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Comparative investigation on radical polymerization of methyl and ethyl methacrylate under multi-site phase-transfer catalytic conditions 多位点相转移催化条件下甲基丙烯酸甲酯和甲基丙烯酸乙酯自由基聚合的比较研究
IF 0.125 Pub Date : 2018-01-25 DOI: 10.1007/s13203-018-0192-y
Vajjiravel Murugesan, Elumalai Marimuthu

Methyl and ethyl methacrylate was polymerized in heterogeneous system with the help of newly synthesized multi-site phase-transfer catalyst and using water-soluble initiator at 60?±?1?°C under unstirred inert atmospheric condition. Polymer yield was increased with increasing molar concentrations of monomer, initiator, catalyst and temperature. Polymerization follows first-order kinetics with respect to monomer and half-order with respect to catalyst and initiator, respectively. PTC has myriads of applications in the synthesis of various organic and polymeric materials because of its fast reaction and high yield in short period of time. Without addition of PTC, polymerization did not occur; this indicates that catalyst plays the pivotal role on initiation of polymerization. It extracts the reactive radical anion from aqueous phase and transfers to the organic phase where acrylates were polymerized. Polymerization reactivity of methyl and ethyl methacrylate under PTC conditions was studied by various parameters. The activation energy (Ea) and other thermodynamic parameters were calculated. The Ea value supports the reactivity of acrylates. The results obtained from this investigation were used for inferring the radical mechanism of phase-transfer-catalyzed polymerization. The obtained polymers were analyzed by spectral and thermal analyses.

利用新合成的多位点相转移催化剂和水溶性引发剂,在60°±1°的温度下,在非均相体系中进行了甲基丙烯酸甲酯和甲基丙烯酸乙酯的聚合。在未搅拌的惰性大气条件下°C。聚合物产率随单体摩尔浓度、引发剂、催化剂浓度和温度的增加而增加。聚合反应对单体遵循一级动力学,对催化剂和引发剂遵循半级动力学。PTC具有反应快、产率短的优点,在各种有机材料和高分子材料的合成中有着广泛的应用。不加入PTC,聚合不发生;这说明催化剂在聚合引发过程中起着关键作用。它从水相中提取活性自由基阴离子并转移到有机相中聚合丙烯酸酯。研究了甲基丙烯酸甲酯和甲基丙烯酸乙酯在PTC条件下的聚合反应性。计算了反应的活化能(Ea)和其他热力学参数。Ea值支持丙烯酸酯的反应性。所得结果用于推测相转移催化聚合的自由基机理。对所得聚合物进行了光谱分析和热分析。
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引用次数: 3
Synthesis and crystal structure of N,N-dimethylformamide solvate of thiocyanuric acid 硫氰尿酸N,N-二甲基甲酰胺溶剂化物的合成及晶体结构
IF 0.125 Pub Date : 2017-11-21 DOI: 10.1007/s13203-017-0191-4
Rashid Altamimi, Abdulaziz A. Bagabas, Hazem A. Ghabbour, Obaid Alruqi, Mohammed Alnogedan

