Optimization of methane conversion to liquid fuels over W-Cu/ZSM-5 catalysts by response surface methodology

The conversion of methane to liquid fuels is still in the development process. The modified HZSM-5 by loading with Tungsten （W） enhanced its heat resistant performance, and the high reaction temperature （800℃） did not lead to the loss of W component by sublimation. The loading of ZSM-5 with Tungsten and Copper （Cu） resulted in an increment in the methane conversion, CO2, and C5＋ selectivities. The high methane conversion and C5＋ selectivity, and low H2O selectivity are obtained by using W/3.0Cu/ZSM-5. The optimization of methane conversion over 3.0 W/3.0Cu/ZSM-5 under different temperature and oxygen concentration using response surface methodology （RSM） are studied. The optimum point for methane conversion is 19% when temperature is 753 ℃, and oxygen concentration is 12%. The highest C5＋ selectivity is 27% when temperature is 751 ℃. and oxwen concentration is 11%.     

Characterization and Activity of Cr, Cu and Ga Modified ZSM—5 for Direct Conversion of Methane to Liquid Hydrocarbons

Direct conversion of methane using a metal-loaded ZSM-5 zeolite prepared via acidic ion exchange was investigated to elucidate the roles of metal and acidity in the formation of liquid hydrocarbons. ZSM-5 (SiO2/A12O3=30) was loaded with different metals (Cr, Cu and Ga) according to the acidic ion-exchange method to produce metal-loaded ZSM-5 zeolite catalysts. XRD, NMR, FT-IR and N2 adsorption analyses indicated that Cr and Ga species managed to occupy the alllmlnum positions in the ZSM-5 framework. In addition, Cr species were deposited in the pores of the structure. However, Cu oxides were deposited on the surface and in the mesopores of the ZSM-5 zeolite. An acidity study using TPD-NH3, FT-IR, and IR-pyridine analyses revealed that the total number of acid sites and the strengths of the BrSusted and Lewis acid sites were significantly different after the acidic ion exchange treatment.Cu loaded HZSM-5 is a potential catalyst for direct conversion of methane to liquid hydrocarbons. The successful production of gasoline via the direct conversion of methane depends on the amount of aluminum in the zeolite framework and the strength of the BrSnsted acid sites.     

Dual-Bed Catalytic System for Direct Conversion of Methane to Liquid Hydrocarbons

A dual-bed catalytic system is proposed for the direct conversion of methane to liquid hydrocarbons. In this system, methane is converted in the first stage to oxidative coupling of methane (OCM) products by selective catalytic oxidation with oxygen over La-supported MgO catalyst. The second bed, comprising of the HZSM-5 zeolite catalyst, is used for the oligomerization of OCM light hydrocarbon products to liquid hydrocarbons. The effects of temperature (650-800℃), methane to oxygen ratio (4 10), and SiO2/Al2O3 ratio of the HZSM-5 zeolite catalyst on the process are studied. At higher reaction temperatures, there is considerable dealumination of HZSM-5, and thus its catalytic performance is reduced. The acidity of HZSM-5 in the second bed is responsible for the oligomerization reaction that leads to the formation of liquid hydrocarbons. The activities of the oligomerization sites were unequivocally affected by the SiO2/Al2O3 ratio. The relation between the acidity and the activity of HZSM-5 is studied by means of TPD-NH:j techniques. The rise in oxygen concentration is not beneficial for the C5 selectivity, where the combustion reaction of intermediate hydrocarbon products that leads to the formation of carbon oxide (CO CO2) products is more dominant than the oligomerization reaction. The dual-bed catalytie system is highly potential for directly converting methane to liquid fuels.     

Non-oxidative conversion of methane into various petrochemical grades over tunable tri-metallic Fe-W-Mo/HZSM-5 catalyst systems

Most mono-metallic catalysts applied in non-oxidative conversion of methane exhibit low catalyst activity and limited selectivity towards useful petrochemicals. In this study, a series of thermally stable and tunable 5.4 wt% metal/support Fe-W-Mo/HZSM-5 catalyst systems were synthesized, characterized, and applied in non-oxidative conversion of methane in a custom-made stainless-steel reactor at various process conditions. Analysis of products from the reactor was done using Shimadzu 2014 gas chromatograph. Varying the amount of Fe, W, and Mo on HZSM-5 greatly influenced catalyst activity in terms of methane conversion and product distribution. When the quantities of Fe and W were increased to 2.25 wt% each and the quantity of molybdenum reduced to 0.9 wt% in the overall 5.4 wt% metal/ HZSM-5 catalyst, the resultant catalyst system became most active in methane conversion (17.4%) at 800 °C. Reducing the quantity of Fe and W each to 1.35 wt% and increasing Mo to 2.7 wt% in the overall 5.4 wt% catalyst, the resultant catalyst system became less selective towards C₂ hydrocarbons and coke, but highly selective towards xylene and benzene. Therefore, this study demonstrates that varying metal loading presents an opportunity to tune the 5.4 wt% binary Fe, W, and Mo on HZSM-5 to achieve desired methane conversion and product distribution.     

