Chemical Industries Plc Halogenation process using a halide carrier and process for regeneration of the halide carrier
US4302619A (en) 1980-06-04 1981-11-24 Mobil Oil Corporation Control of CO emissions in a process for producing gasoline from methanol
US4317934A (en) 1980-08-15 1982-03-02 Ethyl Corporation Preparation of carbonyl compounds
US4320241A (en) 1980-08-28 1982-03-16 Occidental Research Corporation Process for converting oxygenated hydrocarbons into hydrocarbons
US4317943A (en) 1980-09-12 1982-03-02 Texaco Inc. Process for preparing glycol ethers
US4308403A (en) 1980-09-12 1981-12-29 Texaco Inc. Process for preparing glycol ethers
US4301253A (en) * 1980-09-25 1981-11-17 Union Carbide Corporation Process for the selective production of ethanol and methanol directly from synthesis gas
US4333852A (en) * 1980-09-25 1982-06-08 Union Carbide Corporation Catalyst for the selective production of ethanol and methanol directly from synthesis gas
US4431856A (en) 1980-09-29 1984-02-14 Mobil Oil Corporation Fluid zeolite catalyst conversion of alcohols and oxygenated derivatives to hydrocarbons
DE3037093C1 (de) 1980-10-01 1981-11-12 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Herstellung von Cycloocten-4-ol-1 aus Cyclooctadien-1,5
US4543434A (en) 1981-01-28 1985-09-24 Mobil Oil Corporation Process for producing liquid hydrocarbon fuels
US4690903A (en) 1981-02-02 1987-09-01 Mobil Oil Corporation Process for preparing organic fuels and chemicals from biomass
GB2095243A (en) 1981-03-19 1982-09-29 Ici Plc Production of methylene chloride
GB2095245A (en) 1981-03-19 1982-09-29 Ici Plc Chlorination of alkanes
IN157669B (zh) 1981-03-23 1986-05-17 Pfizer
DE3117135A1 (de) 1981-04-30 1982-11-18 Bayer Ag, 5090 Leverkusen Kristallines alumosilicat, verfahren zu dessen herstellung sowie dessen verwendung zur katalytischen umwandlung von methanol und/oder dimethylether in kohlenwasserstoffe
US4389391A (en) 1981-06-28 1983-06-21 Dunn Jr Wendell E Process for beneficiating titaniferous ores
US4373109A (en) * 1981-08-05 1983-02-08 Olah George A Bifunctional acid-base catalyzed conversion of hetero-substituted methanes into olefins
DE3132692A1 (de) * 1981-08-19 1983-03-17 Bayer Ag, 5090 Leverkusen Verfahren zur halogenierung von organischen verbindungen
US4513164A (en) 1981-09-01 1985-04-23 Olah George A Condensation of natural gas or methane into gasoline range hydrocarbons
DE164798T1 (de) 1981-09-01 1986-09-25 George Andrew Beverly Hills Calif. Olah Verfahren zur herstellung von methylmonohalogeniden.
US4523040A (en) * 1981-09-01 1985-06-11 Olah George A Methyl halides and methyl alcohol from methane
US4433192A (en) 1981-09-01 1984-02-21 Olah George A Condensation of natural gas or methane into gasoline range hydrocarbons
US4467130A (en) * 1981-09-01 1984-08-21 Olah George A Condensation of natural gas or methane into gasoline-range hydrocarbons
US4465893A (en) * 1982-08-25 1984-08-14 Olah George A Oxidative condensation of natural gas or methane into gasoline range hydrocarbons
DE3137751A1 (de) 1981-09-23 1983-03-31 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zum erzeugen von benzinkohlenwasserstoffen aus methanol
US4605803A (en) 1981-11-21 1986-08-12 Mobil Oil Corporation Acid-catalyzed organic compound conversion
CA1186345A (en) 1981-12-14 1985-04-30 Martin M.Y. Chang Hydrocarbon production
US4568660A (en) 1982-01-25 1986-02-04 Hercules Incorporated Cycloolefin polymerization catalyst composition
US4489211A (en) 1982-02-04 1984-12-18 Onoda Cement Co., Ltd. Process for producing 2,2,2-trifluoroethanol
US4538014A (en) 1982-03-08 1985-08-27 Mobil Oil Corporation Catalysis over activated zeolites
US4538015A (en) 1982-03-08 1985-08-27 Mobil Oil Corporation Catalysis over activated zeolites
US4384159A (en) 1982-03-12 1983-05-17 The Dow Chemical Company Catalytic dehydrohalogenation process
IT1150678B (it) 1982-03-12 1986-12-17 Anic Spa Procedimento per la produzione di eteri alchil terbutilici in presenza di butadiene
US4433189A (en) 1982-03-18 1984-02-21 Mobil Oil Corporation Catalytic conversion of methanol to light olefins
US4588835A (en) 1982-03-29 1986-05-13 Otsuka Kagaku Yakuhin Kabushiki Kaisha Process for preparing alkoxyphenols
US4499314A (en) 1982-03-31 1985-02-12 Imperial Chemical Industries Plc Methanol conversion to hydrocarbons with zeolites and cocatalysts
DE3216722A1 (de) 1982-05-05 1983-11-10 Hoechst Ag, 6230 Frankfurt 4-halomethylbenzoesaeure-alkylester-imine und verfahren zu deren herstellung
GB2120249B (en) 1982-05-15 1985-11-27 British Petroleum Co Plc Process for the production of methyl or ethyl mono-halide
US4467133A (en) 1982-06-21 1984-08-21 Mobil Oil Corporation Conversion of alcohols and ethers to distillate range hydrocarbons
FR2529883A1 (fr) 1982-07-06 1984-01-13 Ugine Kuhlmann Procede de fabrication de chlorure de vinyle
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4509955A (en) 1982-08-09 1985-04-09 The Lubrizol Corporation Combinations of carboxylic acylating agents substituted with olefin polymers of high and low molecular weight mono-olefins, derivatives thereof, and fuels and lubricants containing same
US4465884A (en) 1982-08-17 1984-08-14 Mobil Oil Corporation Olefin processing
US4814527A (en) 1982-10-18 1989-03-21 The Dow Chemical Company Catalytic process for ethylene dichloride
US4654449A (en) * 1982-12-09 1987-03-31 Mobil Oil Corporation Formation of halogenated hydrocarbons from hydrocarbons
US4655893A (en) * 1983-02-07 1987-04-07 Battelle Development Corporation Cubic boron nitride preparation utilizing a boron and nitrogen bearing gas
US4788377A (en) 1983-04-22 1988-11-29 Mobil Oil Corporation Process for manufacturing olefins
US4547612A (en) 1984-09-25 1985-10-15 Mobil Oil Corporation Production of lubricant and/or heavy distillate range hydrocarbons by light olefin upgrading
US4720600A (en) 1983-06-29 1988-01-19 Mobil Oil Corporation Production of middle distillate range hydrocarbons by light olefin upgrading
US4675410A (en) 1983-07-11 1987-06-23 Nepera Inc. Process for the production of pyridine or alkyl substituted pyridines
US4540826A (en) 1983-08-12 1985-09-10 Phillips Petroleum Company Process for preparing olefinic aldehydes
CA1202610A (en) 1983-08-15 1986-04-01 Ralph M. Dessau Activity enhancement of high silica zeolites
EP0134464B1 (de) 1983-08-25 1988-04-20 Hüls Aktiengesellschaft Verfahren zur Herstellung von 3,3- bzw. 2,3-Dimethylbuten und 2,3-Dimethylbutadien bzw. zur gleichzeitigen Herstellung dieser Olefine und Glykol- bzw. Polyglykol-n-alkyl-3,3- bzw. -2,3-dimethylbutylether aus Mono- und Dichlor-dimethylbutan
US5175382A (en) 1983-09-22 1992-12-29 Werner Hebgen Preparation of 1,2-Dichloroethane
US4524228A (en) 1983-09-29 1985-06-18 Mobil Oil Corporation Production of durene and gasoline from synthesis gas
US4524231A (en) 1983-09-29 1985-06-18 Mobil Oil Corporation Production of durene from alcohols and ethers
US4524227A (en) 1983-09-29 1985-06-18 Mobil Oil Corporation Coproduction of durene and gasoline from synthesis gas and alcohols and separation of durene-gasoline mixtures
US4599474A (en) 1983-10-31 1986-07-08 Chevron Research Company Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal-containing catalyst
US4709108A (en) 1983-10-31 1987-11-24 Chevron Research Company Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal compound-containing catalyst
US4704493A (en) 1983-10-31 1987-11-03 Chevron Corporation Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal compound-containing catalyst (II-A)
US4704488A (en) 1983-10-31 1987-11-03 Chevron Research Company Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal compound-containing catalyst (111-A)
GB8331982D0 (en) 1983-11-30 1984-01-04 British Petroleum Co Plc Hydrocarbons from c1 to c4 alkyl monohalides
EP0150594B1 (en) * 1983-12-16 1988-03-23 The British Petroleum Company p.l.c. Process for the production of hydrocarbons from hetero-substituted alkanes
GB8333613D0 (en) * 1983-12-16 1984-01-25 British Petroleum Co Plc Production of hydrocarbons from c1 to c4 alkyl monohalides
JPS60136525A (ja) 1983-12-26 1985-07-20 Agency Of Ind Science & Technol エタノ−ルの製造法
US4513092A (en) * 1984-01-04 1985-04-23 Mobil Oil Corporation Composite catalyst for halogenation and condensation of alkanes
US4642404A (en) 1984-01-23 1987-02-10 Mobil Oil Corporation Conversion of olefins and paraffins to higher hydrocarbons
US4621161A (en) 1984-01-23 1986-11-04 Mobil Oil Corporation Oxygenate conversion over activated zeolite catalyst
US4550218A (en) 1984-03-05 1985-10-29 Mobil Oil Corporation Hydrocarbon synthesis with zeolite catalyst of improved hydrothermal stability
LU85285A1 (fr) 1984-04-03 1985-11-27 Labofina Sa Procede d'isomerisation d'olefines
US4634800A (en) 1984-04-16 1987-01-06 Atlantic Richfield Company Methane conversion process
GB8410479D0 (en) * 1984-04-24 1984-05-31 British Petroleum Co Plc Conversion process
US4497967A (en) 1984-06-15 1985-02-05 The Halcon Sd Group, Inc. Process for the preparation of ethanol from methanol, carbon monoxide _and hydrogen
US4590310A (en) 1984-08-02 1986-05-20 The Boc Group, Inc. Process for the preparation of 2,2,2-trifluoroethanol
US4550217A (en) 1984-08-29 1985-10-29 Mobil Oil Corporation Conversion of methanol to olefins using large size catalyst particles
GB8429007D0 (en) 1984-11-16 1984-12-27 British Petroleum Co Plc Aromatics from ethane/ethylene
US4696985A (en) 1984-11-16 1987-09-29 Hercules Incorporated Catalyst composition for polymerization of cycloolefins
US4579977A (en) 1984-12-20 1986-04-01 Phillips Petroleum Company Process for the oxidation of organic halides to organic aldehydes
US4764356A (en) 1984-12-21 1988-08-16 Exxon Research & Engineering Co. Process for synthesizing a zeolite catalyst on a pH controlled basis to improve catalyst life
US4544781A (en) 1985-01-09 1985-10-01 Mobil Oil Corporation Control of temperature exotherms in the conversion of methanol to gasoline hydrocarbons
DE194931T1 (de) 1985-03-14 1987-02-26 Societe Nationale Elf Aquitaine (Production), Courbevoie, Fr Verfahren und vorrichtung zur photochemischen sulfochlorinierung von gasfoermigen alkanen.
US5210357A (en) 1985-06-07 1993-05-11 Phillips Petroleum Company Composition of matter and method of oxidative conversion of organic compounds therewith
US4658077A (en) 1985-06-07 1987-04-14 Phillips Petroleum Company Composition of matter and method of oxidative conversion of organic compounds therewith
JPS61242901A (ja) * 1985-04-17 1986-10-29 Toyo Soda Mfg Co Ltd 臭素回収用吸着剤及び臭素回収方法
US5093542A (en) 1985-05-24 1992-03-03 Atlantic Richfield Company Methane conversion process
US5146027A (en) 1985-05-24 1992-09-08 Atlantic Richfield Co. Methane conversion process
US5959170A (en) 1985-05-24 1999-09-28 Atlantic Richfield Company Methane conversion process
