CN1124468A - 用于将c1-4烃转化为c2烯烃的新方法和无机载体催化剂 - Google Patents
用于将c1-4烃转化为c2烯烃的新方法和无机载体催化剂 Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000000969 carrier Substances 0.000 title abstract 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003345 natural gas Substances 0.000 claims abstract description 8
- PXURRFCLQDNZOY-UHFFFAOYSA-L carbon monoxide;dichlororuthenium;triphenylphosphane Chemical compound [Cl-].[Cl-].[Ru+2].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 PXURRFCLQDNZOY-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 4
- 239000010457 zeolite Substances 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- -1 phosphorus compound Chemical class 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 11
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003426 co-catalyst Substances 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 4
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- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 7
- 230000001131 transforming effect Effects 0.000 claims 3
- 239000012046 mixed solvent Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 41
- 150000001875 compounds Chemical class 0.000 abstract description 9
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract 6
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 abstract 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 abstract 1
- 229910019891 RuCl3 Inorganic materials 0.000 abstract 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 abstract 1
- 150000003018 phosphorus compounds Chemical class 0.000 abstract 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 abstract 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 abstract 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 abstract 1
- 229910009112 xH2O Inorganic materials 0.000 abstract 1
- MPSNIORYZNMYEL-UHFFFAOYSA-N ethane ethene Chemical compound C=C.CC.C=C.CC MPSNIORYZNMYEL-UHFFFAOYSA-N 0.000 description 11
- 239000011877 solvent mixture Substances 0.000 description 9
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
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- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