电场增强催化甲烷合成碳二烃催化剂影响研究

本研究提出了在常温、常压电场增强等离子体条件下甲烷直接转化合成碳二烃的洁净工艺 ,在不同的放电电压、放电功率、甲烷进料流量和不同的催化剂作用下 ,甲烷能够以不同的转化率和选择性转变为碳二烃。对影响甲烷转化率和碳二烃选择性的因素 :放电电压、放电功率、甲烷进料流量和催化剂进行了研究 ,对催化剂性能进行了比较 ,并探讨了反应机理。结果表明 ,适宜的工艺条件 :放电电压 2 0kV～ 4 0kV ;输入功率 :2 0W～ 4 0W ;合适的甲烷进料流量 :30mL/min～ 70mL/min。在该条件下 ,碳二烃的选择性可以达到 95 % ;催化剂对甲烷转化率的影响顺序为MnO2 /Al2 O3 >Ni/Al2 O3 >MoO3 /Al2 O3 >Ni/NaY >Pd/ZSM 5 >Ni/H4Mg2 Si3 O4>Ni/ZSM 5 >Co/ZSM 5 >无催化剂。     

Non-oxidative dehydro-oligomerization of methane to higher molecular weight hydrocarbons at low temperatures

The non-oxidative dehydro-oligomerization of methane to higher molecular weight hydrocarbons such as aroma tics and C2 hydrocarbons in a low temperature range of 773-973 K with Mo/HZSM-5,Mo-Zr/HZSM-5 and Mo-W/HZSM-5 catalysts is studied.The means for enhancing the activity and stability of the Mo-containing catalysts under the reaction conditions is reported.Quite a stable methane conversion rate of over 10% with a high selectivity to the higher hydrocarbons has been obtained at a temperature of 973 K.Pure methane conversions of about 5.2% and 2.0% have been obtained at 923 and 873 K,respectively.In addition,accompanied by the C2-C3 mixture,tht- methane reaction can be initiated even at a lower temperature and the conversion rate of methane is enhanced by the presence of tne initiator of C2-C3 hydrocarbons.Compared with methane oxidative coupling to ethylene,the novel way for methane transformation is significant and reasonable for its lower reaction temperatures and high selectivity to the desired prod     

Studies on Mo／HZSM-5 Complex Catalyst for Methane Aromatization

The influence of adding Fe,Cr,Co,and Ga into 3%Mo/HZSM-5 catalyst on methane aromatization,and the influence of additives ratio on methane conversion,selectivity to hydrocarbons and coke,as well as distribution of aromatics were investigated.The experimental results showed that the addition of Fe,Cr,Co and Ga promoted the dehydrogenation and dissociation of methane.The results of NH3-TPD indicated that the acidity of HZSM-5 was changed by adding Fe and Co components,consequently the catalytic properties of Mo/HZSM-5 were changed.It was also revealed that strong acid sites were the center of methane aromatization.The results of XRD characterization showed that the crystallinity of Mo on ZSM-5 zeolite was increased after adding Fe,Co additives.     

焙烧方法和焙烧条件对纳米Au/HZSM-5催化剂金粒径和催化性能的影响

采用负压沉积沉淀法制备了纳米Au/HZSM-5催化剂前体,研究了深床焙烧和等离子体焙烧两种方法,以及焙烧温度和焙烧气氛对催化剂中纳米金粒径和催化性能的影响,并采用ICP、TEM、XRD、UV-vis、XPS等表征方法对催化剂金粒子进行了物化性能表征,采用合成气羰基化制乙酸甲酯反应表征催化性能。结果表明,不同焙烧方法和不同焙烧温度及气氛对负载型纳米Au/HZSM-5催化剂中金粒径、形貌、物化性质和催化性能有明显影响。其中,以等离子体焙烧方法在500℃氮气气氛下制备的纳米1.86%Au/HZSM-5催化剂中的金粒径最小,为2-5 nm。用于催化合成气羰基化制乙酸甲酯反应,原料中CO的转化率为67%,乙酸甲酯选择性可达78%。     

