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Publication numberCN101765574 A
Publication typeApplication
Application numberCN 200880017028
PCT numberPCT/US2008/064922
Publication date30 Jun 2010
Filing date27 May 2008
Priority date24 May 2007
Also published asCA2687589A1, EP2148846A1, US7998438, US20090127163, US20110270003, WO2008148113A1
Publication number200880017028.9, CN 101765574 A, CN 101765574A, CN 200880017028, CN-A-101765574, CN101765574 A, CN101765574A, CN200880017028, CN200880017028.9, PCT/2008/64922, PCT/US/2008/064922, PCT/US/2008/64922, PCT/US/8/064922, PCT/US/8/64922, PCT/US2008/064922, PCT/US2008/64922, PCT/US2008064922, PCT/US200864922, PCT/US8/064922, PCT/US8/64922, PCT/US8064922, PCT/US864922
Inventors迈克尔J.韦斯
ApplicantGrt公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Zone reactor incorporating reversible hydrogen halide capture and release
CN 101765574 A
Abstract
An improved process and a zone reactor for converting a hydrocarbon feedstock into higher hydrocarbons is provided. A first zone in the reactor contains both a material capable of releasing hydrogen halide (HX) and a carbon-carbon coupling catalyst; a second zone is initially empty or contains a halogenation and/or oxyhalogenation catalyst; and a third zone contains both a carbon-carbon coupling catalyst and a material capable of capturing HX. Air or oxygen is introduced into the first zone, a feedstock is introduced into the second zone, and products are produced in the third zone. HX produced during the reaction is reversibly captured and released in zones 1 and 3.
Claims(43)  translated from Chinese
  1. 一种用于将烃原料转化成一种或多种产物的反应器,它包括:该反应器中有限定多个区的一个或多个空心的容器,其中,第一区含有能够释放卤化氢的材料和偶联催化剂;第二区与该第一区相连,而第三区与该第二区相连并且含有碳-碳偶联催化剂以及一种能够俘获卤化氢的材料。 A method for the conversion of a hydrocarbon feedstock into one or more products of the reactor, comprising: the reactor has a plurality of zones defining one or more hollow container, wherein the first region is capable of releasing hydrogen halide containing Materials and coupling catalyst; second region and the first region is connected, and the third region and the second region is connected and contains carbon - carbon coupling catalyst as well as a material capable of trapping a hydrogen halide.
  2. 2. 如权利要求1所述的反应器,其中,该反应器包括一个单一的容器,并且第一区位于该容器的第一端,第二区位于该容器的中间,而第三区位于该容器的第二端,其中,气体可以从第一区流到第二区再从第二区流到第三区。 2. The reactor of claim 1, wherein the reactor comprises a single container, and the first region located at a first end of the container, the second region located in the middle of the container, and the third area is located in the The second end of the container, wherein the gas can flow from the first zone second zone third zone and then flows from the second zone.
  3. 3. 如权利要求l所述的反应器,其中,第一区位于第一容器中,第二区位于第二容器中,而第三区位于第三容器中,其中,气体可以从第一区流到第二区,再从第二区流到第三区。 L reactor according to claim, wherein the first region is located in a first container, a second container located in the second region, and the third area is located in a third container, wherein the gas from the first zone flow to the second region, and then flow to the third zone from the second zone.
  4. 4. 如权利要求1所述的反应器,其中,能够释放卤化氢的材料位于第一区的第一亚区中;第一区中的碳-碳偶联催化剂位于第一区的第二亚区中;第三区中的偶联催化剂位于第三区的第一亚区中;而能够释放卤化氢的材料位于第三区的第二亚区中。 4. The reactor of claim 1, wherein the material is capable of releasing hydrogen halide in the first sub-region of the first region; and a first region of the carbon - carbon coupling catalyst in the second zone of the first sub- zone; third region coupling catalyst in the third sub-region in the first region; and the material capable of releasing hydrogen halide in the third region of the second sub-region.
  5. 5. 如权利要求1所述的反应器,其中,该能够释放卤化氢的材料包括部分卤化的烯烃类。 5. The reactor of claim 1, wherein the material is capable of releasing hydrogen halide include partially halogenated olefins.
  6. 6. 如权利要求5所述的反应器,其中,这些部分卤化的烯烃每个分子具有10-100个碳原子。 6. The reactor of claim 5, wherein the partially halogenated olefin per molecule having 10-100 carbon atoms.
  7. 7. 如权利要求5所述的反应器,其中,这些部分卤化的烯烃每个分子具有15-80个碳原子。 7. The reactor of claim 5, wherein the partially halogenated olefin per molecule having 15-80 carbon atoms.
  8. 8. 如权利要求5所述的反应器,其中,这些部分卤化的烯烃每个分子具有20-50个碳原子。 8. The reactor of claim 5, wherein the partially halogenated olefin per molecule having 20-50 carbon atoms.
  9. 9. 如权利要求5所述的反应器,其中,这些部分卤化的烯烃包括部分卤化的l-十二烯、 1, 12-十二碳二烯、和/或1- 二十烷。 9. The reactor of claim 5, wherein the partially halogenated olefins include partially halogenated l- dodecene, 1, 12-dodecadiene, and / or 1-eicosane.
  10. 10. 如权利要求5所述的反应器,其中,所述能够后释放卤化氢的材料包括部分卤化的有机聚合物类。 10. The reactor of claim 5, wherein, after the material is capable of releasing the hydrogen halide include organic polymers partially halogenated.
  11. 11. 如权利要求10所述的反应器,其中,这些有机聚合物选自部分卤化的聚乙炔、经部分脱氢的和部分卤化的聚乙烯、经部分脱氢的和部分卤化的聚丙烯、以及它们的混合物。 11. The reactor of claim 10, wherein said organic polymer is selected from polyacetylene partially halogenated, partially halogenated polyethylene and partially dehydrogenated, partially dehydrogenated and partially halogenated polypropylene, and mixtures thereof.
  12. 12. 如权利要求IO所述的反应器,其中,所述部分卤化的有机聚合物包括部分卤化的聚丁二烯。 IO 12. The reactor of claim, wherein the partially halogenated organic polymers include partially halogenated polybutadiene.
  13. 13. 如权利要求1所述的反应器,其中,该能够俘获卤化氢的材料包括每个分子具有10-100个碳原子的烯烃类。 13. The reactor of claim 1, wherein the material capable of trapping a hydrogen halide per molecule comprising olefins having 10 to 100 carbon atoms.
  14. 14. 如权利要求13所述的反应器,其中,这些烯烃每个分子具有15-80个碳原子。 14. The reactor of claim 13, wherein each molecule of these olefins having 15-80 carbon atoms.
  15. 15. 如权利要求13所述的反应器,其中,这些烯烃每个分子具有20-50个碳原子。 15. The reactor of claim 13, wherein each molecule of these olefins having 20-50 carbon atoms.
  16. 16. 如权利要求1所述的反应器,其中,该能够俘获卤化氢的材料包括不饱和有机聚合物类。 16. The reactor of claim 1, wherein the material capable of trapping a hydrogen halide include unsaturated organic polymers.
  17. 17. 如权利要求16所述的反应器,其中,这些不饱和有机聚合物选自聚乙炔、经部分脱氢的聚乙烯、经部分脱氢的聚丙烯、以及它们的混合物。 17. The reactor of claim 16, wherein the unsaturated organic polymer is selected from polyacetylene, partially dehydrogenated polyethylene, polypropylene partially dehydrogenated, and mixtures thereof.
  18. 18. 如权利要求16所述的反应器,其中,所述不饱和有机聚合物包括聚丁二烯。 18. The reactor of claim 16, wherein the unsaturated organic polymer comprises polybutadiene.
  19. 19. 如权利要求1所述的反应器,其中,该第二区含有卤化和/或卤氧化催化剂。 19. The reactor of claim 1, wherein the second region comprises halide and / or oxyhalide catalyst.
  20. 20. 如权利要求1所述的反应器,其中,该卤化和/或卤氧化催化剂包括氧化铜。 20. The reactor according to claim, wherein the halide and / or oxyhalide catalyst comprises copper oxide.
  21. 21. 如权利要求1所述的反应器,其中,该卤化和/或卤氧化催化剂包括卤化铜。 21. The reactor according to claim, wherein the halide and / or oxyhalide catalyst comprises a copper halide.
  22. 22. 如权利要求1所述的反应器,其中,该卤化铜包括溴化铜或氯化铜。 22. The reactor according to claim, wherein the copper halide comprises bromide, copper or copper chloride.
  23. 23. 如权利要求1所述的反应器,其中,该偶联催化剂包括微孔材料。 23. The reactor according to claim, wherein the coupling catalyst comprises a microporous material.
  24. 24. 如权利要求23所述的反应器,其中,该微孔材料包括加载型或非加载型沸石类。 23 24. A reactor according to claim, wherein the microporous material comprises a loading or non-loading type zeolites.
  25. 25. 如权利要求24所述的反应器,其中,所述沸石包括掺杂型沸石类。 25. The reactor of claim 24, wherein said zeolite comprises doped zeolites.
  26. 26. 如权利要求24所述的反应器,其中,所述沸石包括ZSM-5型沸石类。 26. The reactor of claim 24, wherein said zeolite comprises ZSM-5 type zeolites.
  27. 27. 如权利要求l所述的反应器,其中,所有三个区都位于单一的空心容器内部,并且相邻的区通过其中具有至少一个开口的分隔件而分离。 27. The reactor of claim l, wherein, all three zones are located inside a single hollow container, and the adjacent region by the partition member having at least one opening and separating.
  28. 28. 如权利要求1所述的反应器,其中,该分隔件包括筛网。 28. The reactor of claim 1, wherein the partition member comprises a mesh.
  29. 29. —种用于将烃原料转化成较高级烃类的反应器,它包括:具有第一区、第二区、和第三区的空心容器,其中,第一区含有部分卤化的烯烃和/或部分卤化的不饱和的有机聚合物以及ZSM-5沸石;第二区与第一区相连,并且含有金属氧化物;而第三区与第二区相连,并且含有微孔偶联催化剂和中_长链烯烃和/或不饱和有机聚合物。 29. - species for hydrocarbon feedstock into the reactor higher hydrocarbons, comprising: a first region, a second hollow container region, and a third region, wherein the first region comprises partially halogenated olefins and / or partially halogenated unsaturated organic polymer and a ZSM-5 zeolite; second region connected to the first region, and contains a metal oxide; and a third region connected to the second region, and the coupling catalyst and containing micropores _ in long chain olefins and / or unsaturated organic polymer.
  30. 30. 如权利要求29所述的反应器,其中,所述金属氧化物包括氧化铜。 29 30. A reactor according to claim, wherein said metal oxide comprises copper oxide.
  31. 31. 如权利要求29所述的反应器,其中,该微孔偶联催化剂包括ZSM-5沸石。 31. The reactor according to claim 29, wherein the coupling catalyst comprises a microporous ZSM-5 zeolite.
  32. 32. 如权利要求29所述的反应器,其中,所述部分卤化的烯烃和/或部分卤化的不饱和有机聚合物位于第一区的第一亚区中;所述ZSM-5沸石位于第一区的第二亚区中;所述微孔偶联催化剂位于第三区的第一亚区中;并且所述中_长链烯烃和/或不饱和有机聚合物位于第三区的第二亚区中。 32. The reactor of claim 29, wherein the partially halogenated olefin and / or an unsaturated organic polymer partially halogenated in a first sub-region of the first region; and the ZSM-5 zeolite located The second sub-area of a region; said micropore coupling catalyst is located in the third region of the first sub-region; and _ the medium long chain olefins and / or unsaturated organic polymer is located in the third region of the second Asian area.
  33. 33. 将烃原料转化成较高级烃类的方法,它包括: 加热在空气或氧中能够释放HX的材料形成卤化氢的第一气流; 使烃原料与该HX的第一气流在空气或氧中反应形成烷基卤化物; 使这些烷基卤化物在第二碳_碳偶联催化剂的存在下反应形成较高级烃类以及HX的第二气流;并且使HX的第二气流与能够俘获HX的材料反应来俘获该HX的第二气流。 33. The hydrocarbon feedstock into higher hydrocarbons, which comprises: heating in air or oxygen in the first gas stream is capable of releasing hydrogen halide HX is formed of a material; the hydrocarbon feedstock with the first gas stream in the air or oxygen HX react to form alkyl halide; these alkyl halide in the presence of a second carbon-carbon coupling catalyst _ reacted to form higher order hydrocarbons and HX second gas stream; and a second gas stream and so HX capable of capturing HX The material response to capture a second flow of the HX.
  34. 34. 如权利要求33所述的方法,进一步包括使该第一偶联催化剂和该第二偶联催化剂除焦。 33 34. The method according to claim, further comprising coupling the first catalyst and the second coupling catalyst decoking.
  35. 35. 如权利要求33所述的方法,其中,该能够释放HX的材料包括部分卤化的烯烃类。 33 35. The method according to claim, wherein the material capable of releasing HX comprises partially halogenated olefins.
  36. 36. 如权利要求33所述的方法,其中,所述烯烃每分子具有10-100个碳原子。 36. The method of claim 33, wherein the olefin per molecule having 10-100 carbon atoms.
  37. 37. 如权利要求33所述的方法,其中,该能够释放HX的材料包括部分卤化的有机聚合物。 33 37. The method according to claim, wherein the material capable of releasing HX including some halogenated organic polymers.
  38. 38. 如权利要求33所述的方法,其中,所述部分卤化的有机聚合物选自部分卤化的聚乙炔、聚丁二烯、经部分脱氢和部分卤化的聚乙烯、经部分脱氢和部分卤化的聚丙烯以及它们的混合物。 38. The method of claim 33, wherein the partially halogenated organic polymer is selected from polyacetylene partially halogenated polybutadiene, partially dehydrogenated and partially halogenated polyethylene, and partially dehydrogenated partially halogenated polypropylene, and mixtures thereof.
  39. 39. 如权利要求33所述的方法,其中,该能够俘获HX的材料包括每分子具有10-100个碳原子的烯烃。 39. The method of claim 33, wherein the material capable of capturing HX per molecule comprising an olefin having 10 to 100 carbon atoms.
  40. 40. 如权利要求33所述的方法,其中,该能够俘获HX的材料包括不饱和有机聚合物。 40. The method of claim 33, wherein the material capable of capturing HX include unsaturated organic polymer.
  41. 41. 根据权利要求40所述的方法,其中,所述有机聚合物选自聚乙炔、聚丁二烯、经部分脱氢的聚乙烯、经部分脱氢的聚丙烯、以及它们的混合物。 41. The method according to claim 40, wherein the organic polymer is selected from polyacetylene, polybutadiene, partially dehydrogenated polyethylene, polypropylene partially dehydrogenated, and mixtures thereof.
  42. 42. 将烃原料转化成较高级烃类的方法,它包括:(a) 在空气或氧中加热能够释放HX的材料形成卤化氢以及一种能够俘获HX的材料;(b) 使烃原料与步骤(a)中形成的HX在空气或氧中反应形成烷基卤化物;(c) 使所述烷基卤化物在偶联催化剂的存在下反应形成较高级烃类以及附加的HX ;并且(d) 用能够俘获HX的材料反应性地俘获步骤(e)中形成的HX而形成能够释放HX的材料。 42. The hydrocarbon feedstock into higher hydrocarbons which comprises: (a) heating in air or oxygen to release the hydrogen halide HX is formed of a material and a material capable of capturing HX; (b) contacting a hydrocarbon feedstock with Step (a) HX formed in the air or oxygen react to form alkyl halide; (c) so that the alkyl halide in the presence of a coupling catalyst to form higher hydrocarbons and additional HX; and ( d) HX with a material capable of capturing HX reactively capture step (e) is formed to form a material capable of releasing HX.
  43. 43. 如权利要求42所述的方法,进一步包括该偶联催化剂的结焦和除焦步骤。 43. The method of claim 42, further comprising the coupling catalyst coking and decoking step.
Description  translated from Chinese