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Abstract
用于通过转化C1-4低级烃如甲烷或纯天然气制备主要含双键的C2低级烃如乙烯的无机载体催化剂Ma′Pc/S，M选自RuCl2(PPh3)3、RuCl2(CO)2(PPh3)2、Ru3(CO)12、RhCl(CO)(PPh3)2、IrCl(CO)(PPh3)2、Pd(PPh3)4、Pt(PPh3)4、RuCl3·xH2O，S为无机载体，选自α-Al2O3、γ-Al2O3、SiO2、SiO2-Al2O3、Y-沸石、MgO和TiO2，P为作为助催化剂的磷化合物，选自PPh3、P(OCH3)3、P(OC2H5)3、P(O)(OC2H5)3，α′为催化剂中金属的重量百分数，选自0.25-5％(重)，C为催化剂中助催化剂重量百分数，为1.0-20.0％(重)。
Description
本发明涉及通式I所示无机载体催化剂，它被用于通过直接转化C1-4低级烃如甲烷、纯天然气(下文称其为LNG)和液化石油气(下文称其为LPG)生产主要具有双键、被用作石油化学工业和精细化工如医药、农业化肥等领域基本活性化合物的C2低级烃如乙烯，这些应用过程包括进行聚合、共聚和缩聚反应，本发明还涉及该催化剂的制备方法。
Ma’Pc/S (I)
此外，本发明提供一种在约500—980℃，以670—850℃为佳的温度下在氮和本发明催化剂存在下直接转化(制备)低级C1-4烷如甲烷或LNG的新方法，与采用相同催化剂但属于不同于本发明技术领域的类似先有技术中通过脱氢合成烃的传统方法反应温度相比要明显地低，其产率之高直至今日仍几乎无法获得，作为基本反应活性化合物的C2低级烯烃如乙烯可通过简单方法在短时间内获得，在反应过程如通过加入氧进行的氧化偶联反应几乎不产生副产物如CO2。
式I中，M选自下列化合物：RuCl2(PPh3)3，RuCl2(CO)2(PPh3)2，Ru3(CO)12、RhCl(CO)(PPh3)2、IrCl(CO)(PPh3)2、Pd(PPh)3)4、Pt(PPh3)4、RuCl3.xH2O，S为选自α—Al2O3、γ—Al2O3、SiO2、SiO2—Al2O3、Y—沸石、MgO和TiO2的无机载体，P为作为助催化剂的磷化合物如PPh3、P(OCH3)3、P(OC2H5)3、P(O)(OC2H5)3，a’为催化剂中金属重量百分数，约为0.25—5％(重)，C为催化剂中助催化剂的重量百分数，1.0—20.0％(重)。
众所周知，先有技术中几乎没有关于催化剂的文献和专利能够通过直接转化甲烷生产乙烯，作为与本发明不同的技术领域，它们的缺点是产生大量副产物如难以分离与脱除的二氧化碳并且可能造成环境污染；通过传统脱氢过程合成烃的方法在约1500—1550℃较高温度下通过热或电裂解反应进行，结果导致能源大量损失，耐高温设备费用昂贵以及热能消耗尤其是反应器被严重腐蚀等问题。
作为先有技术，有关通过氧化偶合与脱氢反应合成烃的内容，有如U.S专利No.5066629,5068486和5118654，加拿大专利No.2016675和日本专利No.04352730，04368342。
因此，在本发明中，预期通过在本发明新型催化剂存在下、在不出现上述问题和不产生诸如氧化偶合反应的CO2之类副产物前提下直接转化甲烷或LNG来制备低级烃如乙烯，这种新型催化剂能够在不象脱氢合成烃过程那样高的温度而是在明显较低(中低)温度下完成转化反应，人们一直在寻求制备这种新型催化剂的新方法的必要条件及使用这种新催化剂转化成为(制备)低级烃如乙烯的新方法。
为了达到上述预期目的，本发明人经过多年研究克服了上述各种缺陷并且完成了新型催化剂及其制备方法的全部开发工作，这是一种用于制备C2-4低级烯烃如乙烯的简单方法，其中在本发明催化剂存在下短时间内直接将低级烃如甲烷或LNG在与脱氢合成烃或氧化偶合反应温度相比明显低的反应温度下转化，从而制得高产率和含痕量杂质的产物并且节省了由于脱氢合成烃或氧化偶合反应所需的能耗。此外，本发明提供一种通过明显地降低杂质即CO2含量从而制备能够充分有效地解决环境污染问题的新型催化剂的方法，该催化剂能够在短时间内以出人意料的高产率将C1-4低级烃如甲烷或LNG转化为C2-4低级烯烃如乙烯。
参照实施例对本发明进行更详细的描述。
首先通过将金属配位化合物与助催化剂承载于无机载体上制备用于生产含双键C2-4低级烃(主要为乙烯)的新型承载催化剂，为求通过甲烷或LNG的脱氢偶合反应直接制备低级烃如乙烯，适合制备C2-4主要含双键低级烃如乙烯的催化剂通过将各种有机金属配位化合物和助催化剂承载于无机载体上被制成。
在此方法中，合成与纯化过程要比其它方法中容易得多。
通过开发该催化剂，可以采用明显地温和的反应条件如反应温度、压力并且高产率地制备低级烃如乙烯。
此外，由于本发明催化剂的作用，简化了低级烃如乙烯的制备，从而大大提高了生产率。
下面对本发明进行详细描述。
在本发明中，低级烃类如甲烷或LNG直接转化为C2-4双键低级烃主要为乙烯，这是该新方法与现有通过脱氢或氧化偶合反应合成烃的方法之间主要技术不同点，整个过程被简化，此外，反应温度被降至约500—980℃，以670—850℃为佳，杂质如CO2量被大大减少。