US4774216A (en) 1985-06-07 1988-09-27 Phillips Petroleum Company Composition of matter for oxidative conversion of organic compounds
US5105045A (en) 1985-06-07 1992-04-14 Phillips Petroleum Company Method of oxidative conversion
US4724275A (en) 1985-07-01 1988-02-09 National Distillers And Chemical Corporation Crystalline aluminosilicates and their use in the conversion of methanol to low molecular weight hydrocarbons
GB8518820D0 (en) 1985-07-25 1985-08-29 British Petroleum Co Plc Chemical process
GB8520977D0 (en) 1985-08-21 1985-09-25 British Petroleum Co Plc Production of aromatics
US4795843A (en) * 1985-08-26 1989-01-03 Uop Inc. Conversion of methane into larger organic hydrocarbons
US4665259A (en) 1985-08-28 1987-05-12 The Standard Oil Company Methane conversion process using phosphate-containing catalysts
US4633027A (en) 1985-09-23 1986-12-30 Mobil Oil Corporation Process for converting olefins to gasoline, distillate and alkylate liquid hydrocarbons
US4658073A (en) 1985-09-23 1987-04-14 Mobil Oil Corporation Control system for multistage chemical upgrading
CA1322768C (en) 1988-12-29 1993-10-05 John E. Stauffer Process for the chlorination of ethane
US4788369A (en) 1985-12-31 1988-11-29 Mobil Oil Corporation Conversion of methanol to gasoline
LU86280A1 (fr) 1986-01-29 1987-09-03 Labofina Sa Procede de production d'essence
GB8613673D0 (en) 1986-06-05 1986-07-09 Bp Benzin Und Petroleum Ag Chemical process
ZA874948B (en) 1986-07-07 1989-02-22 Mobil Oil Corp Aromatisation of aliphatics over gallium-containing zeolites
US4781733A (en) 1986-07-23 1988-11-01 Bend Research, Inc. Semipermeable thin-film membranes comprising siloxane, alkoxysilyl and aryloxysilyl oligomers and copolymers
US4814532A (en) 1986-08-04 1989-03-21 Chemical Company, Ltd. Asahi Process for producing alkylcyclopentadiene derivatives
US4795848A (en) 1986-08-28 1989-01-03 The Standard Oil Company Method for upgrading a low molecular weight alkane with a lead-zirconate catalyst
US5082816A (en) 1986-08-28 1992-01-21 The Standard Oil Company Lead-zirconate catalysts
US4720602A (en) 1986-09-08 1988-01-19 Mobil Oil Corporation Process for converting C2 to C12 aliphatics to aromatics over a zinc-activated zeolite
US5120332A (en) 1986-11-06 1992-06-09 The Haser Company Limited Gas resonance device
US5118899A (en) 1986-12-22 1992-06-02 Phillips Petroleum Company Composition of matter and method of oxidative conversion of organic compounds therewith
US5160502A (en) 1986-12-22 1992-11-03 Phillips Petroleum Company Composition of matter and method of oxidative conversion of organic compounds therewith
US5087787A (en) 1986-12-29 1992-02-11 Phillips Petroleum Company Method of oxidative conversion
DE3700132A1 (de) 1987-01-03 1988-07-14 Dow Chemical Gmbh Verfahren zum herstellen von ethylendichlorid
US4769504A (en) * 1987-03-04 1988-09-06 The United States Of America As Represented By The United States Department Of Energy Process for converting light alkanes to higher hydrocarbons
US4792642A (en) 1987-03-25 1988-12-20 Eastman Kodak Company Process for preparing iodinated aromatic compounds
US4795737A (en) 1987-03-25 1989-01-03 Eastman Kodak Company Process for the iodination of aromatic compounds over solid catalysts
US4886932A (en) 1987-03-30 1989-12-12 Atlantic Richfield Company Thin bed cofeed reaction system for methane conversion
CA1322769C (en) 1988-12-30 1993-10-05 John E. Stauffer Process for the chlorination of ethane
US4777321A (en) 1987-04-29 1988-10-11 Mobil Oil Corporation Feedstock preparation and conversion of oxygenates to olefins
US4775462A (en) 1987-06-22 1988-10-04 Uop Inc. Non-oxidative method of sweetening a sour hydrocarbon fraction
US4808763A (en) 1987-08-05 1989-02-28 Amoco Corporation Process for upgrading light paraffins
US4804797A (en) * 1987-08-24 1989-02-14 Gas Research Institute Production of commodity chemicals from natural gas by methane chlorination
US4783566A (en) 1987-08-28 1988-11-08 Uop Inc. Hydrocarbon conversion process
GB8724373D0 (en) 1987-10-17 1987-11-18 British Petroleum Co Plc Chemical process
US5157189A (en) * 1987-10-19 1992-10-20 Karra Sankaram B Conversion of light hydrocarbons to higher hydrocarbons
US4973786A (en) * 1987-10-19 1990-11-27 Karra Sankaram B Process for the pyrolytic oxidation of methane to higher molecular weight hydrocarbons and synthesis gas
US4814535A (en) 1987-12-15 1989-03-21 Mobil Oil Corporation Conversion of oxygenates to gasoline at variable inlet temperature
US4814536A (en) 1987-12-15 1989-03-21 Mobil Oil Corporation Conversion of oxygenates to gasoline at variable space velocity
GB8802731D0 (en) 1988-02-06 1988-03-09 British Petroleum Co Plc Chemical process
US5059744A (en) 1988-03-03 1991-10-22 Mobil Oil Corporation Reactor and recovery system for upgrading lower olefins
GB8806675D0 (en) 1988-03-21 1988-04-20 Shell Int Research Process for preparing liquid hydrocarbons
US4851602A (en) 1988-04-11 1989-07-25 Mobil Oil Corporation Alkanes and alkenes conversion to high octane gasoline
US4851606A (en) 1988-04-25 1989-07-25 Mobil Oil Corporation Control of waste water chemical oxygen demand in an oxygenate to hydrocarbon conversion process
US4886925A (en) 1988-05-02 1989-12-12 Mobil Oil Corp Olefins interconversion and etherification process
JPH07106998B2 (ja) 1988-05-17 1995-11-15 ダイキン工業株式会社 １，１，１−トリフルオロ−２，２−ジクロロエタンの製造方法
US5013793A (en) 1990-07-26 1991-05-07 Exxon Chemical Patents Inc. Dynamically cured thermoplastic olefin polymers and process for producing the same
US4990711A (en) 1988-06-23 1991-02-05 Mobil Oil Corporation Synthetic polyolefin lubricant blends having high viscosity indices
US4950822A (en) 1988-06-27 1990-08-21 Ethyl Corporation Olefin oligomer synlube process
US4899002A (en) 1988-07-25 1990-02-06 Mobil Oil Corp. Integrated staged conversion of methanol to gasoline and distillate
FR2635101B1 (fr) 1988-08-05 1990-09-28 Rhone Poulenc Chimie Procede de preparation du trifluoroethanol par hydrolyse, en phase gazeuse, du chlorotrifluoroethane
US4939311A (en) 1988-08-17 1990-07-03 Amoco Corporation Catalysts for the oxidative conversion of methane to higher hydrocarbons
US4956521A (en) 1988-10-06 1990-09-11 Uop Adsorption and isomerization of normal and mono-methyl paraffins
US5055634A (en) 1988-10-06 1991-10-08 Uop Adsorption and isomerization of normal and mono-methyl paraffins
US5055633A (en) 1988-10-06 1991-10-08 Uop Adsorption and isomerization of normal and mono-methyl paraffins
US5215648A (en) 1988-10-20 1993-06-01 Chevron Research And Technology Company Hydrocarbon conversion processes using SSZ-31
US4899001A (en) 1988-11-21 1990-02-06 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US5194244A (en) 1988-11-23 1993-03-16 Shell Oil Company Basic alkali metal-zeolite compositions
US4929781A (en) 1988-11-30 1990-05-29 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
US4895995A (en) 1988-12-02 1990-01-23 Uop Process for the simultaneous hydroconversion of a first feedstock comprising unsaturated, halogenated organic compounds and a second feedstock comprising saturated, halogenated organic compounds
EP0372183B1 (en) 1988-12-07 1997-01-22 Sumitomo Chemical Company, Limited Process for the production of 2,3-dimethylbutenes
US4939314A (en) 1988-12-19 1990-07-03 Mobil Oil Corporation Method for on-stream low-pressure regeneration of an oligomerization catalyst from a fluid-bed reactor operating at high pressure with hydrocarbons in a non-liquid phase
US5178748A (en) 1988-12-22 1993-01-12 Imperial Chemical Industries Catalytic reactions using zeolites
GB8829923D0 (en) 1988-12-22 1989-02-15 Ici Plc Zeolites
CA1304419C (en) 1988-12-22 1992-06-30 Raj N. Pandey Conversion of methane to gasoline-range hydrocarbons via isobutene
US4990696A (en) 1988-12-29 1991-02-05 Stauffer John E Methyl alcohol process
US4899000A (en) 1989-01-27 1990-02-06 Stauffer John E Production of allyl chloride
US5436378A (en) 1989-02-16 1995-07-25 Atochem Drying of hydrocarbon/hydrochloric acid/water admixtures
US5107051A (en) 1989-03-14 1992-04-21 Exxon Chemical Patents Inc. Halogen resistant hydrotreating process and catalyst
US4945175A (en) 1989-05-26 1990-07-31 Uop Dehydrocyclodimerization process start-up procedure
US5202511A (en) 1989-08-16 1993-04-13 The Dow Chemical Company Catalyst diluent for oxychlorination process
US5071815A (en) 1989-09-01 1991-12-10 British Columbia Research Corporation Method for producing catalysts
NO904072L (no) 1989-09-19 1991-03-20 Union Carbide Chem Plastic Soelvholdige katalysatorer for oksydativ kobling.
US5073656A (en) 1989-09-19 1991-12-17 Union Carbide Chemicals And Plastics Company, Inc. High ethylene to ethane processes for oxidative coupling
US5073657A (en) 1989-09-19 1991-12-17 Union Carbide Chemicals And Plastics Company Inc. Vapor phase modifiers for oxidative coupling
AU6259890A (en) 1989-09-19 1991-03-28 Union Carbide Chemicals And Plastics Company Inc. Low temperature catalysts for oxidative coupling processes
DE3933656A1 (de) 1989-10-09 1991-04-11 Basf Ag Verdunstungsarme polyesterharze
US5093533A (en) 1989-12-08 1992-03-03 Interstate Chemical, Inc. Blended gasolines and process for making same
US5208402A (en) 1989-12-08 1993-05-04 Interstate Chemical, Inc. Liquid fuels for internal combustion engines and process and apparatus for making same
US5026944A (en) 1989-12-20 1991-06-25 Energy Mines And Resources Canada Synthesis of isobutene from methane and acetylene
US4982024A (en) * 1989-12-26 1991-01-01 Ethyl Corporation Process for the selective dehydrohalogenation of an admixture of alkylhalides
US5004847A (en) 1989-12-27 1991-04-02 Ethyl Corporation Recovery of hexabromocyclododecane particles
US5026937A (en) 1989-12-29 1991-06-25 Uop Aromatization of methane using zeolite incorporated in a phosphorus-containing alumina
US4982041A (en) 1990-01-10 1991-01-01 Union Carbide Chemicals And Plastics Company Inc. Double perovskite catalysts for oxidative coupling
US5055625A (en) 1990-02-06 1991-10-08 Fred Neidiffer Gasoline additive composition and method for using same
US5026934A (en) 1990-02-12 1991-06-25 Lyondell Petrochemical Company Method for converting light hydrocarbons to olefins, gasoline and methanol
US5043502A (en) 1990-03-16 1991-08-27 Uop Production of xylenes from light aliphatic hydrocarbons via dehydrocyclodimerization and methylation
US5228888A (en) 1990-03-23 1993-07-20 The Boc Group, Inc. Economical air separator
US5107061A (en) 1990-04-06 1992-04-21 Exxon Chemical Patents Inc. Removal of organochlorides from hydrocarbon feed streams
US5087786A (en) * 1990-04-25 1992-02-11 Amoco Corporation Halogen-assisted conversion of lower alkanes
US5001293A (en) * 1990-04-25 1991-03-19 Amoco Corporation Halocarbon conversion