使鹵化氢可逆性俘获与释放相结合的区域反应器 Reversibility of the hydrogen halide capture and release of a combination of regions of the reactor

技术领域 FIELD

[0001] 本发明涉及将烃原料转化成较高级烃的一种方法和装置。 [0001] The present invention relates to a method and apparatus for a hydrocarbon feedstock into higher hydrocarbons.

背景技术 BACKGROUND

[0002] 美国专利号6, 525, 230披露了将烷类转化成醇类和/或醚类的一种方法,以及由一个空心的、非隔离而内部限定了第一区、第二区和第三区的区域反应器。 [0002] U.S. Patent No. 6, 525, 230 discloses a method for the conversion of alkanes to alcohols and / or ethers, and by a hollow, non-isolated and interior defining a first zone, second zone and The third zone of the reactor zone. 在其第一实施方案中,空气或氧与金属溴化物在第一区中反应以提供溴;溴与一种或多种烷在第二区中反应以形成烷基溴化物;并且这些烷基溴化物与金属氧化物在第三区反应以形成相应的产物。 In a first embodiment, the metal bromide with air or oxygen in a first reaction zone to provide bromine; bromine with one or more alkoxy in the second reaction zone to form alkyl bromides; and these alkyl groups bromide with a metal oxide in the third zone of the reactor to form the corresponding product. 来自第三区的金属溴化物通过容器输送到第一区,而来自第一区的金属氧化物再循环至第三区。 The metal bromide from the third region through the vessel to the first zone, while the metal oxide from the first zone is recycled to the third zone. 其第二实施方案与该第一实施方案的区别在于金属氧化物通过容器从第一区输送到第三区,而金属溴化物从第三区再循环至第一区。 A second embodiment differs from the first embodiment in that the metal oxide is conveyed from the container through the first zone to the third zone, and the metal bromide is recycled from the third zone to the first zone. 其第三实施方案中,经过容器的气流被逆转以将金属氧化物转化回金属溴化物并且将金属溴化物转化回金属氧化物。 Its third embodiment, the air flow through the vessel is reversed to the conversion of the metal oxide and the metal bromide back to metal bromide back to metal oxide conversion.