在本发明制备低级烃如乙烯的过程中，采用下列催化剂：Ru配位体化合物如RuCl2(PPh3)3、RuCl2(CO)2(PPh3)2，加入三苯膦，于约810℃以高产率制得乙烯，转化率保持在约8—12％，通过循环可转化几乎全部加入的原料(约93—100％)。
也就是说，借助采用Ru配位体化合物的承载催化剂进行的固体表面反应可以明显地降低反应温度和压力，反应条件大大缓和，同时简化了反应设备。
无机载体上承载催化剂的制备方法如下所述。
将金属簇形(化合物)与有机金属配位体化合物溶于主要含有二氯甲烷和丙酮的溶剂混合物。
此外，将无机载体加至该溶液中，催化物质在约20—200℃浸入无机载体，随后将其真空干燥。
本文所用的无机载体为α—Al2O3、γ—Al2O3、SiO2、SiO2—Al2O3、Y—沸石、MgO和TiO2。
所用的催化剂化合物为RuCl2(PPh3)3、RuCl2(CO)2(PPh3)2、Ru3(CO)12、RhCl(CO)(PPh3)2、IrCl(CO)(PPh3)2、Pt(PPh3)4、Pd(PPh3)4、RuCl3、xH2O。
根据本发明的实验，用于制备低级烃如乙烯的理想无机载体为α—Al2O3和MgO，VIII族金属有如Ru、Rh。
在本发明新型催化剂存在下的反应条件如下所述：
举例来说，氮稀释甲烷或LNG的比例为1—6，以1—3为佳。
反应温度约为500—980℃，以670—850℃为佳，以710—810℃为最佳。
催化剂浓度低于5％(重)，以1—3％(重)为佳。
气体的空速约为75—1200小时-1，以150—600小时-1为佳。
反应压力通常约为1—10大气压，以1—5大气压为佳。
C1-4低级烃如甲烷或LNG的转化率以及C2-4低级烯烃如乙烯的产率与选择性如下所述。 
通过气相色谱分析反应物与产物。
实施例1—11描述了新型催化剂及其制备方法，实施例12—22介绍了通过在新型催化剂(式I)存在下完成C1-4低级烃如甲烷或LNG的转化反应制备C2-4主要含双键的低级烃新方法。
实施例1
将5.16克α—Al2O3、1.00克RuCl2(PPh3)3(1.04毫摩尔)、1.09克(4.16毫摩尔)PPh3在大约40℃加入含有20毫升二氯甲烷和10毫升丙酮的溶剂混合物中，搅拌约30分钟。蒸发该悬浮液，减压蒸馏后得到固体，真空干燥约20小时后得到催化剂RuCl2(PPh3)3PPh3/α—Al2O3
实施例2：
将0.56克(0.744毫摩尔)RuCl2(CO)2(PPh3)2、0.78克(2.97毫摩尔)PPh3溶于含有40毫升二氯甲烷和10毫升丙酮的溶剂混合物中，随后加入3.68克α—Al2O3。在约40℃下将该悬浮液搅拌约30分钟，减压蒸除溶剂。随后真空干燥约20小时，制得RuCl2(CO)2(PPh3)2·PPh3/α—Al2O3催化剂。
实施例3
将3.95克α—Al2O3、0.17克(0.266毫摩尔)Ru3(CO)12、0.09克(0.343毫摩尔)PPh3溶于含有10毫升二氯甲烷和100毫升丙酮的溶剂混合物中。
在约40℃下将该悬浮液搅拌约30分钟并减压蒸除溶剂。
真空干燥所获得的残余物约20小时，制得Ru3(CO)12、PPh3/α—Al2O3催化剂。
实施例4
将3.28克α—Al2O3、0.45克(0.652毫摩尔)RhCl(CO)(PPh3)2、0.68克(2.59毫摩尔)PPh3溶于10毫升二氯甲烷和30毫升丙酮的溶剂混合物。
在约40℃搅拌该悬浮液约30分钟并减压蒸除溶剂。
真空干燥所获得的残余物约20小时，制得RhCl(CO)(PPh3)2·PPh3/α—Al2O3催化剂。
实施例5
将3.14克α—Al2O3、0.26克(0.333毫摩尔)IrCl(CO)(PPh3)2、0.35克PPh3(1.33毫摩尔)溶于含有60毫升二氯甲烷和10毫升丙酮的溶剂混合物中。
在约40℃搅拌该悬浮液约30分钟并减压蒸除溶剂。
真空干燥所获得的残余物约20小时，制得IrCl(CO)(PPh3)2PPh3/α—Al2O3催化剂。
实施例6
将3.7克α—Al2O3、0.84克(0.727毫摩尔)Pd(PPh3)4、0.76克(2.90毫摩尔)PPh3溶于由30毫升二氯甲烷和10毫升丙酮组成的溶剂混合物。
在约40℃搅拌该悬浮液约30分钟并减压蒸除溶剂。
真空干燥所获得的残余物约20小时，制得Pd(PPh3)4PPh3/α—Al2O3催化剂。
实施例7
将4.45克α—Al2O3、0.58克(0.466毫摩尔)Pt(PPh3)4、0.49克(1.87毫摩尔)PPh3溶于含有30毫升二氯甲烷和10毫升丙酮的溶剂混合物中。
在约40℃搅拌该悬浮液约30分钟并减压蒸除溶剂。
真空干燥所得到的残余物约20小时，制得Pt(PPh3)4·PPh3/α—Al2O3催化剂。
实施例8
采用实施例1的方法制备RuCl2(PPh3)3PPh3/MgO催化剂，所不同的是使用4.39克MgO和0.93克(3.55毫摩尔)PPh3作为无机载体。
实施例9
按照实施例1制备RuCl2(PPh3)3PPh3/α—Al2O3催化剂，所不同的是采用0.25克(0.261毫摩尔，0.5％(重)Ru)RuCl2(PPh3)3和0.27克(1.03毫摩尔)PPh3作为无机载体。
