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TS-1分子筛催化苯羟基化法制苯酚是一种绿色工艺路线。对以TS-1为催化剂苯与过氧化氢反应制苯酚的本征动力学进行了研究。考察了搅拌速度、苯浓度、过氧化氢浓度以及反应温度等因素对苯酚初始生成速率的影响,并采用幂函数方程进行实验数据拟合。结果表明,在消除内外扩散影响的条件下,反应对于苯、过氧化氢的反应级数分别为0.62和0.55,反应的活化能为101.31 kJ/mol。依据上述结果建立了反应的本征动力学方程,并对模型进行验证,结果显示模型计算得到的苯酚初始生成速率与实验值的平均相对偏差为6.81%,吻合较好。研究得到的动力学模型为TS-1催化苯羟基化-膜分离耦合制备苯酚的条件优化及过程开发提供依据。 相似文献
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以羧酸酯为原料催化加氢同时制备两种不同(或相同)的醇是一条绿色清洁的原子经济工艺路线。研究采用自主开发的20Cu-8Zn O/Si O2-5K2O催化剂用于醋酸异丙酯加氢制备乙醇和异丙醇的反应体系。通过对催化剂各组分作用分析及主副反应剖析,结合反应产物组成及分布,提出了反应机理和反应网络。采用三段控温的固定床反应器,消除内、外扩散影响后在反应压力5 MPa、氢气与醋酸异丙酯进料摩尔比为30~60、醋酸异丙酯进料流量0~0.20 m L?min?1及反应温度250~280℃的条件下,实测了醋酸异丙酯加氢反应的本征动力学数据;在合理简化反应网络的基础上,建立了本征动力学模型,拟合了模型参数,并进行了模型参数物理意义分析和模型适定性检验。结果表明:当氢酯进料摩尔比≥30,催化剂粒径≤0.30 mm,内、外扩散阻力均已消除;以Matlab软件中非线性最小二乘法拟合结果与动力学实验测定数据吻合良好;在实验范围内,建立的本征动力学模型对醋酸异丙酯加氢制备乙醇和异丙醇反应高度适定。 相似文献
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采用双溶剂浸渍法制备得到了粒径为1.9nm±0.6nm高分散性的Ag/MIL-101催化剂。考察了该催化剂在过量NaBH4存在下,还原对硝基苯酚生成对氨基苯酚反应中的催化性能。本文通过研究催化剂浓度、底物浓度和温度对催化活性的影响,获得不同条件下的表观反应速率常数kapp,采用Langmuir-Hinshelwood吸附反应模型对所得动力学数据进行拟合,获得本征反应速率常数k,底物吸附常数K4-NP和KBH4,底物吸附焓、熵以及真实活化能EA,k等热力学参数。研究表明,诱导时间t0直接与该反应速率控制步骤的反应速率常数k有关。 相似文献
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改性竹炭对4-硝基苯酚的吸附行为研究 总被引:4,自引:1,他引:3
采用硝酸对竹炭进行改性,考察了改性竹炭对水溶液中4-硝基苯酚的吸附热力学和动力学特性。结果表明,与原竹炭相比,硝酸改性竹炭的比表面积、孔容及对4-硝基苯酚的吸附量显著提高。在实验条件下,动力学过程用二级吸附动力学模拟具有很好的线性相关性,通过二级吸附模型计算出的平衡吸附量与实验值相符。改性竹炭对4-硝基苯酚的吸附行为可用Langmuir和Freundlich等温式进行描述,相关性都较好,但更符合Langmuir公式。求得热力学参数ΔH=28.36 kJ/mol,ΔS=168.88 J/(K.mol),ΔG分别为-19.41(10℃)、-22.86(30℃)、-26.16(50℃)kJ/mol,表明改性竹炭对4-硝基苯酚的吸附是吸热、自发的过程,以物理吸附为主。 相似文献
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Ho-Shing Wu Chang-Lin Lee 《Chemical engineering journal (Lausanne, Switzerland : 1996)》2002,90(3):2535-251
The mechanism and NaOH effect of the substitution reaction of hexachlorocyclotriphosphazene, (NPCl2)3, with phenol to synthesize the poly(phenoxy)chlorocyclotriphosphazene were investigated by using triphase catalysis in an organic phase/alkaline solution. Four relationships between the ion-exchange reaction and organic reaction were presented and clarified by experimental result. The reaction behaviors varied with different particle sizes of resins. The reaction zone was not the whole resin, and occurred obviously at a shell of the resin when the resin was used larger particle size and higher degree of crosslinkage. The thickness of shell in the resin varied with different NaOH concentrations. The intrinsic reaction kinetics, particle diffusion and film diffusion had to be considered to explain this triphase reaction behavior. The performance of recycle fixed-bed reactor was also investigated. 相似文献
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用阳离子交换树脂催化酯化合成乙酸异丙酯动力学研究 总被引:2,自引:0,他引:2
在间歇反应釜中,采用强酸型阳离子交换树脂(Amberlyst 15-Wet)作催化剂,在液-固两相体系中对乙酸异丙酯合成反应过程进行了研究,系统地考察了搅拌速度、催化剂粒径、温度、催化剂浓度、酸醇比对酯化反应速率的影响。同时通过拟均相动力学模型对反应过程进行了模拟,计算得到了相关的动力学参数。计算结果与与实验值吻合良好,能较好地描述乙酸和异丙醇合成乙酸异丙酯的酯化反应过程。 相似文献
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以Pd/C为催化剂的松香加氢本征动力学 总被引:1,自引:1,他引:1
在温度403~433K,压力3.0~7.0MPa下,研究了以Pd/C为催化剂的松香催化加氢本征动力学,为工业反应过程的开发和操作提供了理论依据.通过减少催化剂粒度和提高搅拌转速,以消除内外扩散的影响,在松香加氢反应过程中,在线跟踪了反应物和产物浓度随反应时间的变化关系.根据实验数据,采用EVIEWS软件对10个可能的反应机理模型进行筛选,认为最可几的反应机理为松香中的主要成分枞酸分子不吸附,枞酸分子与催化剂表面上被吸附的氢原子进行反应,氢原子的吸附为控制步骤;其反应动力学方程为, 据此导出反应速率常数和吸附平衡常数分别为 (Hk =5.695exp((2498.5/T), bs =9.4(10(3exp(1920.8/T). 相似文献
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《分离科学与技术》2012,47(10):1604-1612
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The paper investigates the ability of activated carbons developed from coconut shell to adsorb α-picoline, β-picoline, and γ-picolin from aqueous solution. The developed carbons are designated as SAC (activated carbon derived from coconut shells with out any treatment) and ATSAC (activated carbon derived from acid treated coconut shells). The carbons were, characterized and utilized for the sorption of α-picoline, β-picoline, and γ-picoline at different temperatures, particle size, pH and solid to liquid ratio. All the studies were performed by batch method to determine various equilibrium and kinetic parameters. The