Considerable attention has been paid recently to crystal engineering; which involves the design and preparation of new crystalline molecular solids with desired properties [1,2,3,4]. Crystalline materials with specific properties find applications in petrochemical industry for separation and purification. Moreover, crystal engineering provides products designed for manufacturing catalysts and high-valued chemicals for specific purposes. Recently, crystalline materials find application in pharmaceutical, food and microelectronic industries [5]. The main two strategies that are used for crystal engineering are based on hydrogen bonding and coordination bonding [6]. Since the hydrogen bonding is usually stronger and more directional than the other methods, more new crystal materials have been prepared based on this method. We are here able to design crystalline materials based on hydrogen bonding and study their solid state structures. N, N-dimethylformamide (DMF)-solvate of thiocyanuric acid (TCUA) and dimethyl sulfoxide (DMSO)-solvate of thiocyanuric acid (TCUA) were successfully prepared at room temperature in the presence of aqueous solution of sodium nitrate (NaNO3). To the best of our knowledge, this study presents the easy, modest, and rapid method to prepare co-crystal formation based on thiocyanuric acid (TCUA) and solvent-containing hydrogen bonding functionality. In this paper, we present the most effective method to synthesize the co-crystals of (TCUA), and as evidence, the crystal structure of (TCUA) in DMF is fully studied and presented in this paper. The N,N-dimethylformamide (DMF)-solvate of thiocyanuric acid (TCUA) was successfully prepared at room temperature, and was characterized spectroscopically by nuclear magnetic resonance (NMR) and single-crystal X-ray diffraction (SXRD). The asymmetric unit of the title compound contains one molecule of thiocyanuric acid (TCUA) features an almost planar six-membered ring having exocyclic C-S thione double bonds and one molecule of N,N-dimethylformamide (DMF). It was crystallized in the monoclinic, P21/c with unit cell parameters of a?=?9.6255 (4) ?, b?=?12.6864 (5) ?, c?=?9.1367 (4) ?, β?=?90.095 (2)°, V?=?1115.71 (8) ?3, Z?=?4. The structure is composed of 1-D TCUA ribbons formed via N–H–S hydrogen bonds. The ribbons are separated by DMF molecules, which are bridged to the ribbons by N–H–O hydrogen bonds. The ribbons and their DMF molecules form 2-D sheets which are in turn π-stacked to build up a layered, 3-D structure. The proton and carbon-13 NMR studies confirmed the formation of such solvate between DMF and TCUA.

近年来,晶体工程受到了相当大的关注;这涉及到设计和制备具有理想性能的新型结晶分子固体[1,2,3,4]。具有特殊性质的结晶材料在石油化工行业中用于分离和提纯。此外,晶体工程提供了用于制造特定用途的催化剂和高价值化学品的产品。近年来,晶体材料在制药、食品和微电子等行业得到了广泛的应用[5]。用于晶体工程的两种主要策略是基于氢键和配位键[6]。由于氢键通常比其他方法更强,更有方向性,因此基于这种方法制备了更多新的晶体材料。我们在这里能够设计基于氢键的晶体材料,并研究它们的固态结构。在硝酸钠(NaNO3)水溶液存在下,在室温条件下成功制备了N, N-二甲基甲酰胺(DMF)-硫氰尿酸溶剂(TCUA)和二甲基亚砜(DMSO)-硫氰尿酸溶剂(TCUA)。据我们所知,本研究提出了一种基于硫氰尿酸(TCUA)和含溶剂氢键官能团的简单、适度和快速制备共晶的方法。本文提出了合成(TCUA)共晶的最有效方法,并对DMF中(TCUA)的晶体结构进行了充分的研究和展示。在室温下成功制备了硫氰尿酸(TCUA)的N,N-二甲基甲酰胺(DMF)溶剂化物,并利用核磁共振(NMR)和单晶x射线衍射(SXRD)对其进行了表征。标题化合物的不对称单元包含一个具有外环C-S硫酮双键的几乎平面的六元环的硫氰尿酸分子和一个N,N-二甲基甲酰胺分子(DMF)。晶型为单斜晶型P21/c,晶胞参数为a = - 9.6255(4)°,b = - 12.6864(5)°,c = - 9.1367(4)°,β = - 90.095(2)°,V = - 1115.71(8)°,Z = - 4。该结构由N-H-S氢键形成的一维TCUA带组成。带被DMF分子分开,DMF分子通过N-H-O氢键连接到带上。这些条带和它们的DMF分子形成二维薄片,它们依次π堆叠,形成层状的三维结构。质子和碳-13核磁共振研究证实了DMF和TCUA之间形成了这种溶剂化物。
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引用次数: 1
Technical review on flexible processing middle distillate for achieving maximum profit in China 国内实现利润最大化的中间馏分柔性加工技术综述
IF 0.125 Pub Date : 2017-11-13 DOI: 10.1007/s13203-017-0187-0
Zhanquan Zhang, Wei Zhang, Yalin Zhang, Dewei Ji, Haiyan Jin, Gang Wang, Zhihua Zhang