发明内容 SUMMARY

[0003] 本发明提供了将烃原料转化成一种或多种较高级烃类的改进的区域反应器和一种生产方法。 [0003] The present invention provides a hydrocarbon feedstock into one or more higher hydrocarbons is improved comparing with the zone of the reactor and a method for producing. 在一个实施方案中,一个改进的区域反应器包括具有第一区、第二区、以及第三区的容器,其中该第一区含有能够释放卤化氢(HX)的材料和碳-碳偶联催化剂;该第二区最初是空的(但不是大气环境)或含有卤化和/或卤氧化催化剂;而该第三区含有碳-碳偶联催化剂和能够俘获HX的材料。 In one embodiment, a modified region comprises a reactor having a first region, a second container region, and a third region, wherein the first region contains a group capable of releasing hydrogen halide (HX) materials and carbon - carbon coupling catalyst; the second region is initially empty (but not atmosphere) or containing halide and / or oxyhalide catalyst; and the third region containing a carbon - carbon coupling catalyst and a material capable of capturing HX. 气体可以分别流过第一区、第二区、和第三区。 Gas can flow through the first area, the second area, and the third area. 优选地, 在第一区、第二区和第三区各自配置一个气体进口和/或出口,包括在第二区中用于引入气态烃原料的一个进口。 Preferably, in the first zone, second zone and third zone are respectively arranged at a gas inlet and / or outlet, comprising an inlet for introducing the second zone a gaseous hydrocarbon feedstock.

[0004] 在本发明的另一个方面,一种将烃原料转化成较高级烃的改进方法包括,在空气或氧存在下,通过加热能够释放HX的材料以形成HX ;根据需要,可将碳_碳偶联催化剂除焦;使烃原料与HX在空气或氧的存在下反应以形成烷基卤化物;使这些烷基卤化物在碳-碳偶联催化剂的存在下反应以形成较高级烃和HX(以及并不希望生成的焦炭);并且通过使HX与能够俘获HX的材料反应以俘获HX。 [0004] In another aspect of the present invention, a hydrocarbon feedstock into higher hydrocarbons including improved methods, in the presence of air or oxygen, can be released by heating the material to form HX HX; As required, the carbon _ carbon coupling catalyst decoking; HX is reacted with a hydrocarbon feedstock in the presence of air or oxygen to form alkyl halide; these alkyl halide in a carbon - carbon coupling reaction the presence of a catalyst to form higher hydrocarbons and HX (and do not want to generate coke); and by reaction with HX HX can capture material to capture HX. 优选将该方法重复多次,其中HX可交替释放和俘获,而偶联催化剂的结焦和除焦也交替进行。 Preferably This process was repeated several times, wherein HX may be alternately released and captured, and the coupling catalyst coking and decoking are alternately. 在一个实施方案中,HX是通过将部分卤化的烯烃或聚烯烃脱卤化氢而释放,并且通过使烯烃或聚烯烃加卤化氢而将其俘获。 In one embodiment, HX is formed by partially halogenated olefin or polyolefin dehydrohalogenation is released, and by an olefin or polyolefin and adding a hydrogen halide to be captured.

附图说明 Brief Description

[0005] 当结合附图理解时,本发明以上这些方面和其他方面及其特征将变得更加清晰, 其中: [0005] When DRAWINGS understood that the above aspects of the invention and other aspects and features will become more clear, which:

[0006] 图1是根据本发明的一个实施方案的区域反应器的示意图。 [0006] Figure 1 is a schematic diagram of an embodiment of the zone of the reactor of the present invention.

[0007] 图2是根据本发明的另一个实施方案的改进区域反应器的第二区示意图。 [0007] FIG. 2 is a schematic view of a second zone of the reactor to improve region of another embodiment of the present invention. 具体实施方式 DETAILED DESCRIPTION

[0008] 本发明提供将烃原料转化成一种或多种有用的产物,S卩"较高级的烃"的方法和改进的区域反应器。 [0008] The present invention provides a hydrocarbon feedstock into one or more useful product, S Jie "higher hydrocarbons" method and an improved region of the reactor. 总体上,该方法包括通过在空气或氧中加热能够释放HX的材料,以形成卤化氢的第一气流或第一分量;通过使烃原料与该HX的第一气流在空气或氧中反应以形成烷基卤化物;通过使这些烷基卤化物在第二碳-碳偶联催化剂的存在下反应以形成较高级的烃和卤化物的第二气流或第二分量;并且通过使HX的第二气流与能够俘获HX的材料反应以俘获该HX的第二气流。 Generally, the method comprises heating a material capable of releasing HX in air or oxygen, to form a first component of the first gas stream or the hydrogen halide; hydrocarbon feedstock by reaction with HX in the first stream of air or oxygen forming an alkyl halide; by reacting an alkyl halide in which the second carbon - carbon coupling reaction under the presence of a catalyst to form higher hydrocarbons and a second stream of a second component or halide; and by making the first HX two airflow and material capable of capturing HX HX reaction to capture the second gas stream.

[0009] 在图IA和IB中示意性地描述了改进的区域反应器的一个实施方案的操作模式和总体特征。 Schematically depicts operating modes and features to improve the overall area of the reactor to an embodiment of [0009] In Figure IA and IB in. 以总体上空心的容器的形式存在的区域反应器IO,包括第一区l,该第一区1进一步细分成两个亚区1A和IB ;第二区2 ;以及第三区3,该第三区3进一步细分成亚区3A 和亚区3B。 In the form of generally hollow container presence zone of the reactor IO, comprising a first region l, the first region 1 is further subdivided into two sub-regions 1A and IB; second zone 2; and a third zone 3, the The third area is further subdivided into three sub-regions and sub-regions 3A 3B.

[0010] 如以下所描述的,最初,区1A含有能够释放HX的材料。 [0010] As described below, the first district to release HX 1A containing materials. 区IB含有碳-碳偶联催化剂,该催化剂催化碳_碳键形成以及较高级烃的生成。 IB region containing a carbon - carbon coupling catalyst, the catalyst _ catalyzed carbon-carbon bond formation and the generation of higher hydrocarbons. 虽然并不受理论束缚,但是相信碳_碳键形成是经由烷基卤化物分子的分子间的、以及可能甚至是分子内的复分解反应而进行。 While not bound by theory, it is believed that carbon-carbon bond formation via _, and possibly even the metathesis reaction intramolecular molecule between the alkyl halide molecules performed. 如以下所描述的,在图中,在区lB中的催化剂已被焦炭覆盖和/或浸渍。 As described below, in the figure, the catalyst has been in the area lB coke-covered and / or impregnated. 但当反应器为它的初始运转进行装填时,并不存在焦炭。 However, when the reactor to its initial operation is mounted, and there is no coke. 区2或者是空的或者含有一种卤化和/或卤氧化催化剂或催化反应剂。 Zone 2, or is empty or contain a halide and / or oxyhalide catalyst or catalytic agent. 区3B也含有碳-碳偶联催化剂,而区3A含有能够俘获HX的材料。 Region 3B also contains carbon - carbon coupling catalyst, while zone 3A comprising a material capable of capturing HX.

[0011] 在反应器的左端的第一开口或进口4使空气或氧进入容器。 [0011] In the first opening or the left end of the import of the reactor 4 of air or oxygen into the container. 反应器中间的第二开口或进口5可以使气态的烃原料加入,而在容器的右端的第三开口或进口6使产品可以排出。 The reactor in the middle of the second opening or importing five gaseous hydrocarbon feedstock can join, but in the third opening or importing container 6 so that the right side of the product can be discharged. 此外,各个区和亚区在允许气流进入相邻的区的边界7处相遇。 In addition, each district and sub-district in the permit airflow into the border area adjacent seven encounter. 在一个实施方案中,容器内部无隔断,并且相连的区和亚区彼此没有物理分隔。 In one embodiment, the interior of the container without partition, district and sub-district and connected to each other without physical separation. 在一个实施方案中,相连的区和亚区是通过筛网,或通过壁或其他分隔件而分离,该分隔件具有置于其中的至少一个敞口从而允许气体从一个区或亚区流到下一个区或亚区。 In one embodiment, the region and sub-region are connected through a screen, or are separated by a wall or other partition, the partition member having disposed therein at least one open to allow gas from one region or sub-flow Under a region or sub-region. 各种加热器和/或冷却器(没有示出) 直接地或间接地热偶连于容器,从而使得每个区和亚区的温度控制变得容易。 Various heater and / or cooler (not shown) directly or indirectly connected to the thermocouple container, so that the temperature of each zone and sub-zone can be easily controlled. [0012] 如图1A所示,最初,反应器从左到右运行,空气或氧通过气体进口4进入区1A,使得其中所含的原料释放气态的HX。 [0012] shown in Figure 1A, first, the reactor runs from left to right, air or oxygen through the gas inlet 4 into the area 1A, so that the raw material contained therein to release gaseous HX. 加热的空气或氧以及来自区1A的HX进入区1B并且与碳-碳偶联催化剂接触。 Heated air or oxygen from the area and HX inlet region 1A and 1B with the carbon - carbon coupling catalyst contact. 空气或氧与先前积存在催化剂之中或之上的任何焦炭反应并且将它转化成C02。 Air or oxygen previously accumulated in the catalyst in or on any reaction of coke and to convert it to C02. 在过量的空气或氧的存在下,所形成的任何CO也将转化为C02。 In the presence of excess air or oxygen, any of the formed CO will be converted to C02. [0013] 在区2中,气态的烃原料经过第二气体进口5进入容器,并且使其在空气或氧以及优选的一种卤化和/或卤氧化催化剂或催化反应剂的存在下与HX反应。 [0013] In region 2, the gaseous hydrocarbon feedstock passes through the second gas inlet 5 into the container, and allowed the presence of air or oxygen, and preferably a halide and / or oxyhalide catalyst or catalytic reaction of reactants and HX . 这导致了一种或多种烷基卤化物(RX)和蒸气的形成,这些卤化物和蒸气连同存在的任何HX—起被带到了区3B。 This leads to one or more alkyl halide (RX) and vapors formed, which, together with the presence of halides and vapor was brought from any HX- area 3B. 那里,这些烷基卤化物在碳_碳偶联催化剂的存在下反应而转化成较高级烃和HX。 There, the alkyl halide in the presence of a carbon carbon coupling catalyst reaction _ converted to higher hydrocarbons and HX. 该反应还可能(实际一般都会)导致焦炭的形成,其中焦炭颗粒作为涂层沉积在碳-碳偶联催化剂上和/或沉积在催化剂的间隙中。 The reaction may also be (actual usually) results in the formation of coke, wherein the coke particles are deposited as a coating on a carbon - carbon coupling catalyst and / or catalyst is deposited in the gap. 所形成的HX然后与能够俘获它的材料在区3A 中反应。 HX formed is then reacted with a material capable of capturing it in the region 3A. 气态烃产物、(A、残留的空气(或它的贫氧成分)、以及可能的其他种类通过第三口6带出反应器容器,并且可以收集、分离并且纯化、进一步反应、和/或以一些其他的方式进行处理。 Gaseous hydrocarbon products, (A, residual air (oxygen-depleted or its components), and possibly other species through the third opening 6 out of the reactor vessel, and can be collected, separated and purified, further reaction, and / or some other manner.

