Pt–Sn/Al2O3 catalyst for the selective hydrodeoxygenation of esters

1. Download high-res image (124KB)
2. Download full-size image

     

Kinetic study of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst

The kinetics of propane dehydrogenation and catalyst deactivation over Pt-Sn/Al2O3 catalyst were studied.Performance test runs were carried out in a fixed-bed integral reactor.Using a power-law rate expression for the surface reaction kinetics and independent law for deactivation kinetics,the experimental data were analyzed both by integral and a novel differential method of analysis and the results were compared.To avoid fluctuation of time-derivatives of conversion required for differential analysis,the conversion-time data were first fitted with appropriate functions.While the time-zero and rate constant of reaction were largely insensitive to the function employed,the rate constant of deactivation was much more sensitive to the function form.The advantage of the proposed differential method,however,is that the integration of the rate expression is not necessary which otherwise could be complicated or impossible.It was also found that the reaction is not limited by external and internal mass transfer limitations,implying that the employed kinetics could be considered as intrinsic ones.     

Doping of CoMo?Al2O3 catalyst with Mg and Zn

Effect of Mg (Zn) addition to CoMo–Al₂O₃ catalyst on its activity in hydrogenation of toluene and HDS of thiophene has been determined. These additives decrease the catalyst activity and modify the mechanism of thiophene HDS.

---

Mg (Zn) CoMo/Al₂O₃ () . .

     

Nanostructured ruthenium on γ-Al2O3 catalysts for the efficient hydrogenation of aromatic compounds

Free and trioctylamine (TOA)-stabilized ruthenium nanoparticles have been prepared by decomposition of the metal precursor Ru(η⁶-cycloocta-1,3,5-triene)(η⁴-cycloocta-1,5-diene) under mild conditions (room temperature, hydrogen atmospheric pressure). The nanoparticles have been deposited on γ-Al₂O₃ supports having different surface area. The resulting systems are active in the hydrogenation of methyl benzoate to methyl cyclohexanoate with a reaction rate decreasing in the order Ru(TOA)/γ-Al₂ O₃ (high surface area, catalyst D) > Ru(TOA)/γ-Al₂O₃ (catalyst C) > Ru/γ-Al₂O₃ (high surface area, catalyst B) > Ru/γ-Al₂O₃ (catalyst A). Catalysts A-D are long lived and can be reused without loss of activity; they are considerably more active than a commercial ruthenium on γ-Al₂O₃ sample. High Resolution Transmission Electron Microscopy analyses of such systems show that the nanoparticles are homogeneously dispersed on the support and that the size distribution decreases in the order catalyst A, 2.9 nm > catalyst B, 2.8 nm > catalyst C, 2.4 nm > catalyst D, 2.3 nm. Based on the easy hydrogenation of the aromatic ring to the cyclohexane derivative, an efficient synthesis of 4-carbomethoxyformylcyclohexane, important starting material in the preparation of pharmaceutical products, from the largely available methyl 4-formylbenzoate, has been set up in the presence of catalyst D.     

Ammoxidation of 3- and 4-picolines over V2O5?SnO2/γ?Al2O3 catalyst

The ammoxidation of 3- and 4-picolines has been studied over V₂O₅–SnO₂/–Al₂O₃ catalysts prepared by surface impregnation technique. Best results were obtained for the generation of cyanopyridines in the temperature range 400–450°C and sub-stoichiometric value with respect to O₂. Catalysts that were calcined above 700°C showed no activity.

---

3- 4- V₂O₅–SnO₂/–Al₂O₃, . 400–450°C O₂. , 700 K, .

     

Cu-embedded porous Al2O3 bifunctional catalyst derived from metal–organic framework for syngas-to-dimethyl ether

Dimethyl ether （DME）,as a promising alternative to diesel fuel and liquefied petroleum gas,has attracted considerable attention in catalysis domain.The catalytic direct synthesis of DME from syngas is an upand-coming route but remains a challenge.In this work,we firstly prepared a Cu-embedded porous Al₂O₃bifunctional catalyst （Cu@Al₂O₃-dp） by filling Cu-1,3,5-benzenetricarboxylate metal–organic framework（Cu-BTC MOF） with Al（OH）₃followed by a...     