US5087779A (en) 1990-04-25 1992-02-11 Amoco Corporation Hydrocarbon halogenation
US5019652A (en) 1990-04-30 1991-05-28 The United States As Represented By The United States Department Of Energy Catalysts and method
US5139991A (en) 1990-04-30 1992-08-18 The United States Of American As Represented By The United States Department Of Energy Oxyhydrochlorination catalyst
US5068478A (en) 1990-05-25 1991-11-26 Energia Andina, Ltd. Producing alkenes and alkynes from alkanes and alkenes
GB9013859D0 (en) 1990-06-21 1990-08-15 Ici Plc Zeolites
GB9013916D0 (en) 1990-06-22 1990-08-15 Ici Plc Zeolites
US4988660A (en) 1990-06-25 1991-01-29 Union Carbide Chemicals And Plastics Company Inc. Double perovskite catalysts for oxidative coupling
US5082473A (en) 1990-07-23 1992-01-21 Keefer Bowie Extraction and concentration of a gas component
US5096469A (en) 1990-07-23 1992-03-17 Keefer Bowie Adsorptive gas separator with inertial energy exchange
US5013424A (en) 1990-07-30 1991-05-07 Uop Process for the simultaneous hydrogenation of a first feedstock comprising hydrocarbonaceous compounds and having a non-distillable component and a second feedstock comprising halogenated organic compounds
US5401890A (en) 1990-07-30 1995-03-28 Albemarle Corporation Process and apparatus for heat treating halogenated compounds
US5138112A (en) 1990-08-31 1992-08-11 Uop Process for converting a C2 -C6 aliphatic hydrocarbon to high octane transportable fuel
DE4029875A1 (de) 1990-09-21 1992-03-26 Hoechst Ag Verfahren zur inhibierung und zerstoerung von peroxiden in dialkylethern
JP2970683B2 (ja) 1990-10-12 1999-11-02 日石三菱株式会社 水素化脱アルキル触媒を用いた水素化脱アルキル法
US5085674A (en) 1990-10-25 1992-02-04 Union Carbide Industrial Gases Technology Corporation Duplex adsorption process
US5071449A (en) 1990-11-19 1991-12-10 Air Products And Chemicals, Inc. Gas separation by rapid pressure swing adsorption
US5107032A (en) 1990-11-20 1992-04-21 Noramco, Inc. Process for the preparation of o-phthalaldehydes
CA2097435C (en) * 1990-12-06 2002-02-19 Krishnan Viswanathan Process for the production of ethylene and mixtures containing ethylene
US5055235A (en) 1990-12-12 1991-10-08 Ethyl Corporation Bromination process
US5105046A (en) 1990-12-12 1992-04-14 Amoco Corporation Oxidative conversion of lower alkanes to higher hydrocarbons via fluorine-containing materials
US5223471A (en) 1990-12-12 1993-06-29 Amoco Corporation Fluorine-containing materials
US5233113A (en) 1991-02-15 1993-08-03 Catalytica, Inc. Process for converting lower alkanes to esters
US5306855A (en) 1991-02-15 1994-04-26 Catalytica, Inc. Catalytic process for converting lower alkanes to esters, alcohols, and to hydrocarbons
GB9105167D0 (en) 1991-03-12 1991-04-24 Ici Plc Chemical process
US5237115A (en) 1991-03-15 1993-08-17 Phillips Petroleum Company Integrated olefin processing
US5188725A (en) 1991-03-15 1993-02-23 Mobil Oil Corporation Fluidized catalyst process for production and etherification of olefins
FR2674769B1 (fr) 1991-04-04 1994-04-29 Inst Francais Du Petrole Catalyseur du type galloaluminosilicate contenant du gallium, un metal noble de la famille du platine et au moins un metal additionnel, et son utilisation en aromatisation des hydrocarbures.
EP0510238A1 (en) 1991-04-26 1992-10-28 NOVAMONT S.p.A. Process for producing lower poliols and mixtures thereof
US5288677A (en) 1991-06-28 1994-02-22 Exxon Chemical Patents Inc. Immobilized Lewis acid catalysts
GB9116172D0 (en) 1991-07-26 1991-09-11 Thames Water Utilities A method of and apparatus for treating a fluid
US5399258A (en) 1991-08-15 1995-03-21 Mobil Oil Corporation Hydrocarbon upgrading process
MY108348A (en) 1991-08-16 1996-09-30 Exxon Chemical Patents Inc Ester free ethers.
US5264635A (en) 1991-10-03 1993-11-23 Mobil Oil Corporation Selective cracking and etherification of olefins
US5245109A (en) 1991-10-11 1993-09-14 Amoco Corporation Hydrocarbon conversion
JP3120292B2 (ja) 1991-10-18 2000-12-25 イハラケミカル工業株式会社 脂肪族カルボン酸ハロメチルエステル類の製造法
US5276240A (en) * 1991-10-18 1994-01-04 Board Of Regents, The University Of Texas System Catalytic hydrodehalogenation of polyhalogenated hydrocarbons
US5385650A (en) 1991-11-12 1995-01-31 Great Lakes Chemical Corporation Recovery of bromine and preparation of hypobromous acid from bromide solution
US5268518A (en) 1991-11-15 1993-12-07 The Dow Chemical Company Reactor feed pipe design
US5191142A (en) 1991-12-23 1993-03-02 Amoco Corporation Process for converting methanol to olefins or gasoline
AU3610793A (en) 1992-02-04 1993-09-01 Catalytica, Inc. Cebr3 catalyst and process for producing bromine
US6169218B1 (en) 1992-02-10 2001-01-02 Catalytic Distillation Technologies Selective hydrogenation of highly unsaturated compounds in hydrocarbon streams
CA2088939A1 (en) 1992-03-10 1993-09-11 Istvan T. Horvath Low temperature conversion of alkanes
US5354916A (en) 1992-03-10 1994-10-11 Exxon Research And Engineering Company Low temperature conversion of alkanes
US5202506A (en) 1992-04-02 1993-04-13 E. I. Du Pont De Nemours And Company Oxidative drown process for 2-perfluoroalkylethyl alcohols
US5185479A (en) 1992-04-21 1993-02-09 Stauffer John E Process for methyl alcohol
CA2097090A1 (en) 1992-06-02 1993-12-03 Quang N. Le Process for the production of tertiary alkyl ether rich fcc gasoline
US5395981A (en) 1992-06-22 1995-03-07 Uop Hydrocarbon conversion by catalytic distillation
US5254790A (en) 1992-07-01 1993-10-19 Phillips Petroleum Company Integrated process for producing motor fuels
US5284990A (en) 1992-07-16 1994-02-08 Stratco, Inc. Method for converting a hydrogen fluoride alkylation unit to a sulfuric acid alkylation unit
US5276242A (en) 1992-08-26 1994-01-04 Phillips Petroleum Company Alkylation process
US5243114A (en) 1992-09-08 1993-09-07 Mobil Oil Corporation Oligomerization of alpha-olefins over layered silicate compositions containing pillars of silica and group VIB metal oxide
IT1255710B (it) 1992-10-01 1995-11-10 Snam Progetti Procedimento integrato per produrre olefine da miscele gassose contenenti metano
US5453557A (en) 1992-10-01 1995-09-26 The Dow Chemical Company Processes for converting chlorinated byproducts and waste products to useful materials
US5430214A (en) 1992-10-01 1995-07-04 The Dow Chemical Company Hydrodehalogenation process and catalyst for use therein
US5276226A (en) 1992-10-05 1994-01-04 Exxon Research & Engineering Company Low temperature halogenation of alkanes
US5300126A (en) 1992-10-19 1994-04-05 Mobil Oil Corporation Process for improving olefin etherification catalyst life
US5243098A (en) * 1992-11-04 1993-09-07 Energia Andina Ltd. Conversion of methane to methanol
US5744669A (en) 1992-11-25 1998-04-28 Uop Process for the conversion of a halogenated organic stream containing trace quantities of organic nitrates
US5817904A (en) 1992-12-11 1998-10-06 Repsol Petroleo S.A. Method for the conversion of methane into longer chain hydrocarbons
TW291486B (zh) 1992-12-17 1996-11-21 Exxon Chemical Patents Inc
US5470377A (en) 1993-03-08 1995-11-28 Whitlock; David R. Separation of solutes in gaseous solvents
US5354931A (en) 1993-03-10 1994-10-11 Uop Process for hydrotreating an organic feedstock containing oxygen compounds and a halogen component
US5994604A (en) 1993-03-17 1999-11-30 Lockheed Martin Idaho Technologies Company Method and apparatus for low temperature destruction of halogenated hydrocarbons
GB9407257D0 (en) 1993-04-22 1994-06-08 Ici Plc Vaporisation of liquids
US5382743A (en) 1993-04-26 1995-01-17 Mobil Oil Corporation Skeletal isomerization of n-pentenes using ZSM-35 in the presence of hydrogen
US5465699A (en) 1993-06-01 1995-11-14 Volkswagen Ag Intake pipe arrangement for an internal combustion engine having individual arc-shaped cylinder intake pipes
US5382704A (en) 1993-06-30 1995-01-17 E. I. Du Pont De Nemours And Company Fluorinated methyl ethers
US5382744A (en) 1993-07-12 1995-01-17 Phillips Petroleum Company Control of synthetic isopentane production during alkylation of amylenes
US5510525A (en) 1993-07-22 1996-04-23 Gas Research Institute Direct catalytic oxidative carbonylation of lower alkanes to acids
IT1265051B1 (it) 1993-08-06 1996-10-28 Eniricerche Spa Processo per l'alchilazione di idrocarburi alifatici con olefine
US5500297A (en) 1993-08-09 1996-03-19 The Trustees Of Princeton University Electron acceptor compositions technical field
US5906892A (en) 1993-08-09 1999-05-25 The Trustees Of Princeton University Electron acceptor compositions on polymer templates
US5695890A (en) 1993-08-09 1997-12-09 The Trustees Of Princeton University Heterolamellar photoelectrochemical films and devices
US5430210A (en) 1993-08-27 1995-07-04 Mobil Oil Corporation Selective hydrogen combustion processes
GB9318507D0 (en) 1993-09-07 1993-10-20 Evc Tech Ag Vinyl chloride production process
GB9318505D0 (en) 1993-09-07 1993-10-20 Evc Tech Ag By-product recycling in oxychlorination process
US5371313A (en) 1993-11-24 1994-12-06 Polysar Rubber Corporation Purification of hydrocarbon streams
US5600045A (en) 1993-12-02 1997-02-04 The Dow Chemical Company Process for conversion of crude hydrocarbon mixtures
US5414173A (en) 1993-12-22 1995-05-09 The Dow Chemical Company Process of preparing cyclopentadiene and substituted derivatives thereof
GB9400569D0 (en) 1994-01-13 1994-03-09 Rhone Poulenc Chemicals Process for the production of substituted aromatic hydrocarbons from corresponding anilines by dediazoniation
EP0746529B1 (en) 1994-02-18 2000-01-05 Chevron Chemical Company LLC Zeolite ssz-42
US5565092A (en) 1994-03-16 1996-10-15 Exxon Chemical Patents Inc. Halogen resistant hydrogenation process and catalyst
US5780703A (en) 1994-05-02 1998-07-14 Mobil Oil Corporation Process for producing low aromatic diesel fuel with high cetane index
US5565616A (en) 1994-05-09 1996-10-15 Board Of Regents, The University Of Texas System Controlled hydrothermal processing
US5444168A (en) 1994-05-16 1995-08-22 Mobil Oil Corporation Process for the production of symmetrical ethers from secondary alcohols
US5401894A (en) 1994-06-07 1995-03-28 Uop Process for the treatment of halogenated organic feedstocks
US5591421A (en) 1994-07-11 1997-01-07 Chevron U.S.A. Inc. Zeolite SSZ-41
US5523503A (en) 1994-07-13 1996-06-04 Uop Cocurrent simulated moving bed hydrocarbon alkylation process
GB9414972D0 (en) 1994-07-26 1994-09-14 Bnfl Fluorchem Ltd Halogenation reactions
US5661097A (en) 1994-08-12 1997-08-26 The Dow Chemical Company Supported olefin polymerization catalyst
EP0704424B1 (en) 1994-09-28 1998-12-30 Showa Denko Kabushiki Kaisha 3-Alkoxypropionic ester derivative, olefin polymerization catalyst, and process for preparation of polyolefin
US6117371A (en) 1994-10-05 2000-09-12 Great Lakes Chemical Corporation Continuous bromination process and products thereof