[0014] 图1B表示准备用于从右到左的逆向运行的区域反应器。 [0014] Figure 1B shows the area of the reactor ready for right-to-left reverse operation. 反应器10仍然含有区1-3和亚区1A、1B、3B和3A,但现在,当在空气或氧中加热时,区3A中的材料是能够释放HX 的(即当反应器正向运行时它们已经被氢卤化)。 The reactor still contains 10 district and sub-district 1-3 1A, 1B, 3B and 3A, but now, when heated in air or oxygen, the District 3A is able to release the material HX (ie, when the reactor is running forward When they have been hydrogen halide). 相似地,区3B中的催化剂现在是被焦炭包覆和/或浸渍的,而区1B中的催化剂具有少许焦炭或无焦炭(理想状态)。 Similarly, the region is now 3B catalyst coke coated and / or impregnated, and the region 1B catalysts having little or no coke coke (ideal state). 区1A中的材料是准备与HX反应的,并且由此俘获而储存HX。 Area. 1A material is ready to react with HX, and thereby capture and storage HX. 空气或氧通过区3A中的第三入口6进入, 并且使其中所含的材料释放HX,其中HX连同空气或氧一起流入区3B。 Air or oxygen through the third region 3A into the inlet 6, and the material contained therein to release HX, wherein HX together with air or oxygen flow into the region 3B. 空气或氧气氧化已经沉积在碳_碳偶联催化剂上的焦炭。 Air or oxygen oxidation of coke has deposited on the carbon _ carbon coupling catalyst. 使HX和空气或氧顺流到达区2,在那里,它们与烃原料反应以形成烷基卤化物和蒸气,烷基卤化物和蒸气进入区1B。 HX and air or oxygen so that downstream reach region 2, where they react with the hydrocarbon feedstock and steam to form alkyl halides, alkyl halides, and the vapor inlet region 1B. 这些烷基卤化物在碳-碳偶联催化剂的存在下在区1B中反应,并且形成烃产物、HX、以及焦炭,焦炭沉积在催化剂之上和/或之中。 These alkyl halide in a carbon - carbon coupling the presence of a catalyst in the reaction zone 1B, and form hydrocarbon products, HX, as well as coke, coke deposited on the catalyst and / or during. HX、C(^、空气或它们的成分、蒸气、以及可能的其他气体然后进入区1A,并且HX与其中所含的材料反应并且被它俘获。产品和残留的气体通过第一口4离开。反应器按正向再次准备运行。通过正向和逆向之间循环,反应器可以连续地运行。 [0015] 在另一个实施方案中,气态反应物流一直保持在相同的方向,并且反应区是稳定的。然而,固体是连续再生的。由于耗尽了在区1A中所含的卤化物,固体从那个区以恒定的速率排出,并且输送到区3A。相似地,完全再生的固体不断地从区3A排出并且输送回区1A。在区1A与3A之间的固体输送通过重力、气动输送、和其他机械方式(例如传送机)、或这些方法的组合而变得便捷。以相似的方式,在区1B中再生的碳-碳偶联催化剂不断地排出并且输送到区3B,并且将焦化的碳-碳偶联催化剂从区3B输送到1B用于再生。偶联催化剂的输送通过重力、气动输送、其他机械方式、或这些方法的组合而变得容易。 [0016] 如在这里和权利要求里所用的,关于一种化合物、催化剂或其他材料的单数或复数,并不旨在将该物质限制在具体的分子量数或质量数,也不旨在限制物质的具体的不同类型数,除非另外指出。例如,"较高级的烃"可以包括占优势的一种化合物,或确切存在的一种化合物(例如大量的异辛烷),或者可以是两种或多种不同的化合物(例如,丁烷、苯、 丙烯等)。相似地,"烯烃类"是指占大多数的单一烯烃,或者可以是两种或多种不同的烯烃; "沸石类"是指占大多数的一种沸石,或者可以是多种不同的沸石等。 HX, C (^, or a component of air, vapor, and other gases may then enter the zone 1A, the reaction and the material contained therein and HX and it is captured. The residual product gas through the first port 4 and leave. reactor was again ready for operation in the forward direction by the forward and reverse circulation between the reactor can be run continuously. [0015] In another embodiment, the gaseous reactant stream remains in the same direction, and the reaction zone is a stable However, the solid is continuously reproduced. Since the depletion region 1A of the halide contained in the solid from the discharge zone at a constant rate, and supplied to the area 3A. Similarly, the solid was completely regenerated continuously from 3A and transferred back to the discharge region area 1A. The solid region 1A and 3A between the conveying by gravity, pneumatic conveyance, and other mechanical means (e.g., conveyor), or a combination of these methods become convenient. In a similar manner, 1B in the regeneration zone carbon - carbon coupling catalyst continuously discharged and transported to the area 3B, and the coking of the carbon - carbon coupling catalyst is conveyed from zone 1B to 3B for conveying regenerated coupling catalyst by gravity, pneumatic. transport, other mechanical means, or a combination of these methods and can be facilitated. [0016] As used herein and in the claims as used, relates to a compound, or other catalyst materials singular or plural, and is not intended This material limited to the specific number or mass number molecular weight, nor is it intended to limit the number of different types of concrete material, unless otherwise indicated. For example, "higher hydrocarbons" may include a compound dominant, or rather the presence of a compound (e.g., a large amount of iso-octane), or two or more different compounds (e.g., butane, benzene, propylene, etc.) may be. Similarly, "olefin" refers to a majority of a single olefin, or may be two or more different olefins; "zeolite" refers to a majority of the zeolite, or may be a number of different zeolites.

[0017] 很多烃原料都可考虑用于本发明的实践。 [0017] Many hydrocarbon feedstocks are contemplated for practicing the invention. 非限制性实例包括一种或多种轻质烷类和/或烯烃类,例如,甲烷、乙烷、丙烷、丁烷、乙烯、丙烯、丁烯;天然气;以及烃类的其他混合物。 Non-limiting examples include one or more light alkanes and / or alkenes, for example, methane, ethane, propane, butane, ethylene, propylene, butylene; natural gas; and a mixture of other hydrocarbons. 在大多数实施方案中,原料将在性质上基本是脂肪类的。 In most embodiments, the feedstock will be substantially aliphatic in nature class. 某些炼油厂加工生产的轻质烃流(称作"轻尾气",典型地是C1-C3的烃混合物),它们可以在添加或不添加甲烷的情况下使用。 Some refinery processing light hydrocarbon stream (referred to as "light off-gas", is typically a mixture of C1-C3 hydrocarbons), and they can be used in case of with or without added methane. 总之,原料是作为一种气体而加入反应器的。 In short, as a raw material gas is fed to the reactor.

