Surface Properties and Reactivity of Iron-Doped Titanium Oxides Catalysts in Oxidative Dehydrogenation of Ethylbenzene with CO2

The effect of Fe³⁺ doping level on the surface properties and catalytic performance of a series of iron-doped titanium oxide catalysts (1-7 mol% Fe³⁺) prepared using an acid-catalyzed sol-gel method was investigated in oxidative dehydrogenation of ethylbenzene with CO₂. The characterization of catalysts was carried out by means of x-ray powder diffraction (XRD), temperature programmed reduction (TPR), and the method of Brunauer, Emmett, and Teller (BET). It was found that the capacity of isolated Fe³⁺ centers in titania matrix is responsible for the catalytic performance; the catalysts exhibit the best activity at the loading level of Fe³⁺, about 3 mol%. In addition, it was shown that the appropriate pore size of the catalysts ranges from 5 nm to 25 nm; the selectivity to styrene increases with an increase in the specific surface area of the appropriate pores.     

DC-型乙苯脱氢催化剂的性能与工业应用

在铁系基础上通过引入助剂及改进制备方法开发了DC-型乙苯脱氧制苯乙烯催化剂。其性能达到国内外同类产品的先进水平。工艺条件试验说明可大空速下运转。经不同规模的等温式和绝热式工业应用证明具有高活性、高机械强度和耐水性好等特点。依据绝热式与DC-型催化剂的特点采用双层组合的新工艺,发挥了催化剂的效能。     

改性X分子筛催化乙苯CO2氧化脱氢制取苯乙烯

将改性X分子筛应用于催化乙苯CO2氧化脱氢反应,并比较了不同改性X分子筛的乙苯氧化脱氢催化性能。结果表明,KX、CsX对乙苯CO2选择氧化脱氢反应有良好的催化活性及苯乙烯选择性,并且该反应需要适当的酸碱活性中心协同催化,以使乙苯高效活化并转化生成产物苯乙烯。CsX分子筛催化乙苯CO2选择氧化脱氢的较佳操作条件为反应温度范围545～565℃、质量空速05 h-1、CO2/乙苯摩尔比8。     

纳米碳纤维负载磷氧化物催化剂催化丙烷氧化脱氢研究

考察了纳米碳纤维(CNF)、活性炭、石墨以及CNF负载磷氧化物催化剂催化丙烷氧化脱氢(ODP)反应性能。采用SEM、HRTEM、XRD、TG和BET表征了催化剂的组成和结构。结果表明炭材料自身对于ODP过程具有较高的活性和选择性,尤其是CNF由于其独特的结构特点更适合用作ODP过程催化剂。负载磷氧化物提高了CNF催化剂的适用温度,并提高了丙烯产得率。以磷酸氢二铵为前驱体,负载于经液相氧化处理的CNF上可以得到高选择性的ODP过程催化剂,在500℃下,丙烷转化率为42.07%时,丙烯选择性达到39.63%。     

交联蒙脱土负载型Fe催化剂催化乙苯-CO_2脱氢反应

将蒙脱土原土分别与Al-交联剂、AlCe-交联剂、AlY-交联剂反应,制得交联蒙脱土Al-PILC,AlCe-PILC,AlY-PILC,用X射线衍射和红外光谱对产物进行表征。以制得的交联蒙脱土为载体,用离子交换法制得Fe/Al-PILC,Fe/AlCe-PILC,Fe/AlY-PILC催化剂,并考察了它们在500℃下对乙苯(EB)-CO2脱氢制苯乙烯(ST)反应的催化活性。实验结果表明,Al-PILC,AlCe-PILC,AlY-PILC的比表面积和底面间距均大于蒙脱土原土,交联蒙脱土负载型Fe催化剂对乙苯-CO2脱氢反应的催化活性和苯乙烯选择性明显高于以蒙脱土原土为载体的催化剂,其中Fe/AlY-PILC催化剂上的EB转化率为9.31%,ST选择性为95.0%。     

乙烷在MoV催化剂上氧化脱氢制乙烯的研究进展

综述了近年来MoV催化剂上乙烷氧化脱氢制乙烯的研究进展,O2 N2O和CO2氧化剂的作用和乙烷氧化脱氢制乙烯的反应机理。     

CO_2和CO对铁系乙苯脱氢催化剂活性的影响

在常压、反应温度620℃、液态空速0.6 h~(-1)、乙苯与水的体积比1:2的反应条件下,考察了乙苯脱氢反应中的 CO_2和CO 对工业乙苯脱氧 Fe-K-Ce-Mo-O 系催化剂活性的影响。实验结果表明,通入 CO_2和 CO 后,乙苯转化率下降幅度分别为16～30个百分点和19～36个百分点。利用 X 射线衍射、红外光谱、X 射线光电子能谱技术对催化剂进行了表征,探讨了催化剂活性衰减的原因。表征结果显示,CO_2破坏了催化剂表面上的活性位 Fe—O—K键,随 CO_2含量的增加,催化剂活性降低的幅度增大;催化剂表面 Fe_3O_4(KFeO_2)物相被 CO 还原成 FeO,随 CO 含量的增加,Fe~(2+)/Fe~(3+)比值升高,导致催化剂活性下降。     