Currently, refining business is?experiencing a transformation from refining to chemical business, or integration of refining and chemical business due to the slow economic growth, and decreased demand of clean fuels, particularly diesel product. Diesel products are over-supplied based on the consumption data in China. Refineries are pursuing technologies that could reduce diesel output, particularly the inferior light cycle oil (LCO) fraction. Herein, this article mainly describes the industrialized technologies for LCO processing such as LCO upgrading, LCO blending into available?plants such as fluid catalytic cracking (FCC), and hydro-refining/treating unit, LCO moderate hydrocracking, and LCO to aromatics and gasoline with the integration of selective hydro-refining and optimized FCC. It is figured out that the LCO moderate hydrocracking can provide more gasoline at the expense of high H2 consumption, while LCO to aromatics and gasoline (LTAG) technology needs more steps for clean fuel production and retrofitting of FCC plant. Based on the analyses of current technologies, it is suggested that implementation of such technologies should consider the configuration of refineries, as well as the benefit of employed technologies instead of realizing the target for decreasing diesel product unilaterally.

目前,炼油业务是?由于经济增长缓慢,清洁燃料特别是柴油产品的需求减少,正在经历从炼油业务向化工业务的转型,或炼油和化工业务的整合。从中国的消费数据来看,柴油产品是供过于求的。炼油厂正在寻求能够减少柴油产量的技术,特别是劣质轻循环油(LCO)馏分。本文主要介绍了LCO的工业化加工技术,如LCO升级、LCO掺入可用的?催化裂化装置(FCC)、加氢精制/处理装置、LCO中度加氢裂化装置、选择性加氢精制和优化FCC相结合的LCO制芳烃和汽油装置。结果表明,LCO中速加氢裂化可以以较高的H2消耗为代价提供更多的汽油,而LCO制芳烃和汽油(LTAG)技术在清洁燃料生产和FCC装置改造方面需要更多的步骤。在对现有技术进行分析的基础上,建议在实施这些技术时应考虑炼油厂的配置以及所采用技术的效益,而不是单方面实现减少柴油产品的目标。
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引用次数: 6
Grafting dual polar monomers onto hydroperoxidized polypropylene with the assistant of supercritical carbon dioxide 在超临界二氧化碳的辅助下,将双极性单体接枝到加氢过氧化聚丙烯上
IF 0.125 Pub Date : 2017-11-11 DOI: 10.1007/s13203-017-0190-5
Dengfei Wang, Jian Wang

A hydroperoxidized polypropylene (HPP) was obtained by oxidizing PP porous particle in solid phase, followed by impregnating dual polar monomers of pentaerythritol triacrylate (PETA) and styrene (St) into the HPP with the aid of supercritical carbon dioxide (scCO2). Then, HPP was used as polymerization initiators and PETA/St were grafted onto microporous PP backbone in water medium. Effects of hydroperoxidation temperature, time, oxidant dosage and PP diameter on hydroperoxides concentration and G p and G e were illustrated systematically. Besides, effects of scCO2 swell time, pressure, monomers concentration and ratio, grafting reaction time and temperature on G p and G e were also examined. Results showed that G p can be easily controlled by changing process conditions; G e was observed to be greater than 90% in most of the cases. Gel content of grafted samples was also determined. The structures and thermal properties of grafted copolymers were characterized through FTIR, SEM, TGA and DSC.

将聚丙烯多孔颗粒在固相氧化,然后在超临界二氧化碳(scCO2)的辅助下将季戊四醇三丙烯酸酯(PETA)和苯乙烯(St)的双极性单体浸渍在HPP中,制得加氢过氧化聚丙烯(HPP)。然后以HPP为引发剂,在水介质中将PETA/St接枝到微孔PP骨架上。系统阐述了氢过氧化温度、时间、氧化剂用量和PP直径对氢过氧化物浓度、G和G e的影响。此外,还考察了scCO2膨胀时间、压力、单体浓度和配比、接枝反应时间和温度对G - p和G - e的影响。结果表明,通过改变工艺条件可以很容易地控制G p;在大多数病例中,G≥90%。同时测定了接枝样品的凝胶含量。通过FTIR、SEM、TGA和DSC对接枝共聚物的结构和热性能进行了表征。
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引用次数: 2
Effect of Fe impregnation sequence on ethanol synthesis from syngas over Mn and Fe promoted Rh/γ-Al2O3 铁浸渍顺序对Mn和Fe促进Rh/γ-Al2O3合成气合成乙醇的影响
IF 0.125 Pub Date : 2017-11-06 DOI: 10.1007/s13203-017-0189-y
Fang Li, Weixing Qian