实施例10
按照实施例1制备RuCl2(PPh3)3PPh3/α—Al2O3催化剂，所不同的是采用1.0克(1.04毫摩尔，4.0％(重)Ru)RuCl2(PPh3)3)和PPh31.09克(4.16毫摩尔)作为无机载体。
实施例11
将5.01克α—Al2O3、0.21克(1.012毫摩尔)RuCl3.xH2O、1.06克(4.04毫摩尔)PPh3加至含有20毫升二氯甲烷和10毫升丙酮的溶剂混合物中并在约40℃将其搅拌约30分钟。减压蒸馏该悬浮液得到的固体，真空干燥约20小时，得到RuCl3·xH2O·PPh3/α—Al2O3催化剂。
下表中给出的实施例12—22分析结果为近似值。至于温度，则为基于给定值的邻近温度。
实施例12
将甲烷(或LNG)与氮分别以10毫升/分钟的流速加入固定相连续反应器(内径：0.70厘米，长度40厘米，材料：不锈钢316)，其中催化剂为实施例1制备的RuCl2(PPh3)3PPh3/α—Al2O3(2％(重)Ru)在约1大气压(至5大气压)于每一反应温度下经连续反应形成产物，气相色谱分析结果如表1所示(原料被连续地重复投入转化反应)。 表1
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.23.64.96.08.612.1 | 1.42.53.95.37.711.0 | 0.81.11.00.70.91.1 | 63.669.479.688.389.590.9 | 36.430.620.411.710.59.1 |
实施例13
重复实施例12，所不同的是采用RuCl2(CO)2(PPh3)2·PPh3/α—Al2O3作为催化剂，产物分布情况如表2所示。
表2
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.83.84.65.46.68.6 | 1.93.04.04.85.97.7 | 0.90.80.60.60.70.9 | 67.978.987.088.989.489.5 | 32.121.113.011.110.610.5 |
实施例14
重复实施例12，所不同的是使用Ru3(CO)12·PPh3/α—Al2O3(2％(重)Ru)作为催化剂，产物分布情况见表3。
表3
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.43.54.65.46.88.3 | 1.72.94.04.86.27.8 | 0.70.60.60.60.60.5 | 70.882.987.088.991.294.0 | 29.217.113.011.18.86.0 |
实施例15
重复实施例12，所不同的是采用RhCl(CO)(PPh3)2·PPh3/α—Al2O3(2％(重)Rh)作为催化剂，产物分布如表4所示。
表4
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.22.64.45.56.78.5 | 1.21.83.44.76.07.8 | 1.00.81.00.80.70.7 | 54.569.277.385.589.691.8 | 45.530.822.714.510.48.2 |
实施例16
重复实施例12，所不同的是采用IrCl(CO)(PPh3)2·PPh3/α—Al2O3(2％(重)Ir)作为催化剂，产物分布见表5
表5
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.03.14.55.26.68.2 | 1.22.33.74.55.97.6 | 0.80.80.80.70.70.6 | 60.074.282.286.589.492.7 | 40.025.817.813.510.67.3 |
实施例17
重复实施例12，所不同的是采用Pd(PPh3)4·PPh3/α—Al2O3(2％(重)Pd)作为催化剂，产物分布见表6。
表6
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 1.72.64.15.56.78.6 | 1.12.03.44.86.07.9 | 0.60.60.70.70.70.7 | 64.776.982.987.389.691.9 | 35.323.117.112.710.48.1 |
实施例18
重复实施例12，所不同的是采用Pt(PPh3)4·PPh3/α—Al2O3
表7
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 1.12.23.24.76.07.5 | 0.71.52.54.05.47.0 | 0.40.70.70.70.60.5 | 63.668.278.185.190.093.0 | 36.431.821.914.910.06.7 |
实施例19
重复实施例12，所不同的是采用RuCl2(PPh3)3·PPh3/MgO(2％(重)Ru)作为催化剂，产物分布见表8。
