SYNTHESIS OF LIGHT OLEFINS FROM SYNGAS VIA DIMETHYLETHR——A NEW TECHNIQUE PROCESS

A new route named as SDTO method for the synthesis of lightolefins from syngas has been proposed.That is to convert syngas todimethylether and then to convert dimethylether to light olefins.The catalystsfor the two conversion reactions have been developed.For the first reaction,the catulySt was synthesized by the combination of methanol synthesis catalystwith γ-Al_2O_3or zeolites which possesses both metallic and acidic functions.Thecatalyst for the second reaction was modified SAPO-34 molecular sieve.Thevariables of the reactions have also been investigated.The results from theserial connection of the two conversion steps without any separation show thatthe yield of C_2~-C_4~- olefins Could be>100g/(m~3 syngas).     

合成气制低碳烯烃K－Fe－MnO／MgO催化剂的研究Ⅰ．MnO助剂的作用

采用ＣＯ加氢反应、ＣＯ－ＴＰＤ、ＣＯ／Ｈ＿２－ＴＰＳＲ及Ｃ＿２Ｈ＿４／Ｈ＿２－ＴＰＳＲ等手段，研究合成气制低碳烯烃反应Ｋ－Ｆｅ－ＭｎＯ／ＭｇＯ催化剂中ＭｎＯ的助剂作用。结果表明ＭｎＯ能大幅度提高低碳烯烃的选择性，尤其是乙烯的选择性；ＭｎＯ能抑制催化剂表面的乙烯加氢，因而有利于提高低碳烯烃的选择性及烯／烷的比值。     

EFFECT OF MOLYBDENUM PROMOTER ON THE Cu-Co BASED CATALYSTS

The synthesis of mixed alcohols (C1-C5) from syngas has been studied at 6. 0 MPa over modified Co/CuLaZr catalysts. The molybdenum addition enhanced greatly the activity and the selectivity to alcohols. The improvement of hydrogenation capacity of the system via a reversible spillover effect of hydrogen could explain this effect, together with a great capacity of CO insertion, illustrated by the effect of C2H4 addition as a probe to syngas. Under our experimental conditions, a mixed alcohol production of 147.1g/kg. cat/h containing a proportion of 33. 1% of higher alcohols (C2 OH) was obtained with a selectivity to ROH of 52. 8%.     

K-La-Ni/Si-2催化低碳烷烃与二氧化碳重整制合成气(英文)

Ｎｉ／Ｓｉ２催化剂具有较好的低碳烷烃与二氧化碳重整制合成气的反应性能，添加Ｌａ２Ｏ３助剂和Ｋ２Ｏ助剂可提高催化剂活性和合成气收率，从而进一步改善催化剂的低碳烷烃与ＣＯ２重整制合成气的反应性能，研制的ＫＬａＮｉ／Ｓｉ２催化剂，用于天然气与ＣＯ２重整反应制合成气可达９７％的低碳烷烃转化率和９５％以上的合成气收率。     

Investigation on the Performance of Supported Molybdenum Carbide for the Partial Oxidation of Methane

The performance of uspported and unsupported molybdenum carbide for the partial oxidation of methane (POM) to syngas was investgated.An evaluation of the catalysts indicates that bulk molybdenum carbied has a higher methane conversion during the initial stage but a lower selectivity to CO and H2/CO ratio in the products.The rapid deactivation of the catalyst is also a significant problem.However,the supported molybdenum carbide catalyst shows a much higher methane conversion,increased selectivity and significantly improved catalytic stability.The characterization by XRD and BET specific area measurements depict an improved dispersion of molybdenum carbide when using alumina as a carrier.The bulk or the supported molybdenum carbide exists in the β-Mo2C phase,while it is transformed into molybdenum dioxide postcatalysis which is an improtant cause of molybdenum carbide deactivation.     

担体对Fe—MnO催化剂CO＋H2反应性能的影响

考察氧化物担体对Fe-MnO催化剂反应性能影响的结果表明,担体的类型对Fe-MnO催化剂CO加氢反应性能影响很大,其低碳烯烃选择性相差悬殊,Al_2O_3、SiO_2和MgO担载的Fe-MnO催化剂都不利于低碳烯烃的生成,而TiO_2担载的Fe-MnO催化剂则具有较高的烯烃选择性和催化活性。从担体-金属相互作用本质的差异,研究了担体对金属活性组分化学状态的影响及催化活性相与F-T合成烯烃的关系,发现担体-金属间的电子效应有利于催化剂活性和选择性的提高,其它物理化学效应引起的相互作用则不利于改善催化剂性能;还表明Fe_(?)C是催化活性相,Fe~(2+)物种的存在不利于提高烯烃的选择性。     

在改进的Ni基催化剂上的甲烷部分氧化制合成气反应

 本文采用高温分解和焙烧硝酸盐的方法合成了一系列Ni基六铝酸盐催化剂BaNiyAl12-yO19-δ (y=0.1、0.3、0.6、0.9和1.0)，并对它们在甲烷部分氧化制合成气反应中的催化性能、催化剂表面积碳及活性组分Ni流失等情况进行了考察。结果表明，该催化剂对甲烷部分氧化制合成气反应具有较好的催化活性，在850 ℃，甲烷转化率和CO选择性分别可达92%和95%。并且催化剂BaNiyAl12-yO19-δ (y=0.3)在100小时的POM反应后，催化剂表面积碳很少，积碳量仅为样品净重的0.8%，特别是100小时反应后，催化剂表面活性组分Ni没有发生流失。这种低积碳量和无活性组分Ni流失与催化剂结构中Ni与相邻原子间的强相互作用有关。     

Studies on the Performance and Structure of Supported Catalysts for the Partial Oxidation of Methane to Syngas

The catalytic properties of several supported metal catalysts on different carriers were studied in the partial oxidation of methane (POM) to syngas. In our experiment, supported noble metal catalysts exhibited better performance than the other supported transition metal catalysts. The catalyst performances were significantly influenced by the d-electron configuration of the active metal components and the dispersion of active metal components on the support. A catalyst with a moderate number of unpaired electrons in the d-orbital of the active metal support without obvious acidity or redox activity (e.g. MgO) was suitable for POM performance. The Rh/SiO2 catalyst was the best in the POM reaction, among those investigated. Reaction conditions apparently also affected the POM performance of the catalyst. The conversion of methane and the selectivity for CO increased with the reaction temperature, and a high CH4/O2 ratio was not beneficial for POM performance.     

Ln0.5A0.5MnO3 (Ln=Lanthanide,A= Ca,Sr) Perovskites Exhibiting Remarkable Performance in the Thermochemical Generation of CO and H2 from CO2 and H2O

Perovskite oxides of the Ln_0.5A_0.5MnO₃ (Ln=lanthanide, A=Sr, Ca) family have been investigated for the thermochemical splitting of H₂O and CO₂ to produce H₂ and CO respectively. The amounts of O₂ and CO produced strongly depend on the size of the rare earth ions and alkaline earth ions. The manganite with the smallest rare earth possessing the highest distortion and size disorder as well as the smallest tolerance factor, gives out the maximum amount of O₂, and, hence, the maximum amount of CO. Thus, the best results are found with Y_0.5Sr_0.5MnO₃, which possesses the highest distortion and size disorder. Y_0.5Sr_0.5MnO₃ shows remarkable fuel production activity even at the reduction and oxidation temperatures as low as 1200 °C and 900 °C, respectively.