Reduction of an amorphous NiO?Al2O3/SiO2 catalyst by different olefins and hydrogen

By static magnetic measurements it was found that the ability to reduction of an amorphous NiO–Al₂O₃/SiO₂ catalyst decreases in the order: but-2-eneshydrogen isobutene>but-1-ene>propeneethene. The reduction temperatures are significantly higher than the dimerization reaction temperatures.

---

, NiO–Al₂O₃/SiO₂ : -2>-1> . .

     

Ni/Al2O3 catalysts for CO methanation: Effect of Al2O3 supports calcined at different temperatures

The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.     

化学环制氢中Fe2O3/CeO2/Al2O3载氧体的性能研究

采用浸渍法制备了不同CeO2含量的Fe2O3/CeO2/Al2O3载氧体,利用BET,XRD和TPR对其性能进行表征,并以甲烷为燃料在固定床微型反应器中对载氧体进行化学环制氢性能考察。结果表明:CeO2的加入可以降低铁与铝之间的相互作用,提高铁的分散度,从而提高催化活性。在燃料反应器温度为900℃,蒸汽反应器温度为900℃,常压、剂烷比为2/1,进水量为0.1 m L时经过10次氧化-还原循环,Fe2O3/CeO2/Al2O3载氧体颗粒反应性能稳定,甲烷转化率最高可达到75%,单次循环氢气产量最高可达到35 m L·2.5 gcat-1。     

BF3·SiO2 is a simple and efficient Lewis acid catalyst for the one-pot synthesis of polyfunctionalized piperidin-4-ones

Abstract  

A range of Lewis acid catalysts were used for a series of one-pot multi-component reactions. Of them, silica-supported boron trifluoride (BF₃·SiO₂) was found to be an effective catalyst for the promotion of the modified Mannich condensation of ketones, aldehydes, and ammonium acetate in 1:2:1 molar ratio to afford 3,5-dialkyl-2,6-diarylpiperidin-4-ones in high yields of 80–92%. Also this simple, easily prepared, and reusable catalyst executed the condensation very effectively in a significantly shorter reaction duration (about 1–4 h) than the conventional method, which requires 1 day or more and involves a tedious work-up procedure. Further, this protocol ensures the stereospecificity; accordingly, all the synthesized piperidones adopted a chair conformation with an equatorial orientation of all substituents at C-2, C-3, C-5, and C-6.     

PdZn/α-Al2O3 catalyst for liquid-phase alkyne hydrogenation: effect of the solid-state alloy transformation into intermetallics

1. Download high-res image (149KB)
2. Download full-size image

     

焙烧温度对CeO2改性Pd/Al2O3甲醇分解催化剂性能的影响

考察了焙烧温度对Pd/Al2O3和CeO2改性Pd/Al2O3甲醇分解催化剂反应性能的影响.在300℃～700℃范围内焙烧,Pd/Al2O3和Pd/CeO2/Al2O3催化剂的活性都呈现出先升高后降低的趋势.XRD结果表明高温焙烧时活性组分Pd在γ-Al2O3载体表面发生聚集是Pd/Al2O3催化剂活性降低的原因,而XPS结果却表明,Pd在CeO2改性γ-Al2O3载体表面的浓度与Pd/CeO2/Al2O3催化剂的活性变化并非呈现一致关系,TPR表明活性组分Pd和助剂CeO2在γ-Al2O3上产生了一定的相互作用.从而认为Pd的分散度以及Pd和CeO2之间的相互作用共同决定催化剂的甲醇分解性能.     