表8
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.33.24.14.46.36.4 | 1.32.23.33.65.55.9 | 1.01.00.80.80.80.5 | 56.568.880.581.887.392.2 | 43.531.219.518.212.77.8 |
实施例20
重复实施例12，所不同的是采用RuCl2(PPh3)3·PPh3/α—Al2O3(0.5％(重)Ru)作为催化剂，产物分布见表9。
表9
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 1.31.93.04.67.18.2 | 0.71.22.33.96.47.5 | 0.60.70.70.70.70.7 | 53.863.276.684.890.191.5 | 46.236.823.415.29.98.5 |
实施例21
重复实施例12，所不同的是采用RuCl2(PPh3)3·PPh3/α—Al2O3(4.0％(重)Ru)作为催化剂，产物分布见表10。
表10
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790810 | 2.43.64.96.37.710.5 | 1.62.53.95.46.89.6 | 1.01.01.00.90.90.9 | 66.771.479.685.788.391.4 | 33.328.620.414.311.78.6 |
实施例22
重复实施例12，所不同的是采用RuCl3·xH2O·PPh3/α—Al2O3(2％(重)Ru)作为催化剂，产物分布见表11。
表11
| 反应温度*(℃) | 转化率％ | 产率(％) | 选择性(％) | ||
| 乙烯 | 乙烷 | 乙烯 | 乙烷 | ||
| 710730750770790 | 0.41.11.82.64.4 | 0.00.50.91.73.5 | 0.40.60.90.90.9 | 0.045.550.065.479.5 | 100.054.550.034.620.5 |
Claims (8)
1.用于通过转化C1-4低级烃如甲烷或纯化天然气制备主要含有双键的C2低级烃如乙烯的无机载体催化剂Ma’Pc/S……式(I)其中M选自RuCl2(PPh3)3、RuCl2(CO)2(PPh3)2、Ru3(CO)12、RhCl(CO)(PPh3)2、IrCl(CO)(PPh3)2、Pd(PPh3)4、Pt(PPh3)4、RuCl3·xH2O，S为无机载体，选自α—Al2O3、γ—Al2O3、SiO2、SiO2—Al2O3、Y—沸石、MgO和TiO2，P为作为助催化剂的磷化合物，选自PPh3、P(OCH3)3、P(OC2H5)3、P(O)(OC2H5)3，a’为催化剂中金属的重量百分数，选自0.25—5％(重)，C为催化剂中助催化剂重量百分数，为1.0—20.0％(重)。
2.用于通过转化C1-4低级烃如甲烷或纯化天然气制备主要含有双键的C2低级烃如乙烯的无机载体催化剂Ma’Pc/S(其中M，P，S，a’和c定义如权利要求1)的生产方法，其中将M、P和S加至单一或混合溶剂如以适当比例混合物的二氯甲烷与丙酮，在约20—200℃回流搅拌该悬浮液，减压蒸馏溶剂并真空干燥残余物。
3.用于通过转化C1-4低级烃如甲烷、纯化天然气或液化石油气制备主要含有双键的C2低级烃如乙烯的无机载体催化剂Ma’Pc/S(其中M，P，S，a’和c定义如权利要求1)的生产方法，其中将M、P和S加至单一或混合溶剂如以适当比例混合物的二氯甲烷与丙酮，优选在约40—150℃回流搅拌该悬浮液，减压蒸馏溶剂并真空干燥残余物。
4.主要含双键C2低级烃如乙烯的制备方法，其特征在于C1-4低烃级与氮在权利要求1中通式(I)Ma’Pc/S(M、P、S、a’和c如权利要求1定义)所示催化剂存在下于约500—980℃和1—10大气压下反应。
5.主要含双键C2-4低级烃的制备方法，其特征在于C1-4低级烃与氮在权利要求1中通式(I)Ma’Pc/S(M、P、S、a’和c如权利要求1定义)所示催化剂存在下优选于约670—850℃和1—5大气压下反应。
6.主要含双键C2低级烃如乙烯或如权利要求4和5所述烃的制备方法，其中使用选自甲烷或纯天然气的C1-4低级烃并使含C1-4低级烃的天然气与氮在权利要求1中通式(I)Ma’Pc/S(M、P、S、a’和c如权利要求1定义)所示催化剂存在下优选于约710—810℃和1—5大气压下反应。
7.如权利要求4和/或5所述主要含双键C2低级烃如乙烯的制备方法，其中氮/甲烷(或纯天然气等)摩尔比为1—6，以1—3为佳，进料气的空速为75—1200小时-1，以150—600小时-1为佳。
8.按照权利要求4和/或5的方法，其中催化剂(如权利要求1所述，Ma’Pc/S)浓度小于5％(重)，以1—3％(重)为佳。
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| Application Number | Priority Date | Filing Date | Title |