Fe promoted Rh–Mn/Al2O3 catalysts with different Fe impregnation sequences were used for ethanol formation from syngas. The effect of Fe impregnation sequence on the structure and performance of the catalysts was investigated by means of N2 adsorption, CO adsorption, H2-TPR, H2-TPD, CO-TPD, XPS and DRIFTS. The results showed that the RhMnFe/Al2O3 catalyst prepared by co-impregnation method showed higher ethanol selectivity than those prepared by sequential impregnation methods. Characterization results indicated that the RhMnFe/Al2O3 catalyst exhibited moderate CO hydrogenation and dissociation ability, stronger CO insertion ability and synergistic effect, which was responsible for its higher ethanol selectivity.

采用不同浸渍顺序的Fe促进的Rh-Mn /Al2O3催化剂催化合成气制乙醇。采用N2吸附、CO吸附、H2-TPR、H2-TPD、CO- tpd、XPS和DRIFTS等方法研究了Fe浸渍顺序对催化剂结构和性能的影响。结果表明,共浸渍法制备的RhMnFe/Al2O3催化剂比顺序浸渍法制备的催化剂具有更高的乙醇选择性。表征结果表明,RhMnFe/Al2O3催化剂具有适度的CO加氢解离能力、较强的CO插入能力和协同效应,具有较高的乙醇选择性。
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引用次数: 8
Enterprise-wide optimization in a petrochemical plant: a MILP approach to energy efficiency improvement 石化工厂的企业范围优化:能源效率改进的MILP方法
IF 0.125 Pub Date : 2017-10-28 DOI: 10.1007/s13203-017-0188-z
Delano Mendes de Santana, Sérgio Ricardo Lourenço, Douglas Alves Cassiano

Public policy, dollar rate, market prices, contracts values and equipment efficiency influence the costs of the energy sources at an ethylene plant. The aim of this research is to identify energy efficiency opportunities at the energy management resources in a petrochemical industry. It was proved that using MILP makes it possible to achieve energy efficiency gains. MILP proved to be effective, accurate and robust. It confirmed the importance of modeling and simulation with quick response and its implementation in a higher possible rate, since the potential gains running the model once per day were 81% higher than performing it once a month. The optimal resources choice had an average annual potential saving of US$ 556.000/year.

公共政策、美元汇率、市场价格、合同价值和设备效率影响乙烯工厂的能源成本。本研究的目的是确定能源效率的机会,在能源管理资源在石化行业。事实证明,使用MILP可以实现能源效率的提高。MILP被证明是有效、准确和稳健的。它证实了快速响应的建模和仿真的重要性,并以尽可能高的速度实施,因为每天运行一次模型的潜在收益比每月执行一次模型的潜在收益高出81%。最佳资源选择平均每年可节省55.6万美元。
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引用次数: 2
Kinetic modeling and study of H-ZSM-5 coated silicon carbide ceramic foam in toluene methylation to produce xylene H-ZSM-5包覆碳化硅陶瓷泡沫在甲苯甲基化制二甲苯过程中的动力学建模与研究
IF 0.125 Pub Date : 2017-10-26 DOI: 10.1007/s13203-017-0185-2
Debarpita Ghosal, Uttam Maity, Sonali Sengupta, Jayanta Kumar Basu

This work deals with the toluene alkylation reaction with methanol catalyzed by commercial H-ZSM-5 coated over SiC foam. The main product is xylene which is a well-known building block of many petrochemicals. The foam has been purchased and H-ZSM-5 was coated on it by dip-coating method. The coated foam was used as a catalyst block to study the reaction of toluene with methanol. The effect of variation of different reaction parameters such as reaction temperature, mole ratio of reactants, W/F ratio, partial pressure, feed rate, number of ceramic block coated with catalyst was investigated. Effect of regeneration of the catalyst has also been studied. In addition, comparison of conversion with pellet and coated one was also studied to confirm the usefulness of ceramic foam as catalyst support to get the best conversion to xylene production.