JPH10506910A (ja) 1994-10-05 1998-07-07 グレート・レークス・ケミカル・コーポレーション 連続的臭素化法およびその生成物
GB2294262B (en) 1994-10-20 1998-07-08 Evc Tech Ag Single stage fixed bed oxychlorination of ethylene
CA2203115C (en) 1994-10-20 2006-09-19 Pierluigi Fatutto Single stage fixed bed oxychlorination of ethylene
US5489727A (en) 1994-10-28 1996-02-06 Phillips Petroleum Company Isopentane disproportionation
US5693191A (en) 1994-11-23 1997-12-02 The Dow Chemical Company Process for recovery of anhydrous hydrogen chloride from mixtures with non-condensable gases
CN1051071C (zh) 1994-11-24 2000-04-05 索尔维公司 将氯代烷转化为较低度氯代的烯烃的方法
US5486627A (en) * 1994-12-02 1996-01-23 The Dow Chemical Company Method for producing epoxides
US5639930A (en) 1995-01-04 1997-06-17 Penick; Joe E. Process of producing alkylates
DK171707B1 (da) 1995-02-03 1997-04-01 Topsoe Haldor As Fremgangsmåde til fremstilling af dimetylæter i brændstofkvalitet
US5905169A (en) 1995-03-20 1999-05-18 E. I. Du Pont De Nemours And Company Process for producing polyfluoroacyl compositions
US5600043A (en) 1995-03-27 1997-02-04 The Geon Company Oxychlorination process
DE69614844T2 (de) 1995-04-21 2002-04-11 Procter & Gamble Shampoos mit konditionierungsmittel aus unlöslichen silikon, und kationischem polymer
FR2734172B1 (fr) 1995-05-19 1997-06-20 Air Liquide Dispositif et procede de separation de gaz par adsorption
DE19520612A1 (de) 1995-06-06 1996-12-12 Bayer Ag Verfahren zur Herstellung von Benzylalkohol
US5847224A (en) 1995-06-23 1998-12-08 Global Octanes Corporation Method for improving the color of MTBE, ETBE and TAME
US5977402A (en) 1995-07-20 1999-11-02 Sumitomo Chemical Company, Limited Processes for preparing 4-tert.-butylcyclohexanol and 4-tert.-butylcyclohexyl acetate
FR2736911A1 (fr) 1995-07-20 1997-01-24 Inst Francais Du Petrole Catalyseur liquide d'alkylation aliphatique
US5675052A (en) 1995-09-15 1997-10-07 The Boc Group, Inc. Hydrocarbon alkylation process
US5705712A (en) 1995-10-05 1998-01-06 Uop Integrated process for producing diisopropyl ether, an isopropyl tertiary alkyl ether and isopropyl alcohol
US5705729A (en) 1995-11-22 1998-01-06 Mobil Oil Corporation Isoparaffin-olefin alkylation process
FR2743079B1 (fr) 1995-12-27 1998-02-06 Inst Francais Du Petrole Procede et dispositif d'hydrogenation selective par distillation catalytique comportant une zone reactionnelle a co-courant ascendant liquide-gaz
DE19548876A1 (de) 1995-12-27 1997-07-03 Bayer Ag Verfahren zur kontinuierlichen Herstellung von Benzylalkohol
FR2743510B1 (fr) 1996-01-11 1998-04-03 Total Raffinage Distribution Nouveau catalyseur d'alkylation, son procede de preparation et son utilisation dans des procedes d'alkylation
US6090312A (en) 1996-01-31 2000-07-18 Ziaka; Zoe D. Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions
AU692723B2 (en) 1996-02-01 1998-06-11 Phillips Petroleum Company Catalyst composition and process for selecting hydrogenation of diolefins
US6096933A (en) 1996-02-01 2000-08-01 Phillips Petroleum Company Hydrocarbon hydrogenation and catalyst therefor
DE19603901A1 (de) 1996-02-03 1997-08-07 Krupp Uhde Gmbh Verfahren zur Gewinnung von Reinaromaten aus Reformatbenzin und Vorrichtung zur Durchführung des Verfahrens
SE517561C2 (sv) 1996-03-04 2002-06-18 Aga Ab Förfarande och anordning för framställning av en gas genom separation från en gasblandning
US5663474A (en) 1996-03-07 1997-09-02 Alliedsignal Inc. Alkylation process using hydrogen fluoride-containing alkylation catalysts
US5684213A (en) 1996-03-25 1997-11-04 Chemical Research & Licensing Company Method for the preparation of dialkyl ethers
US5675046A (en) 1996-04-10 1997-10-07 Showa Denko K.K. Process for producing perfluorocarbon
US5898086A (en) 1996-04-19 1999-04-27 Henkel Corporation Process for making alkyl ether glycerols
USRE38493E1 (en) 1996-04-24 2004-04-13 Questair Technologies Inc. Flow regulated pressure swing adsorption system
US6191324B1 (en) 1996-04-24 2001-02-20 Union Carbide Chemicals & Plastics Technology Corporation Processes for producing unsaturated alcohols
CN1078194C (zh) 1996-05-29 2002-01-23 埃克森美孚化学专利公司 从脂族烃制备芳族化合物的方法
AU3232997A (en) 1996-06-07 1998-01-05 Chevron U.S.A. Inc. Zeolite me-utd-1
US5720858A (en) 1996-07-17 1998-02-24 The United States Of America As Represented By The United States Department Of Energy Method for the photocatalytic conversion of methane
US5708246A (en) 1996-08-28 1998-01-13 Battelle Memorial Institute Method of photocatalytic conversion of C-H organics
CN1104402C (zh) * 1996-10-17 2003-04-02 埃克森美孚化学专利公司 使用大晶体沸石催化剂的烃转化方法
HU220573B1 (hu) 1996-11-18 2002-03-28 AGRO-CHEMIE Növényvédőszer Gyártó, Értékesítő és Forgalmazó Kft. Eljárás benzil-éterek előállítására
JP4278067B2 (ja) 1996-11-27 2009-06-10 アルベマーレ ネザーランズ ビー．ブイ． 炭化水素のアルキル化法
US5895831A (en) 1996-12-04 1999-04-20 Uop Llc Solid catalyst alkylation process
US7182871B2 (en) 1996-12-17 2007-02-27 Global Biosciences, Inc. Wastewater treatment with alkanes
US6669846B2 (en) 1996-12-17 2003-12-30 Global Biosciences, Inc. Wastewater treatment with alkanes
US5952538A (en) 1996-12-31 1999-09-14 Exxon Chemical Patents Inc. Use of short contact time in oxygenate conversion
WO1998040333A1 (de) 1997-03-07 1998-09-17 Basf Aktiengesellschaft Verbessertes verfahren zur herstellung von cyclopropylacetylen
US6093306A (en) 1997-04-07 2000-07-25 Solar Reactor Technologies Inc. Comprehensive system for utility load leveling, hydrogen production, stack gas cleanup, greenhouse gas abatement, and methanol synthesis
US5782936A (en) 1997-04-23 1998-07-21 Suburban Propane, L.P. Additive compositions for LPG fuel
SG74047A1 (en) 1997-04-30 2000-07-18 Mitsubishi Chem Corp Process for producing alkylene glycol
US6018088A (en) 1997-05-07 2000-01-25 Olah; George A. Superacid catalyzed formylation-rearrangement of saturated hydrocarbons
DE19721301C1 (de) * 1997-05-21 1998-10-01 Basf Ag Verfahren zur Hydrolyse von Alkylmonohalogeniden
US6056804A (en) 1997-06-30 2000-05-02 Questor Industries Inc. High frequency rotary pressure swing adsorption apparatus
AU8395898A (en) 1997-07-11 1999-02-08 University Of Southern California Charge generators in heterolamellar multilayer thin films
US6465969B1 (en) 1997-08-04 2002-10-15 Lumimove, Inc. Electroluminescent display intelligent controller
US5856584A (en) 1997-08-06 1999-01-05 The Nutrasweet Company Preparation of 3,3-dimethylbutyraldehyde by oxidation of 3, 3-dimethylbutanol
US5928488A (en) 1997-08-26 1999-07-27 David S. Newman Electrolytic sodium sulfate salt splitter comprising a polymeric ion conductor
DK128697A (da) 1997-11-12 1999-05-13 Niels J Bjerrum Katalyseproces
DE19755636A1 (de) 1997-12-15 1999-06-17 Bayer Ag Verfahren zur elektrochemischen Aufarbeitung von HCl-Gas zu hochreinem Chlor
FR2773496B1 (fr) 1998-01-14 2000-03-03 Inst Francais Du Petrole Procede de separation par decantation dans plusieurs zones distinctes
US5882614A (en) * 1998-01-23 1999-03-16 Exxon Research And Engineering Company Very low sulfur gas feeds for sulfur sensitive syngas and hydrocarbon synthesis processes
US5968236A (en) 1998-02-20 1999-10-19 Bassine; Stuart Valve free oxygen concentrator
US6187983B1 (en) 1998-04-29 2001-02-13 Exxon Chemical Patents Inc Converting oxygenates to olefins in the presence of electromagnetic energy
US5998679A (en) * 1998-05-20 1999-12-07 Jlm Technology, Ltd. Methods for converting lower alkanes and alkanes to alcohols and diols
US5983476A (en) 1998-06-09 1999-11-16 Uop Llc Conversion of an HF alkylation unit
US6096932A (en) 1999-07-27 2000-08-01 E. I. Du Pont De Nemours And Company Fluorocarbon manufacturing process
EP0976705A1 (en) 1998-07-30 2000-02-02 Ube Industries, Ltd. Method of producing a phenolalkylether compound
IT1302003B1 (it) 1998-08-05 2000-07-20 Enitecnologie Spa Procedimento per la trasformazione selettiva di idrocarburi.
US6087294A (en) 1998-08-12 2000-07-11 Kansas State University Research Foundation Dispersion and stabilization of reactive atoms on the surface of metal oxides
FR2782280B1 (fr) 1998-08-12 2000-09-22 Inst Francais Du Petrole Catalyseurs supportes utilisables dans des reactions de transformation de composes organiques
US6921597B2 (en) 1998-09-14 2005-07-26 Questair Technologies Inc. Electrical current generation system
US6455650B1 (en) 1998-10-05 2002-09-24 The B.F. Goodrich Company Catalyst and methods for polymerizing cycloolefins
US6903171B2 (en) 1998-10-05 2005-06-07 Promerus, Llc Polymerized cycloolefins using transition metal catalyst and end products thereof
WO2000021912A1 (en) 1998-10-12 2000-04-20 Great Lakes (Uk) Limited Preparation of cyclopropylethyne and intermediates for preparation of cyclopropylethyne
US6127588A (en) 1998-10-21 2000-10-03 Phillips Petroleum Company Hydrocarbon hydrogenation catalyst and process
US6002059A (en) 1998-10-28 1999-12-14 Mobil Oil Corporation Process for upgrading natural gas
EP0999183B1 (fr) 1998-11-02 2003-06-18 Institut Francais Du Petrole Procédé de préparation d'une zéolithe de type structural EUO a l'aide de precurseurs du structurant et son utilisation comme catalyseur d'isomerisation des AC8
DK0999182T3 (da) 1998-11-02 2003-07-14 Inst Francais Du Petrole Fremgangsmåde til fremstilling af en zeolit af strukturtypen EUO ved hjælp af kim af zeolitiske materialer og anvendelse heraf som katalysator til isomerisering af aromatiske forbindelser med otte carbonatomer
US6130260A (en) 1998-11-25 2000-10-10 The Texas A&M University Systems Method for converting natural gas to liquid hydrocarbons
US6936565B2 (en) 1999-01-12 2005-08-30 Hyperion Catalysis International, Inc. Modified carbide and oxycarbide containing catalysts and methods of making and using thereof
US6239057B1 (en) 1999-01-15 2001-05-29 Uop Llc Catalyst for the conversion of low carbon number aliphatic hydrocarbons to higher carbon number hydrocarbons, process for preparing the catalyst and process using the catalyst
US6114593A (en) 1999-01-27 2000-09-05 Phillips Petroleum Company Method for reducing organic fluoride levels in hydrocarbons
US6417422B1 (en) 1999-02-22 2002-07-09 Symyx Technologies, Inc. Ni catalysts and methods for alkane dehydrogenation
US6143939A (en) 1999-02-26 2000-11-07 The United States Of America As Represented By The United States Department Of Energy Method of dehalogenation using diamonds
WO2000056795A1 (en) 1999-03-23 2000-09-28 Carnegie Mellon University Catalytic processes for the controlled polymerization of free radically (co)polymerizable monomers and functional polymeric systems prepared thereby
US7220391B1 (en) 1999-03-25 2007-05-22 University Of Central Florida Research Foundation, Inc. UV photochemical option for closed cycle decomposition of hydrogen sulfide
US6248218B1 (en) 1999-03-25 2001-06-19 Clovis A. Linkous Closed cycle photocatalytic process for decomposition of hydrogen sulfide to its constituent elements