[0018] 区域反应器的产品_ 一种或多种"较高级烃"-将取决于原料、碳_碳偶联催化剂、 以及反应器条件,例如气体流速(它影响反应器停留时间)、温度、和压力。 [0018] _ zone of the reactor product of one or more "higher hydrocarbons" - will depend on the feedstock, carbon _ carbon coupling catalyst, and the reactor conditions, such as gas flow rates (which affect the reactor residence time), temperature , and pressure. 在此所用的术语"较高级烃"是指具有较高碳数目(每个分子中有较多碳原子数)的烃,和/或与烃原料的一种或多种成分相比有较高键级的烃。 As used herein the term "higher hydrocarbons" refers to hydrocarbons with a higher number of carbon (per molecule has more carbon atoms) and / or compared with one or more components of the hydrocarbon feedstock has a higher bond order hydrocarbons. 例如,如果原料是纯甲烷(碳数目l,键级l),最终生产的较高级烃可能是乙烷、丙烷、乙烯、丙烯、更高级的烷类和烯烃类、还可能是炔类、和/ 或芳香族化合物。 For example, if the material is a pure methane (carbon number l, the key level l), the final production of higher hydrocarbons may be ethane, propane, ethylene, propylene, higher alkanes and alkenes, alkynes may be, and / or aromatic compounds. 如果原料是纯乙烷(碳数1 ;键级1),所得的较高级烃可能是丙烷(碳数3;键级1)、乙烯(碳数2,键级2)等。 If the material is a pure ethane (C 1; keys level 1), the resulting higher hydrocarbons may be propane (3 carbon atoms; key stage 1), ethylene (carbon number 2, key stage 2) and the like. 如果原料是天然气-典型的轻质烃类,其中有占优势的甲烷、与较少量的乙烷、丙烷和丁烷,以及甚至少量的更长的烃,例如戊烷、己烷等的混合物,生成的较高级烃可能包括一种或多种C2或更高的烷类,例如乙烷、丙烷、丁烷、C5+烃类、以及其他轻质挥发油;烯烃类,例如乙烯、丙烯、丁烯等;和/或芳香族烃类。 If the feedstock is natural gas - typically light hydrocarbons, which have dominant methane, with lesser amounts of ethane, propane and butane, and even a small amount of longer hydrocarbons, such as mixtures of pentane, hexane, etc. , higher hydrocarbons produced may include one or more C2 or higher alkanes, such as ethane, propane, butane, C5 + hydrocarbons, and other light volatile oil; olefins such as ethylene, propylene, butene and the like; and / or aromatic hydrocarbons. [0019] 某些类型的较高级烃类是特别期望的,包括"汽油范围"的烃类,例如C4-C12的烷类、更优选C5-C10的烷类,有或没有烯属的和/或芳香族的成分。 [0019] Certain types of higher hydrocarbons than are specifically contemplated, including the "petrol" and hydrocarbons, such as C4-C12 alkanes, preferably C5-C10 alkanes, with or without olefinic and / or aromatic ingredients. 具有高芳香族含量而苯含量较低的C5+烷类作为汽油或汽油掺合剂是特别可取的。 With high aromatic content and lower alkyl benzene content of C5 + class as gasoline or gasoline blending agent is particularly desirable. 其他所希望的产物包括芳香族化合物_苯、甲苯、二甲苯(尤其是对二甲苯)、均三甲苯等_以及尤其是苯含量低的芳香族化合物。 Other desired product comprising aromatic compounds _ benzene, toluene, xylenes (especially para-xylene), mesitylene _ and especially a low content of benzene aromatic compound. 在一个实施方案中,产物主要包括苯、或富苯的芳香族化合物。 In one embodiment, the products including benzene or benzene-rich aromatic compounds. 在另一个实施方案中,产物主要包括甲苯、或富甲苯的芳香族化合物。 In another embodiment, the main products include toluene, or toluene-rich aromatic compounds. 在一个实施方案中,产物的芳香族含量通过将非芳香的成分再循环至固体反应器而富集。 In one embodiment, the aromatic content of the product by the non-aromatic component is recycled to the reactor and the solid concentration. 在饱和的脂肪族化合物的情况下,这要求再溴化作用,接着在一种偶联催化剂的存在下进行碳-碳偶联,而在此处所描述的偶联催化剂的存在下烯属化合物可以直接偶联。 In the case of a saturated aliphatic compound, which requires re-bromination, followed by coupling in the presence of a catalyst of carbon - carbon coupling, whereas in the presence of a coupling catalyst described herein olefinic compounds may direct coupling.

[0020] 有代表性的卤化氢(HX)包括溴化氢(HBr)和氯化氢(HC1)。 [0020] Representative hydrogen halide (HX) includes hydrogen bromide (HBr) and hydrogen chloride (HC1). 还考虑到可以使用氟化氢(HF)和碘化氢(HI),但不一定有等效的结果。 Also take into account the hydrogen fluoride may be used (HF) and hydrogen iodide (HI), but not necessarily equivalent results. 与使用氟相关联的一些问题可以通过使用HF的稀释流(例如用氦气、氮气或其他稀释剂携带HF气体)而可能得到解决。 And some of the problems associated with the use of fluorine may be diluted by using HF stream (e.g. portable HF gas helium, nitrogen, or other diluent) which may be solved. 然而,可以预期,由于氟-碳键的强度大,烷基氟化物将需要更强的反应条件实现偶联并形成较高级烃。 However, it is contemplated that due fluoro - high strength carbon bond, alkyl fluoride will require a stronger condition for the coupling reaction and the formation of higher hydrocarbons. 相似地,与HI相关联的问题(例如某些碘反应的吸热性质)可以通过在较高级温度和/或压力下进行卤化和/或偶联反应而可能得到解决。 Similarly, the problems associated with HI (e.g., the endothermic nature of certain iodine reactions) may be carried out by halogenation and / or coupling reactions at higher temperatures and / or pressure may be solved. 优选使用HBr或HCl,HBr是最优选的。 Preferably using HBr or HCl, HBr being most preferred.

[0021] 许多材料能够可逆地俘获和释放HX,并且特别是HC1和HBr。 [0021] Many materials are capable of reversibly trapping and release HX, and in particular, HC1 and HBr. 作为第一实例,这类材料包括中长链的烯烃类,即每个分子具有10-100、优选15-80、更优选20-50个碳原子的烯烃类。 As a first example, such materials include long chain olefins, i.e., each molecule having 10-100, preferably 15-80, more preferably 20-50 carbon atoms olefin. 总体上,这类烯烃每个分子将具有一个以上的碳-碳双键。 In general, such olefins per molecule having one or more carbon - carbon double bond. 非限制性的特定的实例包括1-十二烯、1, 12-十二碳二烯、以及1- 二十烷。 Specific, non-limiting examples include 1-dodecene, 1, 12-dodecadiene, and 1-eicosane. 不饱和烯烃经过与HX的加成反应以形成部分卤化的烯烃或烷烃,并且由此"反应性地俘获"HX。 After the addition reaction of the unsaturated olefin with HX to form partially halogenated alkenes or alkanes, and thereby "reactively capture" HX. 当加热该材料时,它们会释放HX并且复原至烯烃。 When heating the material, they will be released and restored HX to alkenes.

[0022] 作为第二实例,不饱和的有机聚合物可以俘获HX以形成部分卤化的有机聚合物,这些有机聚合物然后可以释放HX。 [0022] As a second example, the unsaturated organic polymer can capture HX to form a partially halogenated organic polymer, then these organic polymers can be released HX. 非限制性实例包括聚乙炔、经部分脱氢的聚乙烯、经部分脱氢的聚丙烯、以及它们的混合物。 Non-limiting examples include polyacetylene, partially dehydrogenated polyethylene, polypropylene partially dehydrogenated, and mixtures thereof. 聚乙烯和聚丙烯可以根据本领域的普通技术人员所熟知的方法,例如通过卤化反应接着再脱卤化氢而脱氢。 Polyethylene and polypropylene can of ordinary skill in the art by well known methods, for example, followed by dehydrohalogenation by halogenation reaction dehydrogenation. 聚丁二烯是可以用于俘获并且然后释放HX的不饱和有机聚合物的另一个实例。 Polybutadiene can be used to capture and then release another instance of unsaturated organic polymers of HX.

[0023] 烯烃和不饱和有机聚合物通过与HX反应来俘获HX以形成部分卤化的化合物。 [0023] -olefin and unsaturated organic polymer by reaction with HX to capture HX to form a compound partially halogenated. 在空气或氧存在下,通过加热这些材料该反应可以逆向进行。 In the presence of air or oxygen, by heating the material of the reaction may be the reverse. 以下反应式是该基本方案的非限制性实例:[0024] The following reaction scheme is a non-limiting example of the basic scheme: [0024]

R R

+uv 获. + Uv is eligible.

释放hf Release hf

伴获 With eligible

R^v^v^R' + 靈 R ^ v ^ v ^ R '+ Spirit

释放 Release

[0025] 在一个实施方案中,不饱和材料携载于载体上,例如硅石、钛,或耐热的、无机的、 [0025] In one embodiment, the unsaturated material carrying on a carrier, such as silica, titanium, or a heat resistant, inorganic,

8总体上惰性的类似材料。 8 generally similar inert material. 作为一个实例,将硅石球粒与聚乙烯混合,将混合物加热到聚乙烯的玻璃化转变温度,这样聚乙烯便包覆在硅石粒料上,然后将卤素加到这些球粒中并且使该组合物暴露于紫外光下,由此该聚合物发生卤化反应。 As one example, the silica is mixed with the polyethylene pellets, the mixture is heated to the glass transition temperature of the polyethylene, so polyethylene pellets then coated onto silica, then the halogen is added to these pellets and to cause the composition were exposed to ultraviolet light, whereby the polymer halogenation reaction.