本文研究了用工业H-ZSM-5包覆碳化硅泡沫,催化甲苯与甲醇的烷基化反应。主要产品是二甲苯,它是许多石油化工产品的著名组成部分。购买了泡沫材料,采用浸涂法对其进行涂敷。以包覆泡沫为催化剂块,研究了甲苯与甲醇的反应。考察了反应温度、反应物摩尔比、W/F比、分压、进料速率、涂覆陶瓷块数等不同反应参数对催化剂性能的影响。并对催化剂再生的影响进行了研究。此外,还研究了颗粒转化和包覆转化的比较,以证实陶瓷泡沫作为催化剂载体的有效性,以获得最佳的二甲苯转化。
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引用次数: 3
Density, viscosity, surface tension, and excess properties of DSO and gas condensate mixtures 密度,粘度,表面张力,以及DSO和凝析气体混合物的过剩性能
IF 0.125 Pub Date : 2017-10-23 DOI: 10.1007/s13203-017-0183-4
Ahmad Khorami, Seyed Ali Jafari, Mohamad Mohamadi-Baghmolaei, Reza Azin, Shahriar Osfouri

Disulfide oil (DSO) mostly burned or stored is known as a low-grade byproduct in gas refining industries. This material is highly perilous to environment. A common way to reduce the environmental impact of DSO is blending in a specific ratio with gas condensate stream in gas refinery. This would improve DSO quality and consequently strengthen its unique application. In this work, density, viscosity and surface tension of DSO and gas condensate mixtures were measured and modeled. Viscosity and density of DSO, gas condensate, and their mixtures were measured in temperature range of 283.15–318.15?K. In addition, surface tension was measured at 298.15?K at different volumetric fractions of DSO–gas condensate mixture. Excess molar volume (V E), viscosity deviation (?μ), deviation of excess Gibbs free energy (?G E), and excess surface tension (σ E) were determined based on measured properties. Results showed a positive and negative trend for excess molar volume and excess surface tension, respectively. While fluctuation was observed in viscosity deviation and deviation of excess Gibbs free energy and results showed positive and negative values in different mole fraction. In addition, Redlich–Kister equation is proposed to predict excess properties of DSO and gas condensate mixtures.

二硫化油(DSO)是天然气炼制工业中的一种低品位副产品,主要用于燃烧或储存。这种材料对环境有很大的危害。减少DSO对环境影响的一种常用方法是在炼油厂与凝析液按一定比例混合。这将提高DSO的质量,从而加强其独特的应用。在这项工作中,测量了DSO和凝析气混合物的密度、粘度和表面张力,并建立了模型。在283.15 ~ 318.15 K的温度范围内测量了DSO、凝析油及其混合物的粘度和密度。此外,测得表面张力为298.15?不同体积分数dso -凝析气混合物的K值。过量摩尔体积(V E),粘度偏差(?μ),过量吉布斯自由能偏差(?G E)和多余表面张力(σ E)根据测量的性能确定。结果表明,过量摩尔体积和过量表面张力分别呈正、负趋势。黏度偏差和过量吉布斯自由能偏差均有波动,且在不同摩尔分数下均为正负。此外,提出了Redlich-Kister方程来预测DSO和凝析气混合物的过剩性质。
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引用次数: 7
Simulation and optimization of different pressure thermally coupled distillation for separating a close-boiling mixture of n-butanol and iso-butanol 正丁醇与异丁醇近沸混合物不同压力热耦合蒸馏分离的模拟与优化
IF 0.125 Pub Date : 2017-10-19 DOI: 10.1007/s13203-017-0186-1
Lixin Liu, Liuliu Zhu, Lanyi Sun, Minyan Zhu, Guili Liu