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| KR1993/8927 | 1993-05-22 | ||
| KR1019930008927A KR960005497B1 (ko) | 1993-05-22 | 1993-05-22 | 메탄 또는 정제된 천연가스의 전환반응용 무기체 담지촉매, 그 제조방법 및 그것을 사용한 에틸렌의 제조방법 |
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| CN1124468A true CN1124468A (zh) | 1996-06-12 |
| CN1054316C CN1054316C (zh) | 2000-07-12 |
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| CN94192208A Expired - Fee Related CN1054316C (zh) | 1993-05-22 | 1994-05-21 | 催化剂、其制备方法及其在乙烯制备中的应用 |
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| Country | Link |
|---|---|
| US (1) | US5900521A (zh) |
| JP (1) | JP2731872B2 (zh) |
| KR (1) | KR960005497B1 (zh) |
| CN (1) | CN1054316C (zh) |
| AU (1) | AU6761494A (zh) |
| RU (1) | RU2113279C1 (zh) |
| WO (1) | WO1994027723A1 (zh) |
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| US6159890A (en) * | 1996-04-30 | 2000-12-12 | Bp Amoco Corporation | Ruthenium-containing catalyst system for olefin metathesis |
| US6793699B2 (en) * | 2001-09-05 | 2004-09-21 | Dennis D. Coleman | Continuous tracer generation apparatus |
| US7223602B2 (en) * | 2001-09-05 | 2007-05-29 | Coleman Dennis D | Continuous tracer generation method |
| US20040157940A1 (en) * | 2003-02-07 | 2004-08-12 | Dalton Robert C. | Method of transport energy |
| US8277525B2 (en) * | 2003-02-07 | 2012-10-02 | Dalton Robert C | High energy transport gas and method to transport same |
| CA2427722C (en) | 2003-04-29 | 2007-11-13 | Ebrahim Bagherzadeh | Preparation of catalyst and use for high yield conversion of methane to ethylene |
| KR100885311B1 (ko) * | 2007-09-04 | 2009-02-24 | 한국화학연구원 | 피셔-트롭쉬 합성용 코발트/인-알루미나 촉매와 이의 제조방법 |
| GB201104522D0 (en) * | 2011-03-17 | 2011-05-04 | Johnson Matthey Plc | Complexes |
| CN104148101B (zh) * | 2013-05-13 | 2016-12-28 | 中国科学院大连化学物理研究所 | 一种甲烷无氧直接制烯烃的方法及其催化剂 |
| WO2016011169A1 (en) * | 2014-07-18 | 2016-01-21 | Sabic Global Technologies B.V. | Hydrogen abstraction from alkanes using hydrogen storage materials |
| JP6298438B2 (ja) * | 2014-11-28 | 2018-03-20 | 旭化成株式会社 | 炭化水素の製造方法 |