CO_2氧化低碳烷烃脱氢制低碳烯烃

对近年来国内外关于CO2氧化低碳烷烃脱氢制低碳烯烃的研究成果进行了综述。CO2作为温和的氧化剂应用于低碳烷烃氧化脱氢可提高反应的平衡转化率,抑制催化剂失活,是一个有应用前景的新工艺。用于此类反应的催化体系主要有Cr系和Ga系,但这两类催化剂的稳定性较差,通过调变催化剂载体表面的性质来改变活性组分与载体间的相互作用,可以提高催化剂的稳定性。不同催化体系中CO2的作用机制不同,Cr系催化剂上主要为氧化还原机理,而Ga系催化剂上则为异裂机理。为进一步提高反应效率,探索和研究同时具有脱氢与活化CO2能力的新催化体系是发展方向。     

乙烷在M_xO_y/SiO_2上氧化脱氢制乙烯

在５００—７００℃的温度范围内研究了不同氧化物负载在ＳｉＯ２上乙烷氧化脱氢（ＯＤＨＥ）行为。结果表明过渡金属氧化物负载型催化剂对ＯＤＨＥ反应有很好的活性，碱土金属、ｓｐ区金属氧化物负载型催化剂的活性较低，只有合适的可还原性催化剂才同时具有较高的乙烷转化率和乙烯选择性。通过Ｍｏ基催化剂上引入活性组份Ｆｅ、Ｖ等进行双金属调变可改善催化剂的乙烯选择性。     

锰系催化剂上湿天然气中乙烷氧化脱氢

在Ｍｎ２Ｏ３／ＳｉＯ２催化剂上,当总空速为２０００ｈ－１,ｎ（Ｃ２Ｈ６）／ｎ（Ｏ２）＝１,反应温度为７５０℃时,乙烷生成乙烯的收率达４５７６％;温度为８８０℃时,乙烯收率为６１４３％。添加水蒸汽可使催化剂活性稳定。根据该反应的宏观动力学研究,推出动力学方程为ｒＣ２Ｈ４＝ｋｐ２Ｃ２Ｈ６,并对反应机理进行了讨论。     

V2O5/MPO4在丙烷氧化脱氢中的催化作用

研制了具有不同酸碱性的磷酸盐ＭＰＯ４（Ｍ＝Ａｌ,Ｚｒ,Ｃａ）载体,并用这些载体负载０６％～６０％的Ｖ２Ｏ５。所制备的催化剂在丙烷氧化脱氢反应中具有较好的催化性能,如３％Ｖ２Ｏ５／Ｃａ３（ＰＯ４）２催化剂在丙烷转化率为１７０％时,丙烯选择性可达５５９％,丙烯收率达９５％。考察了不同反应条件下催化剂的性能,表明在高温高空速条件下,３％Ｖ２Ｏ５／Ｃａ３（ＰＯ４）２催化剂的反应活性较好,而３％Ｖ２Ｏ５／Ｚｒ３（ＰＯ４）４催化剂在低温低空速时,反应活性相对较高。在相同的丙烷转化率下,丙烯的选择性从大到小的顺序为３％Ｖ２Ｏ５／Ｃａ３（ＰＯ４）２＞３％Ｖ２Ｏ５／Ｚｒ３（ＰＯ４）４＞３％Ｖ２Ｏ５／ＡｌＰＯ４。     

掺杂La_2O_3或CeO_2的V_2O_5/γ-Al_2O_3和Fe_2O_3/γ-Al_2O_3催化剂的乙苯脱氢性能

通过掺杂少量的稀土金属氧化物La2O3或CeO2,采用溶胶-凝胶法制备了3%La2O3-17%Fe2O3/γ-Al2O3,3%La2O3-17%V2O5/γ-Al2O3,3%CeO2-17%V2O5/γ-Al2O3催化剂(金属氧化物负载量均为基于载体的质量分数),并用于在CO2气氛下乙苯温和氧化脱氢制苯乙烯的反应。考察了不同催化剂对乙苯和CO2的转化率及苯乙烯选择性的影响。实验结果表明,在常压、600℃、n(CO2)∶n(乙苯)=10∶1、乙苯空速为15mmol/(g.h)、反应时间3h的条件下,3%La2O3-17%V2O5/γ-Al2O3催化剂呈现出良好的乙苯脱氢活性,乙苯转化率和苯乙烯选择性分别为78.0%和98.2%,CO2的初始转化率为5.8%。采用X射线衍射、红外光谱和热重-差热分析表征了反应前后催化剂的体相结构及热失重过程。     

Influence of pressure and CO2 content on the asphaltene precipitation and oil recovery during CO2 flooding

During CO₂ flooding, the crude oil is treated with CO₂, and meanwhile it is displaced by CO₂. Based on the two processes, the influence of pressure and CO₂ content on the asphaltene precipitation and oil recovery efficiency are systematically investigated by indoor simulation experiment. With the increase of the pressure or CO₂ content during CO₂ treatment, the amount of asphaltene precipitation can be increased to a certain value. Correspondingly, the degrees of the changes of oil-water interface, the compositions of crude oil, and reservoir permeability are positively correlated with the amount of asphaltene precipitation. However, during the process, the oil recovery has an optimal value due to the combined action of asphaltene precipitation and the improvement of flow performance of the crude oil. These conclusions can provide a basis for high efficiency development of low permeability oil reservoirs by CO₂ flooding.     