Langmuir and Freundlich isotherm models were applied and the Langmuir model was found to best report the equilibrium isotherm data. The adsorption of α-, β-, and γ-picoline followed the pseudo-second order rate kinetics. On the basis of kinetic studies, various rate and thermodynamic parameters such as effective diffusion coefficients, activation energy and activation entropy were evaluated. It was concluded that in majority of cases, the adsorption is controlled by particle diffusion at temperatures 10° and 25 °C while at 40 °C it is controlled by film diffusion mechanism. Similarly at concentrations 25 and 50 mg/l the adsorption was governed by particle diffusion in most of the cases while at >50 mg/l it was film diffusion controlled. The overall capacity of ATSAC was higher than SAC. The sorption capacity of γ-picoline was found more followed by β-picoline and α-picoline. 相似文献
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采用等温管式积分反应器,在(550~750) K、(2.0~3.5) MPa和空速(15~30) L·(g·h)-1条件下,对新型钴钼系耐硫变换催化剂进行变换反应本征动力学研究。建立了包含压力项的幂函数型动力学模型,根据实验测定数据,结合具有全局寻优能力微粒群算法和求解微分方程的龙格-库塔法,通过迭代寻优对变换反应动力学模型进行参数估计,获得高度显著、可信的动力学模型。结果表明,在催化剂上进行变换反应时,反应速率对CO组分分压变化的敏感性较低,H2O组分分压对反应速率的影响较大,高汽气比下催化活性较高。 相似文献
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The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI) utilizing an aqueous extract of green tea waste as a reductant with ferric chloride. Also, the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI). The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR), scanning electron microscope(SEM), X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET), and zeta potential(ζ). The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis, with silty clay an adequate support. Additionally, the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI. To determine the optimum conditions, the impact of diverse experimental factors(i.e., initial pH, adsorbent dose, temperature, and concentration of phenol) was studied. Langmuir, Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium. The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model. The appropriateness of pseudo_first_order and pseudo_second_order kinetics was investigated. The experimental kinetics data were good explained by the second-order model. The thermodynamic parameters(ΔH0, ΔS0, andΔG0) for NZVI and SC-NZVI were determined. The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI, were found to be 94.8% and 90.1%, respectively. 相似文献
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采用苯酚直接羟基化联产邻、对苯二酚被认为是目前合成苯二酚的绿色工艺路线之一,但关于以TS-1分子筛为催化剂的本征反应动力学尚在研究中。文中借助高效液相色谱技术,研究了在TS-1分子筛催化下以双氧水直接氧化苯酚为苯二酚的本征反应动力学。结果表明,当搅拌器的转速大于380 r/min时,外扩散已基本消除,反应进入动力学控制区。该反应对于苯酚和羟基化试剂双氧水的反应级数为1.2和0.53,反应活化能为76.87 kJ/mol,反应指前因子为7.58×109mol0.73/(L0.73.min)。这可为TS-1催化-膜分离耦合制备苯二酚反应过程开发和工业反应器设计提供基础数据。 相似文献
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S.S. Baral S.N. Das G. Roy Chaudhury Y.V. Swamy P. Rath 《Chemical engineering journal (Lausanne, Switzerland : 1996)》2008,139(2):245-255
Cr(VI) removal studies were carried out by using activated carbon obtained from waste weed, Salvinia cucullata. Effects of various parameters, such as pH, contact time, temperature, adsorbate concentration, adsorbent dose and particle size of the adsorbent on percentage of adsorption were studied. The adsorption studies were carried out at an agitation speed of 600 rpm to minimize the film diffusion. The adsorption kinetics followed dual rate; it was fast during a first stage and then it was reduced. The equilibrium was achieved in 12 h. The kinetics increased with decrease in pH. Adsorbate and adsorbent concentration also influenced the kinetics. The adsorption process was endothermic in nature. The reaction kinetics followed pseudo-second-order kinetic equation. Empirical rate equation developed, which explained the effect of various adsorption parameters, was studied. Theoretical numbers of stages were calculated based on the results. Intra-particle diffusion was found to be the rate-controlling step. Optimization studies were also carried out to establish the upper and lower breakthrough points. 相似文献