US7273957B2 (en) 1999-05-04 2007-09-25 Catalytic Distillation Technologies Process for the production of gasoline stocks
US6545192B2 (en) 1999-05-11 2003-04-08 Shell Oil Company Process for separating olefins from saturated hydrocarbons
FR2793706B1 (fr) 1999-05-18 2001-08-03 Total Raffinage Distribution Support catalytique a base d'oxyde d'un metal du groupe ivb de la classification periodique des elements, sa preparation et ses utilisations
US6444223B1 (en) * 1999-05-28 2002-09-03 Alkermes Controlled Therapeutics, Inc. Method of producing submicron particles of a labile agent and use thereof
US6727400B2 (en) 1999-06-08 2004-04-27 Triosyn Holdings, Inc. Deactivation of toxic chemical agents
AU5381200A (en) 1999-06-09 2001-01-02 Questair Technologies, Inc. Rotary pressure swing adsorption apparatus
US6248931B1 (en) 1999-06-30 2001-06-19 Uop Llc Membrane process for the recovery of halides from hydrocarbon-containing streams
SE520971C2 (sv) 1999-08-20 2003-09-16 Perstorp Ab Förfarande för tillverkning av en eteralkohol
US6309453B1 (en) 1999-09-20 2001-10-30 Xerox Corporation Colorless compounds, solid inks, and printing methods
FR2798922B1 (fr) 1999-09-29 2001-12-14 Inst Francais Du Petrole Procede de preparation d'une zeolithe de type structural mtt utilisant des germes de materiaux zeolithiques
FR2798923B1 (fr) 1999-09-29 2001-12-14 Inst Francais Du Petrole Procede de preparation d'une zeolithe de type structural mtt utilisant des precurseurs specifiques du structurant
US20020102672A1 (en) 1999-10-04 2002-08-01 Joseph Mizrahi Process for producing a purified lactic acid solution
DE19949211A1 (de) 1999-10-13 2001-05-31 Veba Oel Ag Verfahren zur Herstellung von n-Alkanen aus Mineralölfraktionen und Katalysator zur Durchführung des Verfahrens
US6372949B1 (en) 1999-10-15 2002-04-16 Mobil Oil Corporation Single stage process for converting oxygenates to gasoline and distillate in the presence of undimensional ten member ring zeolite
US6265505B1 (en) 1999-11-18 2001-07-24 Univation Technologies, Llc Catalyst system and its use in a polymerization process
US6380328B1 (en) 1999-12-10 2002-04-30 Univation Technologies, Llc Catalyst systems and their use in a polymerization process
US6518474B1 (en) 1999-10-29 2003-02-11 Huntsman International Llc Process for producing isobutylene from tertiary butyl alcohol
US6909024B1 (en) 1999-11-22 2005-06-21 The Dow Chemical Company Process for the conversion of ethylene to vinyl chloride and novel catalyst compositions useful for such process
KR100780562B1 (ko) 1999-11-22 2007-11-29 다우 글로벌 테크놀로지스 인크. 에틸렌을 비닐 클로라이드로 전환시키는 방법 및 당해 방법에 사용하기에 유용한 촉매
US6933417B1 (en) 1999-11-22 2005-08-23 Dow Global Technologies Inc. Process for vinyl chloride manufacture from ethane and ethylene with partial CHl recovery from reactor effluent
US6680415B1 (en) 1999-11-22 2004-01-20 Dow Global Technologies Inc. Oxyhalogenation process using catalyst having porous rare earth halide support
US6797845B1 (en) 1999-11-22 2004-09-28 Dow Global Technologies Inc. Process for vinyl chloride manufacture from ethane and ethylene with immediate HCl recovery from reactor effluent
US6514319B2 (en) 1999-12-09 2003-02-04 Questair Technologies Inc. Life support oxygen concentrator
US6956140B2 (en) 1999-12-14 2005-10-18 Halocarbon Products Corporation Hydrothermal hydrolysis of halogenated compounds
KR100715637B1 (ko) 1999-12-14 2007-05-08 다이셀 가가꾸 고교 가부시끼가이샤 케톤, 알코올 및 하이드로과산화물의 제조 방법
US6376731B1 (en) 2000-01-14 2002-04-23 Arco Chemical Technology, L.P. Selective olefin oligomerization
US7094934B2 (en) 2000-02-02 2006-08-22 Daikin Industries, Ltd. Production process of hydrofluorocarbons
IT1317757B1 (it) 2000-02-03 2003-07-15 Enitecnologie Spa Metodo per la preparazione di idrocarburi idrogenati.
FR2805255B1 (fr) 2000-02-21 2002-04-12 Inst Francais Du Petrole Zeolithe mtt comprenant des cristaux et des agregats de cristaux de granulometries specifiques et son utilisation comme catalyseur d'isomerisation des paraffines lineaires
US6566572B2 (en) 2000-03-06 2003-05-20 Wako Pure Chemical Industries, Ltd. Process for producing 9,10-diphenylanthracene
US6475463B1 (en) 2000-03-07 2002-11-05 Chevron U.S.A. Inc. Zeolite SSZ-55
US6632416B2 (en) 2000-05-31 2003-10-14 Chevron U.S.A. Inc. Zeolite SSZ-53
US6710213B2 (en) 2000-03-31 2004-03-23 Showa Denko K.K. Production process and use for propargyl alcohol and its intermediate
US6395945B1 (en) 2000-03-31 2002-05-28 Phillips Petroleum Company Integrated hydroisomerization alkylation process
CA2306311C (en) 2000-04-20 2007-04-10 Quest Air Gases Inc. Absorbent laminate structures
FR2808533B1 (fr) 2000-05-02 2002-08-16 Inst Francais Du Petrole Huile synthetique a haut indice de viscosite et faible point d'ecoulement
EP1151980A1 (en) 2000-05-03 2001-11-07 Solvias AG Catalytic halogenation of activated methylene and methine compound
AU2001266868A1 (en) 2000-06-30 2002-01-14 Chevron U.S.A. Inc. Synthesis of high quality normal alpha olefins
FR2812301B1 (fr) 2000-07-26 2003-04-04 Inst Francais Du Petrole Procede flexible de production de bases huiles et de distillats moyens a partir de charge contenant des heteroatomes
IT1318680B1 (it) 2000-08-11 2003-08-27 Enichem Spa Processo per la produzione in continuo di ossidi olefinici.
IT1318682B1 (it) 2000-08-11 2003-08-27 Enichem Spa Procedimento integrato per la preparazione di ossidi olefinici.
US6495484B1 (en) 2000-08-28 2002-12-17 Univation Technologies, Llc Catalyst system and its use in a polymerization process
US6585953B2 (en) 2000-09-07 2003-07-01 Wisconsin Alumni Research Foundation Synthesis of 17F labeled fluoroalkanes
FR2813809B1 (fr) 2000-09-11 2003-07-25 Air Liquide Colonne a garnissage d'echange de chaleur et/ou de matiere
US6518476B1 (en) 2000-09-18 2003-02-11 Union Carbide Chemicals & Plastics Technology Corporation Methods for manufacturing olefins from lower alkans by oxidative dehydrogenation
ZA200108461B (en) 2000-10-27 2002-06-06 Celanese Chem Europe Gmbh Process of telomerizing conjugated dienes.
US6552241B1 (en) 2000-10-31 2003-04-22 Conocophillips Company Alkylation process
HUP0204129A3 (en) 2000-11-29 2004-08-30 Vintron Gmbh Method for producing 1,2-dichloroethane
AU2002215752A1 (en) 2000-12-08 2002-06-18 Denis Connor Methods and apparatuses for gas separation by pressure swing adsorption with partial gas product feed to fuel cell power source
CA2329475A1 (en) 2000-12-11 2002-06-11 Andrea Gibbs Fast cycle psa with adsorbents sensitive to atmospheric humidity
FR2818284B1 (fr) 2000-12-15 2006-08-04 Inst Francais Du Petrole Procede flexible ameliore de production de bases huiles et distillats moyens avec une conversion-hydroisomerisation suivie d'un deparaffinage catalytique
US6511526B2 (en) 2001-01-12 2003-01-28 Vbox, Incorporated Pressure swing adsorption gas separation method and apparatus
US6538162B2 (en) 2001-01-30 2003-03-25 Exxonmobil Chemical Patents Inc. Method for converting alkanes to oxygenates
US6509485B2 (en) 2001-02-22 2003-01-21 Sri International Preparation of epoxides from alkanes using lanthanide-promoted silver catalysts
US7064240B2 (en) 2001-02-23 2006-06-20 Showa Denko K.K. Process for producing perfluorocarbons and use thereof
US20030196680A1 (en) 2002-04-19 2003-10-23 Dielectric Systems, Inc Process modules for transport polymerization of low epsilon thin films
US7019182B2 (en) * 2001-04-18 2006-03-28 Grt, Inc. Method of hydrocarbon preservation and environmental protection
US7230150B2 (en) 2001-04-18 2007-06-12 Grt, Inc. Zone reactor
US6472572B1 (en) 2001-06-20 2002-10-29 Grt, Inc. Integrated process for synthesizing alcohols and ethers from alkanes
US6452058B1 (en) * 2001-05-21 2002-09-17 Dow Global Technologies Inc. Oxidative halogenation of C1 hydrocarbons to halogenated C1 hydrocarbons and integrated processes related thereto
WO2002094752A1 (en) 2001-05-23 2002-11-28 Dow Global Technologies Inc. Process for vinyl chloride manufacture from ethane and ethylene with air feed and alternative hcl processing methods
JP4275952B2 (ja) 2001-05-23 2009-06-10 ダウ グローバル テクノロジーズ インコーポレイティド Ｃ３＋炭化水素の酸化的ハロゲン化および任意的な脱水素
CN1649808A (zh) 2001-05-23 2005-08-03 陶氏环球技术公司 从单碳原料的卤乙烯生产
DK1527035T3 (da) 2001-06-08 2015-06-08 Albemarle Netherlands Bv Kontinuerlig fremgangsmåde til alkyleringen af carbonhydrider
US7001872B2 (en) 2001-06-11 2006-02-21 Halliburton Energy Services, Inc. Subterranean formation treating fluid and methods of fracturing subterranean formations
US20030078456A1 (en) * 2001-06-20 2003-04-24 Aysen Yilmaz Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes
US7161050B2 (en) * 2001-06-20 2007-01-09 Grt, Inc. Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes
US6465699B1 (en) * 2001-06-20 2002-10-15 Gri, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US6486368B1 (en) * 2001-06-20 2002-11-26 Grt, Inc. Integrated process for synthesizing alcohols, ethers, and olefins from alkanes
US20030069452A1 (en) * 2001-06-20 2003-04-10 Sherman Jeffrey H. Method and apparatus for synthesizing from alcohols and ethers from alkanes, alkenes, and aromatics
US20050192468A1 (en) * 2001-06-20 2005-09-01 Sherman Jeffrey H. Hydrocarbon conversion process improvements
US6518471B1 (en) 2001-06-25 2003-02-11 Exxonmobil Chemical Patents Inc. Selective production of meta-diisopropylbenzene
US6440894B1 (en) 2001-06-25 2002-08-27 Exxonmobil Chemical Patents, Inc. Methods of removing halogen from non-zeolitic molecular sieve catalysts
EP1404443A4 (en) 2001-06-28 2009-09-23 Honeywell Int Inc PROCESS FOR PREPARING A FLUORATION CATALYST
US20030065239A1 (en) 2001-06-29 2003-04-03 Peter Zhu Non-hazardous basic neutralization of aldehydes
US6646102B2 (en) 2001-07-05 2003-11-11 Dow Global Technologies Inc. Process for manufacturing an alpha-dihydroxy derivative and epoxy resins prepared therefrom
US6540905B1 (en) 2001-07-13 2003-04-01 Chevron U.S.A. Inc. Hydrocarbon conversion using zeolite SSZ-58
US6616830B2 (en) 2001-07-13 2003-09-09 Chevron U.S.A. Inc. Hydrocarbon conversion using zeolite SSZ-57
US6547958B1 (en) 2001-07-13 2003-04-15 Chevron U.S.A. Inc. Hydrocarbon conversion using zeolite SSZ-59
US6867302B2 (en) 2001-07-13 2005-03-15 Board Of Trustees Of Michigan State University Process for the catalytic synthesis of biaryls and polymers from aryl compounds
US7094936B1 (en) 2001-07-20 2006-08-22 Great Lakes Chemical Corporation Process for preparing halogenated alkanes
EP1414777A1 (en) 2001-08-03 2004-05-06 Eastman Chemical Company Vapor phase carbonylation process using iridium-gold co-catalysts
FR2828193B1 (fr) 2001-08-03 2004-04-02 Atofina Nouveau procede de preparation du 1,1,1,-trifluoro-2,2-dichloroethane
US6858770B2 (en) 2001-08-21 2005-02-22 Catalytic Distillation Technologies Paraffin alkylation