乙烷和C1—C2混合气中乙烷氧化脱氢制乙烯

对纯乙烷和Ｃ１－Ｃ２混合气中乙烷氧脱氢制乙烯从催化剂、反应工艺条件、反应动力学及反应机理等几个方面进行了比较。指出二者的催化剂体系分为以下几类：（１）碱金属和碱土金属氧化物,（２）过渡金属氧化物,（３）稀土金属氧化物等。     

Economical Evaluation of CO2-EOR Projects in the Middle East

Abstract

Recently, there is a growing interest the in oil industry to utilize carbon dioxide (CO₂) to enhance oil production from mature reservoirs. Conversely, there is a rising global attention to reduce CO₂ emissions from burning fossil fuels due to environmental concerns. Synchronization between these two objectives is promising through CO₂ Capture and Storage (CCS) projects where CO₂ is captured from large emission sources and then storedin safe geological structures. Economical evaluation of CO₂-EOR projects is a crucial measure in order to ensure a project's viability.

In this study, an efficient model was developed to predict the economics of CO₂-EOR projects. The developed model consists of five modules that are linked together to allow for fast prediction of CO₂-EOR economics.

The model was used to predict the economics of a case study where CO₂-EOR application is considered for a Middle Eastern reservoir. Moreover, the case study was subjected to sensitivity analyses to evaluate the effects of several parameters on the various economical components of CO₂-EOR projects.     

Oil recovery and CO2 storage in CO2 flooding

In this study, the interfacial tension (IFT) of crude oil-carbon dioxide mixtures was measured to determine the minimum miscibility pressure. CO₂ flooding with sand packs, long cores, and heterogeneous cores was conducted to investigate the oil recovery and storage efficiency. The experiment results show that the interfacial tension decreases linearly with increasing pressure at two different pressure ranges. Under immiscible condition, the oil recovery and storage efficiency are increased by 30.1% and 52.4% when the injection pressure is increased from 13 to 22 MPa, and improved by 16.3% and 22.04% when the permeability is decreased from 270 to 10 mD, respectively. Under miscible condition, increase of injection pressure can only lead to much slower increase of oil recovery and storage efficiency, and permeability almost has no influence on oil recovery and storage efficiency. The oil recovery and storage efficiency can be remarkably reduced by heterogeneity. Water alternating CO₂ injection can improve the oil recovery and storage efficiency by 35.5% and 13.55%, respectively, compared with continuous injection.     

复合SiO2-WO3催化剂的制备、表征及氧化脱除苯并噻吩性能

 采用溶胶-凝胶法制备了SiO₂-WO₃催化剂,并采用XRD、FT-IR、BET、TG-DTA等方法对催化剂进行表征。以苯并噻吩(BT)为模型化合物,H₂O₂为氧化剂,考察了催化剂的活性元素、制备方法、n(W)/n(Si)和焙烧温度对其催化氧化脱硫活性的影响。结果表明,W的引入降低了SiO₂的比表面积,SiO₂-WO₃催化剂中W的主物相为WO₃。在以W为活性组元,且n(W)/n(Si)为0.1时,500℃焙烧得到的SiO₂-0.1WO₃催化剂具有最好的催化脱硫活性。在模拟油20 mL、催化剂SiO₂-0.1WO₃用量0.04 g、n(H₂O₂)/n(S)为15.9、乙腈/模拟油体积比0.3、65℃反应60 min的条件下,苯并噻吩模拟油脱硫率可达99.3%。     

CO2氧化1-丁烯脱氢制1,3-丁二烯反应热力学分析

通过热力学分析了CO2氧化1-丁烯脱氢制1,3-丁二烯反应及反应限度.计算结果表明:目标反应在常温下不能发生,而在实验室最佳反应温度873.15 K下可逆进行;CO2的引入促进了1-丁烯脱氢反应的进行;反应可以通过氧化脱氢反应的一步路径和直接脱氢与逆水煤气变换耦合的二步路径进行.并且,在热力学上异构化反应比氧化脱氢反应...     

Screening of Oil Pools on Alaskan North Slope and Phase Behavior Study of Viscous Oil and CO2 System in Conjunction with CO2 Sequestration

Abstract

Carbon dioxide gas, a greenhouse gas (GHG), is released in the atmosphere by combustion of solid waste, wood, and fossil fuels for energy generation. Due to conspicuous absence of CO₂ sequestration studies for Alaska, the study of CO₂ sequestration options on North Slope has a very important role to play. The screening of the oil reservoirs to evaluate the technical feasibility with respect to their CO₂-EOR potential was performed by calculating the rank of the oil reservoirs with parametric approach. CMG-WinProp® simulator was used to predict phase behavior for CO₂ injection in viscous oil by tuning the equation-of-state.