CH_4在Mo/HZSM-5及其改性催化剂上的无氧芳构化(英文)

运用微型固定床反应器装置,研究了Mo/HZSM-5催化剂的Mo载量、金属助剂改性、载体模数对甲烷无氧芳构化反应性能的影响。结果表明,Ni/Mo摩尔比为0.1的Mo-Ni/HZSM-5(SiO2/Al2O3=25)催化性能最好,其稳定性较好,芳烃收率最高可达15.74%;此时甲烷转化率60.24%,芳烃选择性26.13%。     

Effect of dispersion and distribution of tungsten on W/HZSM-5 for selective catalytic reduction of NO by acetylene

Catalytic performance of W/HZSM-5 in selective catalytic reduction of NO by acetylene was investigated in a reaction system with 1600 ppm of NO, 800 ppm of C2H2, and 9.95% of O2 in He. It was found that promotional effect of tungsten on the reaction is strongly affected by catalyst preparation conditions and Si/Al ratio of the parent zeolite. A better dispersion of tungsten on HZSM-5 and relatively more monomeric tungsten species were found on 8%W/HZSM-5 prepared by impregnation of the zeolite with lower SiO2/A1203 ratio （25） in ammonic ammonium tungstate solution and calcination of the resulting material at higher temperature （550 ℃）. The highest NO conversion to N2 of 86.3% in the reaction system was obtained at 350 ℃ over the catalyst thus prepared. The mechanism of monomeric tungsten species improving the C2H2-SCR can be attributed to accelerating the formation of active nitrate species.     

HZSM-5分子筛上C_(6～8)混合链烃和邻二甲苯的加氢裂化

在连续流动固定床装置上,探讨了不同酸性HZSM-5上C6~8混合链烃(以下简称混合烃)和邻二甲苯加氢裂化的变化规律,并在稳定条件下考察了反应温度、质量空速以及氢烃体积比等反应参数的影响。混合烃的加氢裂化伴随着芳构化反应,酸性较弱的HZSM-5主要发生加氢裂化反应,裂化产物以正构烷烃为主,甲烷和异构烷烃较少。酸性强的HZSM-5上,起初以芳构化反应为主,稳定之后产物分布与弱酸催化剂接近。混合烃的加氢裂化反应表现出明显的温度效应,而质量空速和氢烃体积比的影响较小。在380℃、3.0 MPa、质量空速1.02 h-1、氢烃体积比1 000的条件下,100 h内混合烃的转化率均在99%以上,稳定的裂化反应选择性在95%以上。邻二甲苯发生加氢裂化及异构、歧化反应,酸性强的HZSM-5裂化产物收率高,裂化产物分布与混合烃的基本相同。稳定的邻二甲苯裂化反应选择性小于10%。     

Dealuminated ZSM-5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance     

甲烷芳构化反应催化剂的研究——Mo-M/HZSM-5在无氧条件下的催化性能和表面性质

苯;甲烷芳构化反应催化剂的研究——Mo-M/HZSM-5在无氧条件下的催化性能和表面性质     

CATALYTIC CRACKING OF LIGHT ALKANES IN THE PRESENCE OF O_2 AND SELECTIVE CONTROL OF OLEFIN PRODUCTS

lntroductionThesmallolefinslikeethylene,propeneandbutenearethec0mmerciallydesirablepetrochemicalfeedstocksandarefoundincreasingusageinchemicalindustry.Theyareusuallyobtainedfromthepyrolysis0fpetroleumhydrocarb0nswithsteaInatveryhightemPeratUreandarealsoavailablefromFCCprocess.TheimProvedFCCcatalystforeIhancingtheolefinproducthasbeenreportedll].However,FCCisalrnostimPossiblefortheshortchainalkanefeedstockscutfrompetroleum0robtuinedfromrefinerygasornatUralgassincecrackingofhydrocarbonsbeco…     

Ethylene Conversion to Higher Hydrocarbon over Copper Loaded BZSM-5 in the Presence of Oxygen