US6632971B2 (en) 2001-08-30 2003-10-14 Exxonmobil Chemical Patents Inc. Process for converting natural gas to higher value products using a methanol refinery remote from the natural gas source
US6797851B2 (en) 2001-08-30 2004-09-28 Exxonmobil Chemical Patents Inc. Two catalyst process for making olefin
US6552238B1 (en) 2001-08-31 2003-04-22 Vulcan Chemicals Separation of heavy ends from streams of halogenated alkanes
WO2003022827A1 (en) 2001-09-11 2003-03-20 Grt, Inc. Process for synthesizing olefin oxides
JP4256777B2 (ja) 2001-09-14 2009-04-22 東ソ−・エフテック株式会社 ２，２，２−トリフルオロエタノールの製造方法
JP4014856B2 (ja) 2001-11-14 2007-11-28 株式会社トクヤマ ジハロゲン化アダマンタンの製造方法
WO2003043575A2 (en) 2001-11-19 2003-05-30 Merck & Co., Inc. Process for the synthesis of (r)-1-(3,5-bis(trifluoromethyl)-phenyl)ethan-1-ol and esters thereof by dynamic kinetic resolution
ZA200209011B (en) 2001-11-20 2003-05-26 Rohm & Haas Electroactive catalysis.
DE10159615A1 (de) 2001-12-05 2003-06-12 Basf Ag Verfahren zur Herstellung von 1,2-Dichlorethan
US6844447B2 (en) 2001-12-18 2005-01-18 Metabolix Inc. Methods of making intermediates from polyhydroxyalkanoates
US7199255B2 (en) 2001-12-18 2007-04-03 Univation Technologies, Llc Imino-amide catalysts for olefin polymerization
EP2277847A3 (en) * 2002-01-24 2011-07-27 GRT, Inc. Integrated Process for Synthesizing Alcohols, Ethers, and Olefins from Alkanes
ATE419217T1 (de) 2002-01-25 2009-01-15 Council Scient Ind Res Herstellung von ungefährlichen bromierungsreagenzien
US7091270B2 (en) 2002-01-31 2006-08-15 Bromine Compounds Ltd. Pentabromobenzyl alkyl ethers and their use as fire retardants
AU2003214158A1 (en) 2002-03-13 2003-09-29 University Of Florida Process for trifluoromethylation of sulfates
WO2003076048A1 (en) 2002-03-14 2003-09-18 Questair Technologies Inc. Gas separation by combined pressure swing and displacement purge
US20040152929A1 (en) 2002-05-08 2004-08-05 Clarke William D Process for vinyl chloride manufacture from ethane and ethylene with air feed and alternative hcl processing methods
WO2004039918A2 (en) 2002-05-10 2004-05-13 Wisconsin Alumni Research Foundation Low-temperature hydrocarbon production from oxygenated hydrocarbons
US6545191B1 (en) 2002-06-13 2003-04-08 John E. Stauffer Process for preparing ethanol
KR100986958B1 (ko) 2002-07-31 2010-10-11 다이소 가부시키가이샤 광학활성 할로게노히드록시프로필 화합물 및 글리시딜화합물의 제조법
EP1386664B1 (en) 2002-07-31 2016-05-11 Ineos Technologies (Vinyls) Limited A hollow parallelepiped pellet suitable as carrier of catalysts for selective exothermic reactions
US7238846B2 (en) 2002-08-14 2007-07-03 Exxonmobil Chemical Patents Inc. Conversion process
US6831032B2 (en) 2002-08-19 2004-12-14 Novolen Technology Holdings C.V. Ziegler-Natta catalyst and methods of making and using same
AU2003265591A1 (en) 2002-08-22 2004-03-11 E.I. Du Pont De Nemours And Company Cobalt-substituted chromium oxide compositions, their preparation, and their use as catalysts and catalyst precursors
US6953870B2 (en) 2002-08-26 2005-10-11 Tsoung Y Yan Self-propelled liquid fuel
US6753390B2 (en) 2002-09-04 2004-06-22 Univation Technologies, Llc Gas phase polymerization process
DE10242223A1 (de) 2002-09-12 2004-03-25 Clariant Gmbh Verfahren zur Hydrodechlorierung von kernchlorierten ortho-Xylolen
US6740146B2 (en) 2002-09-12 2004-05-25 Edward L. Simonds Oxygen concentrator
FR2845077A1 (fr) 2002-09-26 2004-04-02 Atofina Procede d'abaissement de la teneur en matieres organiques et produits azotes contenus dans des effluents bromures
KR100531128B1 (ko) 2002-09-26 2005-11-28 한국화학연구원 분리막 반응기를 이용한 디메틸에테르의 제조방법
US6852896B2 (en) 2002-10-11 2005-02-08 John E. Stauffer Concerted process for the production of an alkenyl substituted aromatic compound
US6869903B2 (en) 2002-11-07 2005-03-22 Univation Technologies, Llc Synthesis of polymerization catalyst components
CN1203032C (zh) 2002-11-12 2005-05-25 石油大学(北京) 以复合离子液体为催化剂制备烷基化油剂的方法
US7060865B2 (en) 2002-11-12 2006-06-13 Exxonmobil Chemical Patents Inc. Recovery of C4 olefins from a product stream comprising C4 olefins, dimethyl ether and C5+ hydrocarbons
US7199083B2 (en) 2002-12-06 2007-04-03 Self Generating Foam Incoporated Self-generating foamed drilling fluids
DE10257499A1 (de) 2002-12-10 2004-07-01 Oxeno Olefinchemie Gmbh Verfahren zur Herstellung von 1-Olefinen durch katalytische Spaltung von 1-Alkoxyalkanen
JP4426527B2 (ja) 2002-12-20 2010-03-03 エクソンモービル・ケミカル・パテンツ・インク 重合プロセス
ATE469923T1 (de) 2002-12-20 2010-06-15 Exxonmobil Chem Patents Inc Polymere mit neuen sequenzverteilungen
EP1440939A1 (en) 2003-01-07 2004-07-28 Humboldt-Universität zu Berlin Method for the preparation of amorphous metal fluorides
DE10303304A1 (de) 2003-01-28 2004-07-29 Ruhrgas Ag Verfahren zum Herstellen nichtaromatischer Kohlenwassersstoffe
US7265193B2 (en) 2003-01-31 2007-09-04 Exxonmobil Chemical Patents Inc. Polymerization process
US20040158108A1 (en) 2003-02-06 2004-08-12 Snoble Karel A.J. Purification of alcohol
KR100501922B1 (ko) 2003-02-19 2005-07-18 에스케이 주식회사 메탄올로부터 디메틸에테르의 제조방법
US6875339B2 (en) 2003-03-07 2005-04-05 Conocophillips Company Octane improvement of a hydrocarbon stream
US7091391B2 (en) 2003-03-19 2006-08-15 Stauffer John E Methane to olefins
FR2852866B1 (fr) 2003-03-25 2006-07-14 Bp Lavera Snc Compose metallique fixe sur un support, procede de preparation et utilisation du compose dans des reactions de metathese d'hydrocarbure
US20040187684A1 (en) 2003-03-26 2004-09-30 Saleh Elomari Using molecular sieve SSZ-65 for reduction of oxides of nitrogen in a gas stream
US20040188324A1 (en) 2003-03-26 2004-09-30 Saleh Elomari Hydrocarbon conversion using molecular sieve SSZ-65
US7083714B2 (en) 2003-03-26 2006-08-01 Chevron U.S.A. Inc. Hydrocarbon conversion using molecular sieve SSZ-65
US7011811B2 (en) 2003-03-26 2006-03-14 Chevron U.S.A. Inc. Molecular sieve SSZ-65 composition of matter and synthesis thereof
US20040220433A1 (en) 2003-03-28 2004-11-04 Evert Van Der Heide Process for the preparation of propylene glycol
US7301060B2 (en) 2003-03-28 2007-11-27 Ab-Cwt, Llc Process for conversion of organic, waste, or low-value materials into useful products
JP4111035B2 (ja) 2003-03-31 2008-07-02 日本ゼオン株式会社 重合トナーの製造方法
US6822123B2 (en) 2003-04-02 2004-11-23 John E. Stauffer Formaldehyde process
EP1622857B1 (en) 2003-04-09 2011-10-05 Shell Internationale Research Maatschappij B.V. Process for the preparation of alkanediol
US7057081B2 (en) 2003-05-09 2006-06-06 Conocophillips Company Method for treating alkanes
US6953868B2 (en) 2003-06-05 2005-10-11 Dow Global Technologies Inc. Oxyfunctionalization of polyolefins
OA13183A (en) 2003-06-21 2006-12-13 Alan K Richards Anhydrous processing of methane into methane-sulfonic acid, methanol, and other compounds.
US7193093B2 (en) 2003-06-30 2007-03-20 Shell Oil Company Process for producing alkylene oxide
RU2366642C2 (ru) 2003-07-15 2009-09-10 Джи Ар Ти, Инк. Синтез углеводородов
US20050171393A1 (en) 2003-07-15 2005-08-04 Lorkovic Ivan M. Hydrocarbon synthesis
UA84436C2 (ru) 2003-08-08 2008-10-27 Солвей (Сосьетэ Аноним) Способ регенерации катализатора гидрирования и способ получения мономера винилхлорида
DE10338581A1 (de) 2003-08-22 2005-03-17 Oxeno Olefinchemie Gmbh Verfahren zur Erzeugung von tert.-Butanol
US6958306B2 (en) 2003-08-28 2005-10-25 Univation Technologies, Llc Activated catalyst systems from substituted dialuminoxane complexes
US7045670B2 (en) 2003-09-03 2006-05-16 Synfuels International, Inc. Process for liquid phase hydrogenation
GB0320684D0 (en) 2003-09-03 2003-10-01 Bp Chem Int Ltd Process
US6825383B1 (en) 2003-09-22 2004-11-30 Council Of Scientific And Industrial Research Catalytic process for regiospecific chlorination of alkanes, alkenes and arenes
US7105710B2 (en) 2003-09-26 2006-09-12 Shell Oil Company Process of preparing an alkylene glycol
DK1675813T3 (da) 2003-10-13 2008-03-03 Serono Lab Fremgangsmåde til fremstilling af para-phenylalkynylbenzaldehyder
US7335802B2 (en) 2003-10-15 2008-02-26 Shell Oil Company Methods of preparing branched aliphatic alcohols
WO2005035121A2 (en) 2003-10-16 2005-04-21 Universiteit Gent Schiff base metal complexes for use as catalysts in organic synthesis
US6838576B1 (en) 2003-10-23 2005-01-04 3M Innovative Properties Company Process for preparing functional group-containing olefinic compounds
US7196239B2 (en) 2003-11-19 2007-03-27 Exxonmobil Chemical Patents Inc. Methanol and ethanol production for an oxygenate to olefin reaction system
ATE359279T1 (de) 2003-11-28 2007-05-15 Firmenich & Cie Moschus-geruchsstoffe
WO2005054120A2 (en) 2003-12-05 2005-06-16 Idaho Research Foundation, Inc. Polymer-supported metal nanoparticles and method for their manufacture and use
US7244795B2 (en) 2003-12-08 2007-07-17 Univation Technologies, Llc Polymerization process using metallocene catalyst systems
WO2005056525A2 (en) 2003-12-09 2005-06-23 Bio-Technical Resources Deacetylation of n-acetylglucosamine
EP1697287B1 (en) 2003-12-18 2015-08-26 ExxonMobil Chemical Patents Inc. Improvements in or relating to hydrogenation
US7064238B2 (en) 2004-01-02 2006-06-20 Marathon Oil Company Conversion of alkanes to oxygenates
FR2865731B1 (fr) 2004-01-30 2007-09-07 Solvay Procede de fabrication d'un hydrofluoroalcane
FR2866023B1 (fr) 2004-02-05 2007-10-12 Rhodia Chimie Sa Procede de preparation d'un compose fluoaromatique a partir d'un compose aminoaromatique
WO2005090272A1 (en) 2004-03-12 2005-09-29 University Of Utah Cyclone reactor and associated methods
WO2005095310A2 (en) 2004-03-23 2005-10-13 Shell Internationale Research Maatschappij B.V. The utilization of zirconium and zirconium based alloys for the containment of halogen containing environments used in the production of olefins, alcohols, ethers, ethoxylates glycols, and olefin oxides from alkanes
JP4452130B2 (ja) 2004-04-05 2010-04-21 東洋エンジニアリング株式会社 液化天然ガスからの炭化水素分離方法および分離装置
MXPA06011655A (es) 2004-04-16 2007-01-23 Marathon Oil Co Proceso para convertir alcanos gaseosos en hidrocarburos liquidos.
US20060100469A1 (en) 2004-04-16 2006-05-11 Waycuilis John J Process for converting gaseous alkanes to olefins and liquid hydrocarbons
US20080275284A1 (en) 2004-04-16 2008-11-06 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7244867B2 (en) 2004-04-16 2007-07-17 Marathon Oil Company Process for converting gaseous alkanes to liquid hydrocarbons
US7674941B2 (en) 2004-04-16 2010-03-09 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
US8173851B2 (en) 2004-04-16 2012-05-08 Marathon Gtf Technology, Ltd. Processes for converting gaseous alkanes to liquid hydrocarbons
CN1972868B (zh) 2004-04-20 2010-04-21 环球油品公司 结晶铝硅酸盐沸石组合物：uzm-15
US7462752B2 (en) 2004-04-21 2008-12-09 Shell Oil Company Process to convert linear alkanes into alpha olefins