[0026] 在区2中,烷基卤化物是通过使烃原料与HX和02反应(卤氧化反应),和/或通过使烷基卤化物与&反应(卤化反应)而形成的。 [0026] In region 2, the alkyl halide is a hydrocarbon feedstock by reaction of HX and 02 (halo oxidation reaction), and / or by reacting with an alkyl halide & reaction (halogenation reaction) to form and the. UV光和/或热可以推进该反应。 UV light and / or heat may promote the reaction. 在一个优选的实施方案中,该反应是在一种卤化和/或卤氧化催化剂或催化反应剂的存在下发生的。 In one preferred embodiment, the reaction is carried out in the presence of a halide and / or a halogen catalyst or catalytic oxidation of reactants. 非限制性实例包括金属氧化物类,例如氧化铜(CuO),和金属卤化物类,例如CuC^、CuBi^等。 Non-limiting examples include metal oxides, such as copper oxide (CuO), and metal halides, e.g. CuC ^, CuBi ^ like. 可以使用多种催化剂的混合物。 Possible to use mixtures of various catalysts. 催化的材料可以是加载的或不加载的。 The catalytic material may be loaded or not loaded. [0027] 在图1中,催化剂遍布整个区2。 [0027] In Figure 1, the catalyst throughout the region 2. 在图2所示的另一个实施方案中,卤化和/或卤氧化催化剂是限制在区2的下游和上游区域8的,留下一个空的中心区域9。 In another embodiment shown in Figure 2, the halide and / or oxyhalide catalyst is limited to regions downstream and upstream region 2 8, leaving an empty central area 9. [0028] 在区1B和区3B中,碳-碳偶联催化剂用于使烷基卤化物转化成较高级烃类变得容易。 [0028] In the area 1B, and area 3B, the carbon - carbon coupling catalyst for reacting the alkyl halide is converted to higher hydrocarbons can be facilitated. 在此所用的术语"碳_碳偶联催化剂"是指能够催化碳_碳键形成的一种材料,可包括"真正的"催化剂,据推测这种催化剂是在机械学的水平上参与到反应中的,其在过程中不被消耗;也包括"催化反应剂",所述催化反应剂在反应过程中会被化学转化,但它们可以经由再生反应回复到它们的原始形式。 The term "carbon-carbon coupling catalyst _" as used herein refers to a material capable of catalyzing _ carbon-carbon bond formation, may include a "real" catalyst, this catalyst is presumably at the level of the mechanics involved in the reaction in, which is not consumed in the process; also includes "catalytic agent", the catalytic reaction in the reaction process will be chemically converted, but they can return to their original form by the regeneration reaction. 例如,在碳-碳偶联反应过程中,其催化反应剂中的氧原子便由卤原子代替了,但在随后的再生步骤中它又被再生(即卤素再被氧取代),例如通过将空气或氧经过该已发生转化的催化反应剂材料而使其再生。 For example, in a carbon - carbon coupling reaction, which catalyzes the reaction agent will be replaced by an oxygen atom a halogen atom, but in a subsequent regeneration step it is regenerated (i.e., halogen-substituted oxy again), for example, by air or oxygen through the catalytic conversion of the reactant material has occurred and regenerated. 碳_碳偶联催化剂还可以称作"低聚反应"催化剂,或简称为"偶联催化剂"。 Carbon-carbon coupling catalysts may _ also referred to as "oligomerization" catalyst, or simply referred to as "coupling catalyst."

[0029] 偶联催化剂的非限制性实例包括非结晶的铝硅酸盐类(无定形的固体酸)、钨/氧化锆超酸、硫酸化的锆、磷酸铝类例如SAP0-34以及其骨架取代的类似物(例如用Ni或Mn取代)、沸石,例如ZSM-5和其离子交换的类似物,以及骨架取代的ZSM-5(用Ti、Fe、Ti+Fe、B或Ga取代),以及其他微孔矿石。 [0029] Non-limiting examples of coupling catalysts include amorphous aluminosilicates (amorphous solid acids), tungsten / zirconia super acids, sulfated zirconia, aluminum phosphate and its skeleton classes e.g. SAP0-34 substituted analogs (e.g., substituted with Ni or Mn), the zeolite, e.g., ZSM-5 and the like ion exchange, and the framework-substituted ZSM-5 (with Ti, Fe, Ti + Fe, B or Ga-substituted), and other microporous minerals. 催化剂可以是天然的或合成的、掺杂的或未掺杂的、负载的或非负载的。 The catalyst may be natural or synthetic, doped or undoped, or non-load the load.

[0030] 用于生产室温液态烃类的优选催化剂包括其所含SiO乂A1^3比例小于300 : 1、优 Preferably the catalyst [0030] for the production of liquid hydrocarbons include room temperature which contains SiO qe A1 ^ 3 ratio is less than 300: 1, preferably

选小于ioo : 1、最优选为30 : l或更小的离子交换的zsM-5。 Preferably less than ioo: 1, most preferably from 30: l or less of ion-exchanged zsM-5. 优选的交换离子的非限制 Unrestricted preferred ion exchange

性实例包括Ag、 Ba、 Bi、 Ca、 Fe、 Li、 Mg、 Sr、 K、 Na、 Rb、 Mn、 Co、 Ni、 Cu、 Ru、 Pb、 Pd、 Pt和Ce的离子。 Examples include Ag, Ba, Bi, Ca, Fe, Li, Mg, Sr, K, Na, Rb, Mn, Co, Ni, Cu, Ru, Pb, Pd, Pt, and Ce ions. 这些离子可以作为纯盐或作为盐的混合物而交换。 These ions can be used as a pure salt or as a mixture of salts and to exchange. 掺杂的沸石的制备以及它们作为碳-碳偶联催化剂的用途,在专利公开号2005/0171393 Al中的4_5页描述过,该专利通过引用它的全文结合于本文中。 Preparation of doped zeolites and their use as a carbon - carbon coupling catalysts for, in Patent Publication No. 2005/0171393 Al in 4_5 page described, which is incorporated by reference in its entirety herein.

[0031] 沸石可从各禾中来源获取,包括Zeolyst International (Valley Forge,PA)。 [0031] The zeolite can be obtained from various sources Wo, including Zeolyst International (Valley Forge, PA). 具体实例包括掺杂的ZSM-5和掺杂的丝光沸石(其中,例如钙和/或镁是掺杂剂)。 Specific examples include doped ZSM-5 and doped mordenite (where, e.g., calcium and / or magnesium is a dopant). 在本发明的一个实施方案中,使用其Si02/Al203之比为30的Mn交换的ZSM-5作为偶联催化剂。 In one embodiment of the present invention, the use of which Si02 / Al203 ratio of Mn 30-exchanged ZSM-5 as a coupling catalyst. 在一定工艺条件下,用它可以生产选择性预先设定的液体烃产物。 Under certain conditions, it can be produced using a liquid hydrocarbon product selectivity preset.

[0032] 产品分布可以通过改变沸石或其他催化剂的特性向有利于形成更多的芳香族含量、或较少的芳香族含量、汽油等级材料方面变换。 [0032] The product distribution can change the characteristics of the zeolite or other catalyst to favor the formation of an aromatic content of more or less aromatic content, aspect gasoline grade materials transform. 可预期孔径大小和酸度对反应很重要。 Can be expected to pore size and acidity are important for the reaction. 酸度可以用于控制产品的链长度和官能度,而孔径大小可以控制链长度和官能度。 Acidity may be used to control the chain length and product functionality, and pore size may control chain length and functionality. 具有特定孔径的沸石可以选择性地生产苯、甲苯、对二甲苯、邻二甲苯、间二甲苯、混合的二甲苯、乙苯、苯乙烯、直链的烷基苯、和/或其他芳香族产物。 Zeolite having a specific pore size may be selectively produce benzene, toluene, xylene, o-xylene, m-xylene, mixed xylene, ethylbenzene, styrene, linear alkyl benzene, and / or other aromatic product. 也可以预期孔径大小会影响非芳香族产物的形成。 Pore size can be expected to affect the formation of non-aromatic products.

9[0033] 在本发明的不同的方面,空气和氧是用于完成所希望的结果,例如,除焦、卤氧化、HX释放、催化反应剂再生等。 9 [0033] In a different aspect of the invention, air and oxygen is used to accomplish the desired result, e.g., decoking, oxyhalides, HX is released, the catalytic reagent regeneration. 本文中的术语"空气或氧",可理解为包括大量基于氧的或含氧的气流的任何一种。 The term "air or oxygen", it is understood to include any of a large number of oxygen-based or oxygen-containing gas stream. 非限制性实例包括普通的空气、纯的氧气(02)、含有较小量的其他气态成分的氧气、在载气(例如氦)中稀释的氧气流、富氧的空气等。 Non-limiting examples include ordinary air, pure oxygen (02), oxygen other gaseous constituents containing smaller amounts, diluted in a carrier gas (e.g., helium) flow of oxygen, oxygen-enriched air or the like.

