CN1054316C - 催化剂、其制备方法及其在乙烯制备中的应用 - Google Patents
催化剂、其制备方法及其在乙烯制备中的应用 Download PDFInfo
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- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 abstract 3
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- 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
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- 229910052682 stishovite Inorganic materials 0.000 abstract 1
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- 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
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 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
- 238000013019 agitation 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
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Abstract
用于通过转化转化甲烷或纯天然气制备乙烯的无机载体催化剂Ma’Pc/S及其制备方法。M选自Ru Cl2(PPh3)3、Ru Cl2 (CO)2(PPh3)2、Ru3 (CO)12、Rh Cl(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所示用于制备乙烯的无机载体催化剂，它被用于包括石油化工与精细化工领域中的聚合、共聚和缩聚反应在内的基本反应，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670-850℃，以710-810℃为佳的温度下在氮和本发明催化剂存在下直接转化甲烷或纯天然气以便制备乙烯的新方法，本发明与通过脱氢合成烃的传统方法反应温度相比要明显地低，借助该方法，可以在短时间内以高产率且在不产生诸如CO、CO2之类副产物的前提下制备乙烯，这与通过加入氧进行的氧化偶联反应相反。
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。
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以及使用这种新催化剂转化成为乙烯的新方法。
为了达到上述预期目的，本发明人经过多年研究完成了新型催化剂及其制备方法以及在本发明催化剂存在下短时间内将甲烷或纯天然气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乙烯的方法全部开发工作，这样，在明显低的温度下完成的直接转化甲烷的过程节省了由于脱氢合成烃或氧化偶合反应所需的能耗并且通过降低杂质即CO2含量从而充分有效地解决环境污染问题。
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新型催化剂，即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，催化剂的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乙烯。
此外，由于本发明催化剂的作用，简化了乙烯的制备方法，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，甲烷或纯天然气直接转化为乙烯，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670-850℃，以710-810℃为佳，杂质如CO2量被大大减少。
在本发明中，向Ru配位体化合物如RuCl2(PPh3)3、RuCl2(CO)2(PPh3)2中加入助催化剂三苯膦，于约810℃以高产率制得乙烯，转化率保持在约8-12％，通过连续循环使加入的原料转化率达到最大值。
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，在约20-200℃被搅拌下金属簇形(化合物)和有机金属配位体化合物浸入无机载体，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。
所用的金属簇形(化合物)与有机金属配位体化合物为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，用于制备乙烯的最佳无机载体为α-Al2O3和MgO，VIII族金属为Ru、Rh。
在本发明新型催化剂存在下的反应条件如下所述：
氮稀释甲烷或纯天然气的比例以甲烷为基准计为1-6，以1-3为佳。
反应温度约为670-850℃，以710-810℃为佳。
催化剂浓度低于5.0％(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1-5大气压，以常压为佳。
甲烷或纯天然气的转化率以及乙烯的产率与选择性如下所述。 
或者
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存在下完成甲烷或纯天然气的转化反应制备乙烯的新方法。
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)3PIh3/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 | 2.43.54.96.37.710.5 | 1.62.53.95.46.89.6 | 1.01.01.00.90.90.9 | 65.771.479.685.788.391.4 | 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 (7)
1.用于通过转化甲烷或纯天然气制备乙烯的承载于无机载体上的催化剂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.用于通过转化甲烷或纯天然气制备乙烯的承载于无机载体上的催化剂Ma’Pc/S的生产方法，其中M、P、S、a’和c如权利要求1限定，该方法包括将M、P和S加至二氯甲烷与丙酮的单一或混合溶剂中，在约30-250℃回流搅拌该悬浮液，随后减压蒸馏溶剂并真空干燥残余物。
3.按照权利要求2的方法，其中悬浮液在40-150℃下被回流搅拌。
4.乙烯的制备方法，其特征在于甲烷或纯天然气与氮在其中M、P、S、a’和c如权利要求1定义的通式(I)Ma’Pc/S所示催化剂存在下于约670-850℃和1-5大气压下反应。
5.按照权利要求4的方法，其中甲烷或纯天然气在约710-810℃与常压下反应。
6.按照权利要求4或5的方法，其中氮/甲烷或纯天然气的稀释比为1-6，进料气的空速为75-1200小时-1。
7.按照权利要求4或5的方法，其中催化剂浓度小于或等于5％(重)。
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| US4255283A (en) * | 1978-03-23 | 1981-03-10 | The Standard Oil Company | Oxydehydrogenation process for alkylaromatics and catalyst therefor |
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| 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 |
-
1993
- 1993-05-22 KR KR1019930008927A patent/KR960005497B1/ko not_active IP Right Cessation
-
1994
- 1994-05-21 JP JP7500489A patent/JP2731872B2/ja not_active Expired - Lifetime
- 1994-05-21 US US08/549,718 patent/US5900521A/en not_active Expired - Fee Related
- 1994-05-21 RU RU95122281/04A patent/RU2113279C1/ru not_active IP Right Cessation
- 1994-05-21 AU AU67614/94A patent/AU6761494A/en not_active Abandoned
- 1994-05-21 WO PCT/KR1994/000054 patent/WO1994027723A1/en active Application Filing
- 1994-05-21 CN CN94192208A patent/CN1054316C/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54119451A (en) * | 1978-03-09 | 1979-09-17 | Ajinomoto Co Inc | Preparation of alpha-halogen substituted-gamma-butyrolactone |
| JPS57118527A (en) * | 1981-01-16 | 1982-07-23 | Mitsubishi Chem Ind Ltd | Preparation of ethylene glycol |
| DD256514A1 (de) * | 1987-01-23 | 1988-05-11 | Leipzig Chemieanlagen | Verfahren zur katalytischen herstellung von aromaten aus methan |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6761494A (en) | 1994-12-20 |
| US5900521A (en) | 1999-05-04 |
| RU2113279C1 (ru) | 1998-06-20 |
| JP2731872B2 (ja) | 1998-03-25 |
| KR960005497B1 (ko) | 1996-04-25 |
| JPH08506053A (ja) | 1996-07-02 |
| WO1994027723A1 (en) | 1994-12-08 |
| CN1124468A (zh) | 1996-06-12 |
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