The successful production of higher hydrocarbons from methane depends on the stability or the oxidation rate of the intermediate products. The performances of the BZSM-5 and the modified BZSM-5 catalysts were tested for ethylene conversion into higher hydrocarbons. The catalytic experiments were carried out in a fixed-bed micro reactor at atmospheric pressure. The catalysts were characterized using XRD, NH3-TPD, and IR for their structure and acidity. The result suggests that BZSM-5 is a weak acid. The introduction of copper into BZSM-5 improved the acidity of BZSM-5. The conversion of ethylene toward higher hydrocarbons is dependent on the acidity of the catalyst. Only weaker acid site is required to convert ethylene to higher hydrocarbons. The loading of Cu on BZSM-5 improved the selectivity for higher hydrocarbons especially at low percentage. The reactivity of ethylene is dependent on the amount of acidity as well as the presence of metal on the catalyst surface. Cu1%BZSM-5 is capable of converting ethylene to higher hydrocarbons. The balances between the metal and acid sites influence the performance of ethylene conversion and higher hydrocarbon selectivity. Higher loading of Cu leads to the formation of COx.     

Catalytic Combustion of Methane over High Copper-Loading ZSM-5 Catalysts

Two series of Cu/ZSM-5 catalysts,loading from 5 to 20 wt% CuO,were prepared by the deposition-precipitation and impregnation methods,respectively.The catalysts prepared by the impreg- nation method showed better catalytic performances than those prepared by the deposition-precipitation method and the increase of copper loading favored methane conversion.20Cu(I)/ZSM-5 had the highest activity with T_(90%)of 746 K,and for 20Cu(D)/ZSM-5,T_(90%)was as high as 804 K.The characteriza- tion of X-ray diffraction(XRD),temperature-programmed reduction(TPR),temperature-programmed desorption(TPD),and X-ray photoelectron spectroscopy(XPS)revealed that the dispersion of cop- per species could be improved by using the deposition-precipitation method instead of the impregnation method,but the fraction of surface CuO,corresponding to active sites for methane oxidation,was larger on 20Cu(I)/ZSM-5 than 20Cu(D)/ZSM-5.The results of Pyridine-Fourier transform infrared spectrum (Py-FT-IR)showed that a majority of Lewis acidity and a minority of Brφnsted acidity were present on Cu/ZSM-5 catalysts.20Cu(I)/ZSM-5 presented more Lewis acid sites.The number of Lewis acid sites changed significantly with preadsorption of oxygen.Adsorption of methane and oxygen on acid sites was observed.The properties of Cu/ZSM-5 catalysts were correlated with the activity for methane oxidation.     

DEHYDROGENATION AND AROMATIZATION OF METHANE IN THE ABSENCE OF OXYGEN OVER DOPED Mo/HZSM-5 CATALYSTS

研究了在Ｍｏ／ＨＺＳＭ－５催化剂上添加助剂以及不同的反应预处理温度对甲烷无氧脱氢芳构化反应的影响。实验结果表明，由于第二组分的添加，Ｍｏ／ＨＺＳＭ－５催化剂的活性和选择性都得到了较大程度的改善。预处理温度是影响催化剂反应性能的关键因素。Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂经过８７３Ｋ空气预处理后，甲烷在９７３Ｋ的转化率约为１０％，催化剂的稳定性也得到较大程度的提高。ＴＰＳＲ实验结果表明，Ｒｕ的加入降低了芳烃生成的温度。ＴＰＯ和ＤＴＡ实验结果表明，在Ｍｏ－Ｒｕ／ＨＺＳＭ－５催化剂上可生成较多的碳物种，结合反应结果，可以认为反应过程中生成的碳物种对甲烷的无氧脱氢芳构化反应是起积极作用的     

Low-temperature activation of methane over rare earth metals promoted Zn/HZSM-5 zeolite catalysts in the presence of ethylene

At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons (C2–C4) and aromatics (C6–C10), through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.     

Dealuminated ZSM—5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Broensted acid sites in the formation of higher hydrocarbons,The oligomeriztion of olefins,dependent on the acidity of ZSM-5 zeolite ,is an important step in the conversion of natural gas to liquied fuels,The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst,ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios,The FT-IR analysis revealed that the integrated framework aluminum band,non-framework aluminum band,and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated,The performanc of the dealuminated zeolite was tested for ethylene oligomerization.The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion,but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite ,The characterization results revealed the amount of aluminum in the zeolitic framework,the crystallinity of the ZSM-5 zeolite,and the Si/Al ration affected the formation of Broensted acid sites,The number of the Broensted acid sites on the catalyst active sites is important in the olefin conversion to liquied hydrocarbons.