[0034] 为了使HX俘获或释放、催化剂除焦、卤化和/或卤氧化、以及形成产物的不同步骤变得容易,反应器中的不同的区是在合适的压力和温度下运行的,同时考虑了原料、催化剂、气体流速、以及所希望的产物。 [0034] In order to capture or release HX, catalyst decoking, halides and / or oxyhalides, and the formation of the different steps of the product is easy, the reactor is in a different zone under suitable pressure and temperature operation, while considered raw material, catalyst, gas flow rate, and the desired product. 在一个实施方案中,反应器是在(或稍微大于)大气压力下运行的。 In one embodiment, the reactor is at (or slightly greater than) the atmospheric pressure operation. 将区1A或3A加热到从0到500C 、优选100到400C 、更优选200到300C的温度从而使HX释放变得容易。 The region 1A or 3A is heated to from 0 to 500 C, preferably 100 到 400 C, more preferably 200 to 300 C temperature 到 so HX release easier. 将区3A或区1A加热到稍微较低的温度,例如0到400C、优选100到30(TC、更优选150到25(TC,从而使HX俘获变得容易。偶联催化剂的除焦是通过将区1B或3B加热到较高级温度,例如约50(TC而变得容易。烃原料的卤化和/或卤氧化发生在区2,将该区加热到150到60(TC、优选400到60(TC、更优选450到515。C的温度。产物形成(碳_碳偶联)是通过将区3B或1B加热到150到600C 、优选275到425C的温度而变得容易。有很多可替代的实施方案来实施本发明。例如,代替限定三个区的单一容器,区域反应器可以包括三个分离的容器,各自限定一个分离的区,1、2、或3。作为另一个实例,某些反应器的设计提供了改进热传递的可能性。因此,反应器可以配置为一系列的小管(内径小于6英寸,优从2到4英寸)。作为一个第三实例,代替串联构型,这些管可以并联安排,并且附在一个较大的容器内,合适的热传递流体在其中循环。此外,可以有空气或另一种惰性气体定向越过这些管束表面,从而使冷却和/或加热变得容易。[0035] 在一些应用中,其中从区2排除的物料必须在进入产品形成(复分解)区(区1B或3B)之前进行冷却,则可以使用预冷器。在一个实施方案中,预冷器包括空气冷却的管束或附在一个壳内的多个管子,该壳内有合适的热传递流体在这些管周围循环。使用预冷器可以减少复分解区中所需的反应器容量。在复分解过程中除热的要求可以很强地影响反应器的设计。 The area or region 1A 3A is heated to a slightly lower temperature, e.g., 0 到 400 C, preferably 100 到 30 (TC, and more preferably 150 到 25 (TC, so that the capture HX easier. Decoking coupling catalyst by the part 1B or 3B is heated to a higher temperature, e.g., about 50 (TC becomes easy. halogenated hydrocarbon feedstock and / or a halogen oxidation occurs in zone 2, the zone is heated to 150 到 60 (TC, preferably 400 to 60 (TC, and more preferably at a temperature of 450 to 515.C. product formation (carbon-carbon coupling _) by the area 3B or 1B heated to 150 到 600 C, preferably 275 到 temperature of 425 C becomes easy. There are many alternative embodiments of the present invention is implemented. For example, instead of a single container defining three zones, zone of the reactor may include three separate containers, each define a separation zone, 1, 2, or 3. As another example, in some reactor designs offer the possibility of improved heat transfer. Thus, the reactor can be configured as a series of small tube (inner diameter of less than 6 inches, preferably from 2 to 4 inches). As a third example , instead of the tandem configuration, the tubes can be arranged in parallel, and attached to a larger container, suitable heat transfer fluid circulating therein. In addition, there may be air or another inert gas is directed over the surfaces of these tubes, so that the cooling and / or heating can be facilitated. [0035] In some applications, where the material from zone 2 must be excluded before entering the product forming (metathesis) region (region 1B or 3B) is cooled, you can use the pre-cooler. In one embodiment, the precooler comprises a tube bundle or a plurality of tubes attached to one shell of an air-cooled, the shell has a suitable heat transfer fluid circulated around the tubes using a pre-cooler can be reduced in the metathesis zone The required capacity of the reactor. In the metathesis process of heat removal requirements can strongly affect the design of the reactor.

[0036] 另一个替代方案是在反应器自身内部使用惰性的热载体。 [0036] Another alternative is to use an inert in the reactor itself inside the heat carrier. 例如,可以加入过量的烷原料以分散热,由此使反应器形成填充床构型而不是管-壳布局。 For example, adding an excess of an alkoxy feedstock to dissipate heat, thereby forming a packed bed reactor configuration instead of tube - shell layout. 使用内部的热载体可以使反应器绝热地运行。 Using the internal heat carrier can run the reactor adiabatically. 也可以使用容易从反应产物流中分离出来的惰性流作为此构型中的热载体。 Can also be used easily separated from the reaction product stream out of the inert stream as this configuration the heat carrier. 绝热填充床方案预期可以显著地降低反应器成本。 Adiabatic packed bed scheme can be expected to significantly reduce the cost of the reactor.

[0037] 在本发明的另一个实施方案中,区域反应器与用ZSM-5沸石或能使汽油范围的烃类生成变得容易的其他材料填充的后反应器床联合使用的。 [0037] In another embodiment of the present invention, the zone of the reactor with the hydrocarbon with a ZSM-5 zeolite or make gasoline range can be easily generated after the other material filling the reactor bed for use in combination. 例如,区域反应器可以用于形成轻质烯烃,这些烯烃然后进料到沸石床,从而使轻质烯烃偶联成汽油范围内的烃类变得容易。 For example, the zone of the reactor may be used to form light olefins, such olefins and then fed to a zeolite bed, so that the coupling of light olefins to gasoline range hydrocarbons becomes easy.

[0038] 很多构建材料可以用于增加区域反应器的寿命。 [0038] The material of construction may be used to increase the number of regions of the reactor lifetime. 非限制性实例包括哈司特镍基合金、富铝和富铬的金属合金,钛、锆、钽和镍金属以及它们的合金,包覆的硅石、氧化铝、以及氧化锆的金属,以及传导热的陶瓷材料例如碳化硅。 Non-limiting examples include Hastelloy-based alloys, metal alloy aluminum rich and rich chrome, titanium, zirconium, tantalum and nickel metals and their alloys, coated silica, alumina, zirconia and metal, as well as conduction Thermal ceramic material such as silicon carbide. 反应器容器还可以由绝缘的、抗腐蚀的材料构成,例如铝、硅石、和锆,或各自有抗腐蚀的内衬。 The reactor vessel may also be composed of, corrosion-resistant insulating material, such as aluminum, silica, and zirconium, or each of which has corrosion-resistant lining. 但不一定用耐温的材料,例如聚四氟乙烯。 But not necessarily with a temperature resistant material, such as polytetrafluoroethylene. 在一些条件下,容器可以等温地运行,其中由热转移流体提供加热和/或冷却,而这些热转移流体,由以上列出的不同类型的热传导材料制成的管路来输送。 Under some conditions, the container can be run isothermally, wherein the heat transfer fluid is supplied by a heating and / or cooling, and these heat transfer fluids, comprised of different types of line thermally conductive materials listed above made to transport. 此外,反应器也可以绝热地运行。 In addition, the reactor may be run adiabatically. [0039] 实施例 [0039] EXAMPLE

[0040] 以下是本发明的非限制性实施例。 [0040] The following are non-limiting embodiment of the present invention. [0041] 能够释放并俘获HBr的材料的制备[0042] 试剂A和B Preparation of [0041] can be released and capture material HBr [0042] Reagents A and B

[0043] 高表面积(> 300m2/g)硅石粒料,通过混合粒料和聚乙烯并将其加热到高于聚乙烯的玻璃化转变温度的温度而使聚乙烯包覆粒料。 [0043] The high surface area (> 300m2 / g) silica pellets by mixing the pellets and the polyethylene and the polyethylene is heated to above the glass transition temperature of the polyethylene leaving the coated pellets. 将溴加入粒料并且将组合物暴露与UV光下,导致聚合物的溴化作用。 Bromine was added and the pellet composition is exposed to UV light, resulting in bromination of the polymer. 将材料的一半进行分离并且加热到225t:,从而释放HBr,由此形成能够俘获HBr的材料,即试剂A。 Half of the material was isolated and heated to 225t :, thereby releasing HBr, a material capable of trapping HBr thus formed, i.e., reagent A. 材料的另一半,即试剂B,用作能够释放HBr的材料。 Materials other half, i.e. the reagent B, is used as the material capable of releasing HBr. [0044] 试剂C禾口D [0044] Reagent C D Hekou

[0045] —种吸附剂的形成。 [0045] - adsorbents formation. 高表面积(> 300m2/g)硅石粒料通过混合粒料和聚乙烯,并且将其加热到高于聚乙烯的玻璃化转变温度的温度而使聚乙烯包覆粒料。 High surface area (> 300m2 / g) silica pellets by mixing the pellets and the polyethylene, and the polyethylene is heated to above the glass transition temperature of the polyethylene leaving the coated pellets. 将氯加入粒料并且将组合物暴露于UV光下,导致聚合物的氯化作用。 Adding chlorine to the pellets and the composition is exposed to UV light, resulting in the chlorination of the polymer. 将材料的一半进行分离并且加热到225t:,从而释放HCl。 Half of the material was isolated and heated to 225t :, thereby releasing HCl. 材料的另一半不作处理,用作含HC1的吸附剂。 The other half will not be processed material, used as an adsorbent containing HC1 in. [0046] 实施例1 [0046] Example 1

[0047] 如图1所示的区域反应器是用以下材料装填的: [0047] zone of the reactor shown in Figure 1 is packed with the following materials:

[0048] 区IA:试剂B。 [0048] zone IA: Reagent B.