Substantial quantities of energy are required in conventional distillation columns applied in high-purity separation of close-boiling mixtures. To achieve energy saving of distillation, a novel different pressure thermally coupled distillation (DPTCD) was proposed for separating the close-boiling mixture of n-butanol and iso-butanol. Both this intensified energy integration technique and two other processes, namely conventional distillation (CD) and vapor recompression column (VRC), were simulated in process simulator Aspen Plus. The optimization was carried out to determine the optimal values of design and operating variables on the basis of minimizing energy consumption. Subsequently, the energy saving and economic efficiency of the DPTCD scheme were evaluated through the comparison with the other two processes. The results showed that, compared to the CD and VRC processes, the energy consumption of DPTCD process was decreased by 65.21 and 15.79%, respectively, and the total annual cost (TAC) of DPTCD process can be reduced by 33.75 and 10.46%. It demonstrated that DPTCD scheme was the most promising alternative to reduce the total energy consumption and TAC with high purity (99.1?wt%) n-butanol and iso-butanol products among these separation processes.

传统精馏塔用于近沸点混合物的高纯度分离需要大量的能量。为实现精馏节能,提出了一种新型的异丁醇和正丁醇近沸混合物的差压热耦合精馏(DPTCD)方法。在过程模拟器Aspen Plus上对该强化能量集成技术以及常规蒸馏(CD)和蒸汽再压缩塔(VRC)两种工艺进行了模拟。以能耗最小为目标,进行优化,确定设计变量和运行变量的最优值。随后,通过与其他两种工艺的比较,对DPTCD方案的节能经济性进行了评价。结果表明,与CD和VRC工艺相比,DPTCD工艺的能耗分别降低65.21%和15.79%,DPTCD工艺的年总成本(TAC)分别降低33.75%和10.46%。结果表明,在这些分离工艺中,DPTCD方案是最有希望降低总能耗和TAC的选择,可以获得高纯度(99.1?wt%)的正丁醇和异丁醇产品。
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引用次数: 3
Oxidative dehydrogenation of ethane with carbon dioxide over Cr2O3/SBA-15 catalysts: the influence of sulfate modification of the support Cr2O3/SBA-15催化剂上乙烷氧化脱氢:硫酸盐改性对载体的影响
IF 0.125 Pub Date : 2017-09-20 DOI: 10.1007/s13203-017-0182-5
P. Thirumala Bai, S. Srinath, K. Upendar, T. V. Sagar, N. Lingaiah, K. S. Rama Rao, P. S. Sai Prasad

Unmodified and sulfate-modified SBA-15-supported Cr2O3 catalysts were prepared by impregnation method. The physico-chemical properties of the supports and catalysts were determined by nitrogen adsorption/desorption, powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), laser-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), UV–Vis diffuse reflectance spectroscopy (UV-DRS), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM) and temperature-programmed reduction (TPR) techniques. Oxidative dehydrogenation of ethane to ethylene (ODE) with CO2 as oxidant was carried out on these catalysts in a fixed-bed reactor at temperatures in the range of 600–700?°C and at atmospheric pressure. The changes in structural and textural properties because of sulfate modification were identified. Sulfate modification affected the nature of interaction of CrO x species with the SBA-15 support. During the evaluation, it was observed that sulfate modification enhances ethane conversion and ethylene selectivity of the catalyst. Better dispersion of CrO x and the increase in Cr6+/Cr3+ ratio seem to be the reasons for the higher performance of the sulfate-modified catalysts compared to that of the unmodified catalyst.

采用浸渍法制备了未改性和硫酸盐改性的sba -15负载Cr2O3催化剂。采用氮吸附/脱附、粉末x射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、激光拉曼光谱、x射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-DRS)、电感耦合等离子体发射光谱(ICP-OES)、透射电子显微镜(TEM)和程序升温还原(TPR)等技术对载体和催化剂的理化性质进行了表征。在固定床反应器中,在600 ~ 700℃的温度范围内,以CO2为氧化剂,在这些催化剂上进行了乙烷氧化脱氢制乙烯(ODE)。°C和大气压下。确定了硫酸盐改性后结构和织构性能的变化。硫酸盐改性影响了CrO - x与SBA-15载体相互作用的性质。在评价过程中,硫酸盐改性提高了催化剂的乙烷转化率和乙烯选择性。与未改性催化剂相比,硫酸盐改性催化剂具有更好的CrO x分散性和Cr6+/Cr3+比值的提高。
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引用次数: 11
期刊
Applied Petrochemical Research
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