US7091387B2 (en) 2004-04-21 2006-08-15 Shell Oil Company Process to convert alkanes into primary alcohols
EP1756004B1 (en) 2004-04-23 2010-08-18 Uop Llc High silica zeolites uzm-5hs
WO2005110953A1 (en) 2004-04-30 2005-11-24 Shell Internationale Research Maatschappij B.V. Derivatives of alcohols and olefins
US7435760B2 (en) 2004-05-14 2008-10-14 Battelle Memorial Institute Method of generating hydrocarbon reagents from diesel, natural gas and other logistical fuels
DE602005017627D1 (de) 2004-06-16 2009-12-24 Dow Global Technologies Inc Vorrichtung und verfahren für die ziegler-natta-forschung
EP1760057A4 (en) 2004-06-23 2008-05-21 Tokuyama Corp METHOD FOR PRODUCING POLYHALOGENATED DIAMANTAN AND DERIVATIVES THEREOF
DE102004030943B4 (de) 2004-06-26 2013-10-02 Evonik Oxeno Gmbh Verfahren zur Herstellung von tert.-Butanol aus Isobuten-haltigen Kohlenwasserstoffgemischen
KR101225402B1 (ko) 2004-07-21 2013-01-23 다우 글로벌 테크놀로지스 엘엘씨 다중히드록시화-지방족 탄화수소 또는 그의 에스테르의클로로히드린으로의 전환
US7429683B2 (en) 2004-07-27 2008-09-30 Eastman Kodak Company Process of maing naphthacene from propargyl alcohol
WO2006015824A1 (en) 2004-08-13 2006-02-16 Exxonmobil Chemical Patents Inc. Process for producing sec-butyl benzene
US7371916B1 (en) 2004-09-16 2008-05-13 Uop Llc Conversion of an alcoholic oxygenate to propylene using moving bed technology and an etherification step
US7271303B1 (en) 2004-09-22 2007-09-18 Uop Llc Multi-zone process for the production of diesel and aromatic compounds
WO2006039213A1 (en) 2004-09-30 2006-04-13 Chevron U.S.A. Inc. Molecular sieve ssz-65
WO2006040863A1 (ja) 2004-10-15 2006-04-20 Toagosei Co., Ltd. 金属酸化物触媒の製造方法
GB0423586D0 (en) 2004-10-22 2004-11-24 United States Borax Inc Selective oxidation of organic compounds
CN101128257B (zh) 2004-11-12 2010-10-27 万罗赛斯公司 使用微通道技术进行烷化或酰化反应的方法
TWI332418B (en) 2004-11-18 2010-11-01 Rohm & Haas Hybrid catalyst systems and hybrid process for converting alkanes to alkenes and to their corresponding oxygenated products
WO2006067155A2 (en) 2004-12-21 2006-06-29 Albemarle Netherlands Bv Attrition-resisitant catalyst, a process for its preparation and its use
US7618544B2 (en) 2004-12-22 2009-11-17 Massingill John Lee Jr Fiber film reactors to effect separation and reaction between two immiscible reaction components
EP1843839A2 (en) 2004-12-22 2007-10-17 E.I. Dupont De Nemours And Company Copolymers of perfluoro (alkyl venyl ether) for photochemical reactor, process for increasing fluorine content and production of olefinic compound by photochlorination
ZA200705543B (en) 2004-12-23 2009-01-28 Chevron Usa Inc Molecular sieve SSZ-70 composition of matter and synthesis thereof
PL1831265T3 (pl) 2004-12-23 2011-08-31 Solvay Sposób wytwarzania 1,2-dichloroetanu
US7537685B2 (en) 2004-12-23 2009-05-26 Chevron U.S.A. Inc. Hydrocarbon conversion using molecular sieve SSZ-71
WO2006067190A1 (en) 2004-12-23 2006-06-29 Solvay (Société Anonyme) Process for the manufacture of 1,2-dichloroethane
KR20070094936A (ko) 2004-12-23 2007-09-27 솔베이(소시에떼아노님) 1, 2 - 디클로로에탄의 제조를 위한 공정
AU2005318154B2 (en) 2004-12-23 2011-07-14 Solvay (Societe Anonyme) Process for the manufacture of 1,2-dichloroethane
KR101237446B1 (ko) 2004-12-23 2013-02-26 셰브런 유.에스.에이.인크. 분자체 ｓｓｚ-70 조성물 및 이의 합성
DE102005003109B4 (de) 2005-01-22 2015-02-12 Air Liquide Global E&C Solutions Germany Gmbh Verfahren zur Herstellung von synthetischen Kraftstoffen aus Oxigenaten
US7253328B2 (en) 2005-01-24 2007-08-07 John Stauffer Method for producing vinyl chloride monomer
WO2006104909A2 (en) 2005-03-28 2006-10-05 Shell Internationale Research Maatschappij B.V. Catalytic distillation process for primary haloalkanes
US20060229475A1 (en) * 2005-04-11 2006-10-12 Weiss Michael J Synthesis of hydroxylated hydrocarbons
US20060229228A1 (en) * 2005-04-11 2006-10-12 Zachary John Anthony Komon Method of making alkoxylates
KR101347419B1 (ko) 2005-04-15 2014-02-06 이 아이 듀폰 디 네모아 앤드 캄파니 아릴-에틸렌 치환된 방향족 화합물 및 유기 반도체로서의 이의 용도
ITMI20050723A1 (it) 2005-04-21 2006-10-22 Consiglio Nazionale Ricerche Metodo di produzione del biodiesel
ATE493373T1 (de) 2005-05-04 2011-01-15 Dow Global Technologies Inc Oxidative halogenierung von c1- kohlenwasserstoffen zu halogenierten c1- kohlenwasserstoffen
EP1890988A2 (fr) 2005-05-20 2008-02-27 Solvay S.A. Procede de fabrication d'une chlorhydrine
WO2007017900A2 (en) 2005-05-26 2007-02-15 Sisir Kumar Mandal Preparation of para dichlorobenzene from benzene or mono chlorobenzene
US20060270863A1 (en) 2005-05-27 2006-11-30 Amyris Biotechnologies Conversion of amorpha-4,11-diene to artemisinin and artemisinin precursors
CA2510093C (en) 2005-06-16 2009-09-29 Apotex Pharmachem Inc. Novel process for the preparation of.alpha.-chlorovinyl, .alpha.,.alpha.-dichloro, and acetylenes from ketones
US7442354B2 (en) 2005-06-23 2008-10-28 Chevron U.S.A. Inc. Treatment of engine exhaust using molecular sieve SSZ-56
KR101310994B1 (ko) 2005-06-23 2013-09-24 셰브런 유.에스.에이.인크. 분자체 ｓｓｚ-56 조성물 및 이의 합성
US7390395B2 (en) 2005-06-23 2008-06-24 Saleh Elomari Hydrocarbon conversion using molecular sieve SSZ-56
CN101242887B (zh) 2005-06-23 2011-12-14 切夫里昂美国公司 分子筛ssz-56组合物及其合成
US7226569B2 (en) 2005-06-23 2007-06-05 Chevron U.S.A. Inc. Reduction of oxides of nitrogen in a gas stream using molecular sieve SSZ-56
US7084308B1 (en) 2005-07-29 2006-08-01 Stauffer John E Manufacture of formaldehyde from methyl bromide
US8957259B2 (en) 2005-09-30 2015-02-17 Battelle Memorial Institute Dimethyl ether production from methanol and/or syngas
JP5027815B2 (ja) 2005-10-07 2012-09-19 バジャー・ライセンシング・エルエルシー 高収率のビスフェノール−ａの製造方法
US7683230B2 (en) 2005-10-27 2010-03-23 Stauffer John E Methyl bromide to olefins
EP1951646A1 (en) 2005-10-28 2008-08-06 Shell Internationale Research Maatschappij B.V. Process for preparing internal olefins
US7888520B2 (en) 2005-12-21 2011-02-15 University Of Saskatchewan Process for the preparation of biodiesel
US20070213545A1 (en) 2005-12-22 2007-09-13 Bolk Jeroen W Method Of Installing An Epoxidation Catalyst In A Reactor, A Method Of Preparing An Epoxidation Catalyst, An Epoxidation Catalyst, A Process For The Preparation Of An Olefin Oxide Or A Chemical Derivable From An Olefin Oxide, And A Reactor Suitable For Such A Process
US20070197801A1 (en) 2005-12-22 2007-08-23 Bolk Jeroen W Method of installing an epoxidation catalyst in a reactor, a method of preparing an epoxidation catalyst, an epoxidation catalyst, a process for the preparation of an olefin oxide or a chemical derivable from an olefin oxide, and a reactor suitables for such a process
US7473807B2 (en) 2005-12-28 2009-01-06 Chevron Usa, Inc. Acylation using molecular sieve SSZ-74
US7357904B2 (en) 2005-12-28 2008-04-15 Chevron Corporation Reduction of oxides of nitrogen in a gas stream using molecular sieve SSZ-74
US7485766B2 (en) 2005-12-28 2009-02-03 Chevron U.S.A., Inc. Oxygenate conversion using molecular sieve SSZ-74
US7510697B2 (en) 2005-12-28 2009-03-31 Chevron U.S.A. Inc. Molecular sieve SSZ-74 composition of matter and synthesis thereof
US7762059B2 (en) 2005-12-28 2010-07-27 Chevron U.S.A. Inc. Treatment of engine exhaust using molecular sieve SSZ-74
US20070149778A1 (en) 2005-12-28 2007-06-28 Chevron U.S.A. Inc. Beckmann rearrangement using molecular sieve ssz-74
US7422732B2 (en) 2005-12-28 2008-09-09 Chevron U.S.A. Inc Synthesis of amines using molecular sieve SSZ-74
US20080115666A1 (en) 2005-12-28 2008-05-22 Chevron U.S.A. Inc. Gas separation using molecular sieve ssz-74
ZA200806549B (en) 2005-12-28 2009-11-25 Chevron Usa Inc Molecular sieve SSZ-74 composition of matter and synthesis thereof
CA2641348C (en) 2006-02-03 2014-12-23 Grt, Inc. Continuous process for converting natural gas to liquid hydrocarbons
GB0602424D0 (en) 2006-02-07 2006-03-22 Sinclair Pharmaceuticals Ltd Compounds
EP2004579A2 (en) 2006-03-23 2008-12-24 Velocys Inc. Process for making styrene using microchannel process technology
EP1837320A1 (en) 2006-03-23 2007-09-26 ETH Zürich Production of saturated C2 to C5 hydrocarbons
JP2007269708A (ja) 2006-03-31 2007-10-18 Sumitomo Chemical Co Ltd 第３級オレフィンおよび脂肪族アルコールの製造方法
US20070238905A1 (en) 2006-04-05 2007-10-11 Victor Manuel Arredondo Processes for converting glycerol to glycerol ethers
BRPI0601460B1 (pt) 2006-04-26 2015-11-10 Petroleo Brasileiro Sa processo para hidroconversão de mistura de óleos orgânicos de diferentes origens
EP2035140A1 (en) 2006-05-08 2009-03-18 ExxonMobil Chemical Patents, Inc., A Corporation of the State of Delaware Improved catalyst composition
CN101437783B (zh) 2006-05-08 2012-12-12 埃克森美孚化学专利公司 有机化合物转化方法
US7304193B1 (en) 2006-05-18 2007-12-04 Uop Llc Integrated process for aromatics production
US7268263B1 (en) 2006-05-18 2007-09-11 Uop Llc Integrated process for aromatics production
US7651603B2 (en) 2006-06-08 2010-01-26 Chevron U.S.A. Inc. Hydrocarbon conversion using molecular sieve SSZ-75
EP2029507A1 (en) 2006-06-08 2009-03-04 High Point Pharmaceuticals, LLC Process for preparing phenoxy acetic acid derivatives
WO2007142745A1 (en) 2006-06-09 2007-12-13 Exxonmobil Chemical Patents Inc. Intergrown molecular sieve, its synthesis and its use in the conversion of oxygenates to olefins
CN101516506A (zh) 2006-09-21 2009-08-26 雅宝公司 用于将甲烷转化为有用烃的方法及其中使用的催化剂
US20100087308A1 (en) 2006-09-21 2010-04-08 Albemarte Corporation Methods for conversion of methane to useful hydrocarbons, catalysts for use therein, and regeneration of the catalysts
BRPI0810060A2 (pt) 2007-02-28 2014-10-21 Albemarle Corp Processos para produizir hidrocarbonetos mais altos de metano e bromo
WO2008157043A1 (en) 2007-06-14 2008-12-24 Albemarle Corporation Processes for producing higher hydrocarbons from methane
WO2008157045A1 (en) 2007-06-14 2008-12-24 Albemarle Corporation Processes for producing higher hydrocarbons from hydrocarbon feed sources
WO2008157047A1 (en) 2007-06-14 2008-12-24 Albemarle Corporation Processes for producing hydrogen from hydrocarbon feed sources
WO2008157046A1 (en) 2007-06-14 2008-12-24 Albemarle Corporation Processes for producing higher hydrocarbons from methane
WO2008157044A1 (en) 2007-06-14 2008-12-24 Albemarle Corporation Processes for producing higher hydrocarbons from methane
US8282810B2 (en) 2008-06-13 2012-10-09 Marathon Gtf Technology, Ltd. Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery
US20090312586A1 (en) 2008-06-13 2009-12-17 Marathon Gtf Technology, Ltd. Hydrogenation of multi-brominated alkanes
CN102177112A (zh) 2008-10-07 2011-09-07 国际壳牌研究有限公司 同时生产芳烃及乙烯和丙烯的整合方法
WO2010093710A1 (en) * 2009-02-10 2010-08-19 Industrial Origami, Inc. Sheet of material with bend-controlling structures and method
US20110015458A1 (en) 2009-07-15 2011-01-20 Marathon Gtf Technology, Ltd. Conversion of hydrogen bromide to elemental bromine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6525230B2 (en) * 2001-04-18 2003-02-25 Grt, Inc. Zone reactor