| US10472303B2 (en) * | 2017-08-30 | 2019-11-12 | Uchicago Argonne, Llc | Alkane activation with single and bi-metallic catalysts |
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| JPS54119451A (en) * | 1978-03-09 | 1979-09-17 | Ajinomoto Co Inc | Preparation of alpha-halogen substituted-gamma-butyrolactone |
| US4255283A (en) * | 1978-03-23 | 1981-03-10 | The Standard Oil Company | Oxydehydrogenation process for alkylaromatics and catalyst therefor |
| JPS57118527A (en) * | 1981-01-16 | 1982-07-23 | Mitsubishi Chem Ind Ltd | Preparation of ethylene glycol |
| CA1250318A (en) * | 1984-04-16 | 1989-02-21 | Gennaro J. Maffia | Natural gas conversion |
| DD256514A1 (de) * | 1987-01-23 | 1988-05-11 | Leipzig Chemieanlagen | Verfahren zur katalytischen herstellung von aromaten aus methan |
| US5105053A (en) * | 1989-06-26 | 1992-04-14 | Exxon Research And Engineering Company | High surface area oxide compositions with a pyrochlore structure, methods for their preparation, and conversion processes utilizing same |
| GB2253858A (en) * | 1991-03-21 | 1992-09-23 | Shell Int Research | Hydrocarbon production |
| US5177294A (en) * | 1991-05-15 | 1993-01-05 | The United States Of America As Represented By The United States Department Of Energy | Catalysts for conversion of methane to higher hydrocarbons |
-
1993
- 1993-05-22 KR KR1019930008927A patent/KR960005497B1/ko not_active IP Right Cessation
-
1994
- 1994-05-21 US US08/549,718 patent/US5900521A/en not_active Expired - Fee Related
- 1994-05-21 JP JP7500489A patent/JP2731872B2/ja not_active Expired - Lifetime
- 1994-05-21 CN CN94192208A patent/CN1054316C/zh not_active Expired - Fee Related
- 1994-05-21 WO PCT/KR1994/000054 patent/WO1994027723A1/en active Application Filing
- 1994-05-21 AU AU67614/94A patent/AU6761494A/en not_active Abandoned
- 1994-05-21 RU RU95122281/04A patent/RU2113279C1/ru not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08506053A (ja) | 1996-07-02 |
| RU2113279C1 (ru) | 1998-06-20 |
| US5900521A (en) | 1999-05-04 |
| KR960005497B1 (ko) | 1996-04-25 |
| CN1054316C (zh) | 2000-07-12 |
| AU6761494A (en) | 1994-12-20 |
| WO1994027723A1 (en) | 1994-12-08 |
| JP2731872B2 (ja) | 1998-03-25 |
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