助剂CeO2对Co/Al2O3催化剂上F-T合成反应性能的影响

在用于F-T合成的Co/Al     

Fe2O3/Al2O3氧载体制备方法的研究

采用溶胶-凝胶法、共沉淀法、水热合成法、低热固相合成法、机械混合法、燃烧合成法和冷冻成粒法制备铁基氧载体Fe₂O₃/Al₂O₃,并通过物理和化学表征手段来筛选和优化制备方法和制备工艺。对煅烧后的氧载体进行硬度测试,结果表明,溶胶-凝胶法、共沉淀法、机械混合法、燃烧合成法和冷冻成粒法制备的氧载体硬度较高;载体的X射线衍射(XRD)谱图表明,各种制备方法均能制得物相组成为Fe₂O₃/Al₂O₃的氧载体,且随着煅烧温度的提高、煅烧时间的延长,氧载体的结晶度、晶体粒径逐渐增大,煅烧温度1 200℃的氧载体的机械性能、晶体结构、晶相组成更稳定。借助化学吸附仪的程序升温还原(TPR)实验表征氧载体的反应活性,并计算氧载体活性度。综合物理和化学表征实验结果表明,最优制备方法为溶胶-凝胶法和冷冻成粒法。     

Catalytic performance in hydrodesulfurization of thiophene and ir investigation of Co and no adsorption over Co?Mo/Al2O3 and Ru?Co?Mo/Al2O3 catalysts

A new Ru–Co–Mo/Al₂O₃ catalyst has been prepared by impregnation of Ru salt as a secondary promoter onto Co–Mo/Al₂O₃ catalyst, and it was found that the Ru–Co–Mo/Al₂O₃ exhibited higher activity than Co–Mo/Al₂O₃ in hydrodesulfurization of thiophene to hydrocarbons. Ir studies on Ru–Co–Mo/Al₂O₃ revealed that the Co and NO adspecies increased significantly in intesnities and displayed a bathochromic shift in frequencies, as compared with Co–Mo/Al₂O₃.

---

Ru–Co–Mo/Al₂O₃ Ru, , Co–Mo/Al₂O₃. Co–Mo/Al₂O₃. CO NO, Co Mo, Co–Mo/Al₂O₃. , Mo , Mo³⁺ Mo³⁺ Co Ru–Co–Mo/Al₂O₃.

     

Ni/Al2O3催化甲烷裂解

分别通过浸渍法和共沉淀法制备了不同Ni负载量的Ni/Al2O3催化剂。考察了Ni负载量、制备方法以及反应温度对Ni/Al2O3催化甲烷裂解性能的影响。结果表明,在550℃,浸渍法制备的Ni/Al2O3催化剂,当Ni负载量为20%(质量分数)、Ni金属平均粒径为11.25 nm时,具有最佳的甲烷催化裂解效果,其每摩尔Ni的氢气产量和每克Ni碳产量分别为164 mol和15.30 g。催化剂制备方法对Ni/Al2O3甲烷催化裂解反应有显著影响,相同Ni负载量共沉淀法制备的Ni/Al2O3甲烷催化裂解总体效果要好于浸渍法制备的Ni/Al2O3,而且反应过程中生成的碳纤维较长,管径也较均一。550℃时,共沉淀法制备的Ni负载量为41.2%(质量分数)的Ni/Al2O3催化剂在反应至350 min时,仍保持着30%以上的转化率。     

Deuterium exchange reaction of ethylbenzene over an Fe2O3?K2CO3?Cr2O3 catalyst

Isotope exchange reaction of ethylbenzene with water or hydrogen has been examined over Fe₂O₃–K₂CO₃–Cr₂O₃ catalyst. The participation of the hydrogen attached to -carbon or phenyl group was observed. The exchange rate of the -hydrogen was compared for different alkylbenzenes and found that toluene was the most active, whereas cumene was inactive. This order suggested that the -hydrogen dissociated as a proton. -Adsorbed state was supposed as an intermediate of dehydrogenation, which dissociates the -hydrogen reversibly as a proton on a basic site. Including the results of exchange reaction of styrene, the overall route of dehydrogenation is discussed.     

Synthesis, characterization and catalytic performance of a novel magnetic SO42?-Y2O3-Fe3O4-ZrO2 solid acid catalyst

A novel magnetic SO₄ ²⁻-Y₂O₃-Fe₃O₄-ZrO₂ solid acid catalyst was prepared by the co-precipitation method. The results revealed that the introduction of Y₂O₃ improved markedly the thermal stability of tetragonal zirconia. The catalyst exhibited high catalytic activity and stability in cyclohexanone condensation.