[0049] 区IB :ZSM-5偶联催化剂。 [0049] zone IB: ZSM-5 catalyst coupling.

[0050] 区2:氧化铜催化剂。 [0050] Zone 2: copper oxide catalyst.

[0051] 区3B :ZSM-5偶联催化剂。 [0051] Area 3B: ZSM-5 catalyst coupling.

[0052] 区3A:试剂A。 [0052] Area 3A: Reagent A.

[0053] 在步骤l中,空气在225t:的温度下经过区lA,试剂B转化成试剂A,并且释放HBr。 [0053] In step l, the air in the 225t: temperature through zone lA, Reagent B converted into reagent A, and the release of HBr. 来自区1A的空气和HBr在50(TC的温度下首先进入区1B(在随后的运行中,这将再生(除焦)偶联催化剂),并且然后进入区2,天然气在这里在40(TC被溴氧化。区2的产物在40(rC经过区3B中的偶联催化剂,生产较高级烃和HBr。在区3A中,HBr是在150C的温度下用试剂A俘获的(试剂A转化为试剂B)。 Air from the area 1A and HBr at 50 (at a temperature of TC first enters zone 1B (in subsequent runs, this will regeneration (decoking) coupling catalyst), and then enters zone 2, where the gas 40 (TC by bromine oxidation. The product region 2 at 40 (rC through region 3B of the coupling catalyst, the production of higher hydrocarbons and HBr. 3A, in the area, HBr at a temperature of 150 C with the capture reagent A of (Reagent A converted to reagent B).

[0054] 在步骤2中,空气在225C的温度下经过区3A,试剂B转化成试剂A,并且释放HBr 。 [0054] In step 2, the air at a temperature of 225 C through area 3A, Reagent B is converted to the reagent A, and the release of HBr. 来自区3A的空气和HBr在50(TC的温度下进入3B,再生(除焦)偶联催化剂。在区2中,天然气在40(TC被溴氧化。区2的产物在40(TC经过区1B的偶联催化剂,生产较高级烃和HBr。在区A中,HBr是在150C的温度下用试剂A俘获的(试剂A转化为试剂B)。[0055] 实施例2 Area 3A from air and HBr 50 (under TC temperature entering 3B, regeneration (decoking) coupling catalyst in zone 2, natural gas at 40 (TC by bromine oxidation. The product zone 2 in 40 (TC through the area 1B the coupling catalyst, to produce higher hydrocarbons and HBr. In zone A, HBr at a temperature of 150 C with the capture reagent A (reagent A into reagent B). [0055] Example 2

[0056] 实施例1的烃产物在350到450C的温度经过ZSM-5催化剂,从而改变产物的平均分子量。 [0056] The hydrocarbon product of Example 1 at a temperature of 350 through 450 C 到 ZSM-5 catalyst, thereby changing the average molecular weight of the product.

[0057] 实施例3 [0057] Example 3

[0058] 按照实施例1的程序,但使用氧化鸨和氧化锆的混合物(WZA)代替ZSM-5,作为 [0058] The procedure of Example 1, but using bustards oxide and zirconium oxide mixture (WZA) instead of the ZSM-5, as

碳-碳偶联催化剂。 Carbon - carbon coupling catalyst. [0059] 实施例4 [0059] Example 4

[0060] 实施例3的烃产物在350到450C的温度经过ZSM_5催化剂,从而改变产物的平均 Hydrocarbon products [0060] Example 3 at a temperature of 350 到 450 C through ZSM_5 catalyst, thereby changing the average product

分子量。 Molecular weight.

[0061] 实例5[0062] 如图1所示的区域反应器是用以下材料装填的: [0061] Example 5 [0062] zone of the reactor shown in Figure 1 is packed with the following materials:

[0063] 区1A:试剂D。 [0063] Zone 1A: Reagent D.

[0064] 区IB :ZSM-5偶联催化剂。 [0064] zone IB: ZSM-5 catalyst coupling.

[0065] 区2:氧化铜催化剂。 [0065] Zone 2: copper oxide catalyst.

[0066] 区3B :ZSM-5偶联催化剂。 [0066] Area 3B: ZSM-5 catalyst coupling.

[0067] 区3A :试剂C。 [0067] Area 3A: Reagent C.

[0068] 在步骤l中,空气在225t:的温度下经过区1A,试剂D转化成试剂C,并且释放HC1。 [0068] In step l, the air in 225t: temperature through zone 1A, reagent D is converted to the reagent C, and the release of HC1. 来自区A的空气和HC1在500C的温度下进入区IB (在随后的运行中,这将再生(除焦)偶联催化剂),并且然后进入区2,天然气在这里在40(TC被氯氧化。区2的产物在40(TC经过区3B中的偶联催化剂,生产较高级烃和HC1 。在区3A中,HC1是在150C的温度下用试剂C俘获的(试剂C转化为试剂D)。 Air from the zone A into the zone IB and HC1 at a temperature of 500 C (in the subsequent runs, this will regeneration (decoking) coupling catalyst), and then enters zone 2, where the natural gas at 40 (TC is oxychloride. The product region 2 at 40 (TC through region 3B of coupling catalyst, to produce higher hydrocarbons and HC1. in area. 3A, HC1 at a temperature of 150 C with a capture reagent of C (reagent C Conversion reagent D).

[0069] 在步骤2中,空气在225C的温度下经过区3A,试剂D转化成试剂C,并且释放HC1 。 [0069] In step 2, the air at a temperature of 225 C through area 3A, reagent D is converted to the reagent C, and the release of HC1. 来自区3A的空气和HC1在50(TC的温度下进入区3B,再生(除焦)偶联催化剂。在区2中,天然气在40(TC被溴氧化。区2的产物在40(TC经过区1B中的偶联催化剂,生产较高级烃和HC1 。在区1A中,HC1是在150C的温度下用试剂C俘获的(试剂C转化为试剂D)。[0070] 实例6 Area 3A from air and HC1 in 50 (under TC temperature into the area 3B, regeneration (decoking) coupling catalyst in zone 2, natural gas 40 (TC by bromine oxidation. The product zone 2 in 40 (TC after region 1B in the coupling catalyst, the production of higher hydrocarbons and HC1. in area. 1A, HC1 at a temperature of 150 C with the capture reagent C (reagent C into reagent D). [0070] Example 6

[0071 ] 实例5的烃产物在350到450C的温度下经过ZSM-5催化剂,从而改变产物的平均 [0071] Examples of the hydrocarbon product after 5 ZSM-5 catalyst at a temperature of 350 到 450 C, thus changing the average product

分子量。 Molecular weight.

[0072] 实例7 [0072] Example 7

[0073] 按照实例5的程序,但使用氧化鸨和氧化锆的混合物(WZA)代替ZSM-5 ,作为 [0073] The procedure of Example 5, but using bustards oxide and zirconium oxide mixture (WZA) instead of the ZSM-5, as

碳-碳偶联催化剂。 Carbon - carbon coupling catalyst. [0074] 实例8 [0074] Example 8

[0075] 实例7的烃产物在350到450C的温度下经过ZSM-5催化剂,从而改变产物的平均分子量。 [0075] Examples of the hydrocarbon product 7 through ZSM-5 catalyst at a temperature of 350 到 450 C, thus changing the average molecular weight of the product.

[0076] 本发明已经参考不同的实施方案、图、以及实例进行描述,但并非限制于此。 [0076] The present invention has been described with reference to various embodiments, diagrams, and examples will be described, but not limited thereto. 本领域的普通技术人员将理解的是,本发明可以按多种方式进行更改而不脱离本发明,本发明仅由附属的权利要求书以及它的等效物来限定。 Ordinary skill in the art will appreciate that the present invention may be changed in various ways without departing from the present invention, the present invention only the book and its equivalents by the claims appended hereto.

Classifications
International ClassificationC07C2/00
Cooperative ClassificationC01B7/135, C07C17/152, B01J8/0438, B01J8/0442, B01J2208/00265, C07C1/30, C01B7/093, B01J8/12, C07C2523/30, B01J8/10, C07C2521/06, C07C2529/40, C01B7/01, B01J2208/025, C10G50/00, B01J2208/00752, B01J8/0496, B01J8/0492, B01J2208/0053, B01J8/067, B01J2208/00761, C01B7/191
European ClassificationC01B7/13B, C01B7/09B, C07C17/152, C01B7/01, C01B7/19B, C07C1/30, C10G50/00, B01J8/06H, B01J8/04H, B01J8/10, B01J8/04F, B01J8/12, B01J8/04B4D, B01J8/04B4F
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