Also Published As

Publication number Publication date
US20080200740A1 (en) 2008-08-21
EG26651A (en) 2014-05-04
US20060100469A1 (en) 2006-05-11
AU2006302939A1 (en) 2007-04-26
EA022696B1 (ru) 2016-02-29
WO2007046986A3 (en) 2007-06-07
AU2006302939B2 (en) 2013-03-14
KR101363300B1 (ko) 2014-02-18
JP2009512754A (ja) 2009-03-26
ZA200803330B (en) 2009-11-25
EP1945598A4 (en) 2011-07-06
US8008535B2 (en) 2011-08-30
AR058123A1 (es) 2008-01-23
WO2007046986A2 (en) 2007-04-26
AP2008004417A0 (en) 2008-04-30
UA105476C2 (uk) 2014-05-26
CA2625459A1 (en) 2007-04-26
MY151088A (en) 2014-04-15
JP5396082B2 (ja) 2014-01-22
PE20070737A1 (es) 2007-08-02
ECSP088361A (es) 2008-05-30
CA2625459C (en) 2014-11-04
TNSN08176A1 (en) 2009-10-30
CN101291891A (zh) 2008-10-22
NO20082252L (no) 2008-05-16
EP1945598A2 (en) 2008-07-23
KR20080063329A (ko) 2008-07-03
EA200801115A1 (ru) 2008-10-30
NZ567480A (en) 2011-08-26
BRPI0617707A2 (pt) 2011-08-02

Similar Documents

Publication Publication Date Title
CN101291891B (zh) 将气态烷烃转化为烯烃和液态烃的方法
CN101018751B (zh) 用于将气态烷烃转化为液态烃的方法
CN102056867A (zh) 将气态烷烃转化为液态烃的方法
KR101170773B1 (ko) 기체상 알칸을 액상 탄화수소로 전환시키는 방법
US9206093B2 (en) Process for converting gaseous alkanes to liquid hydrocarbons
CN102947249A (zh) 使用微通道反应器将气态烷烃转化为液态烃的方法
JP2007532760A5 (zh)
CN103998397A (zh) 用于在循环催化剂反应器-再生器系统中将烷基溴化物转化为较高分子量烃的方法和系统

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
ASS Succession or assignment of patent right

Owner name: MALASOEN TECHNOLOGY CO., LTD.

Free format text: FORMER OWNER: MALASOEN PETROLEUM CO., LTD.

Effective date: 20090424

C41 Transfer of patent application or patent right or utility model
TA01 Transfer of patent application right

Effective date of registration: 20090424

Address after: Texas in the United States

Applicant after: Marathon Gtf Technology Ltd.

Address before: Texas in the United States

Applicant before: Marathon Oil Co.

C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: GTC TECHNOLOGY US LLC

Free format text: FORMER OWNER: MARATHON GTF TECHNOLOGY LTD.

Effective date: 20150527

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20150527

Address after: Texas in the United States

Patentee after: MARATHON GTF TECHNOLOGY LTD

Address before: Texas in the United States

Patentee before: Marathon Gtf Technology Ltd.

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

Granted publication date: 20130327

Termination date: 20150913

EXPY Termination of patent right or utility model