2-氧代-4-苯基丁酸乙酯不对称加氢滴流床反应器模型

研究了滴流床反应器中2-氧代-4-苯基丁酸乙酯在10,11-二氢辛可尼定修饰的Pt/A l2O3作用下不对称催化加氢反应特征,实验在4个不同催化床层中进行。考虑催化剂部分润湿和静、动持液量,结合复杂的传质和反应过程,建立了不对称催化加氢滴流床反应器模型。在本征动力学研究的基础上,用模型模拟了滴流床中反应物和产物沿反应器轴向的浓度分布,并对不同操作条件下不对称加氢反应的转化率和光学收率进行了预测,与实验数据比较一致,表明此反应器模型对非均相不对称催化反应的工程化有重要的指导意义。     

《化工学报》2006年第57卷第4期目次

热力学蒸发焓及沸点估算的基团拓扑空间方法大孔吸附树脂对红霉素的平衡吸附行为及其热力学性质传递现象移动床中颗粒接触传热的数学模型复合粉末多孔表面管的沸腾传热多相流移动床空腔现象及空腔尺寸基于小波变换的鼓泡塔内气液两相湍流多尺度结构分析催化、动力学与反应器Ce1-xCuxO2-x/Al2O3催化剂的制备及其甲烷催化燃烧性能MCM–41在微孔分子筛Y上的附晶生长滴流床反应器的非定态操作负载杂多酸(盐)的表征及其在苹果酯合成反应中的催化性能TiO2–SiO2复合氧化物的理化性质及其对柴油加氢精制性能的影响Pd/ZnO催化剂上甲醇水蒸气…     

滴流床反应器催化湿式氧化法处理碱渣废水

在自行研制的滴流床反应器中,以MnOx/γ-Al2O3为催化剂,研究了反应温度、进水有机物浓度、液体流率等主要工艺参数对酸化中和预处理后的碱渣废水催化湿式氧化效果的影响。结果发现反应温度和液体流率对氧化反应效果的影响显著:温度升高,反应速率加快;液体流率越慢,反应效果越好。在滴流床处理碱渣废水最开始连续运转的15 h中出水中金属离子溶出现象比较严重,但随后趋于稳定,催化剂的活性并没有受到影响。由于滴流床中高的催化剂-液相比,废水在滴流床中表现出高的降解速率。     

滴流床反应器处理有机废水的研究进展

介绍了滴流床反应器催化湿式氧化处理有机废水的发展概况和工艺特点,对滴流床反应器的主要影响因素,反应动力学和反应器数学模型等方面的研究现状进行了综述。     

催化湿式氧化法滴流床反应器处理污水的研究和应用

主要研究催化湿式氧化法滴流床反应器发展过程、研究进展和实际应用,论述了在湿式氧化法中滴流床反应器的特点和影响因素,并且对进一步的深入研究,工艺上的改进及其应用前景提出了参考建议。     

其他

吉林石化分公司研究院滴流床反应器获国家专利由吉林石化分公司研究院与大连理工大学共同研制的滴流床反应器 ,近期获国家实用新型专利 (专利号 :0 2 2 382 84 4 )。这种滴流床反应器为气固液三相反应器 ,一般为绝热式 ,在液相加氢中应用较多。对于列管式滴流床反应器 ,由于设     

滴流床反应器上α-甲基苯乙烯加氢影响因素分析

以α-甲基苯乙烯、氢气为原料在滴流床反应器中催化加氢合成异丙苯。本文主要考察反应温度、压力、循环量及进料α-MS的浓度、氢油比、催化剂、床层设计等因素对加氢反应的影响。结果表明,反应温度提高只在60～120℃范围内能够加快反应速率;压力在0.7～0.8 MPa时加氢反应速率最快,处理能力最大;氢油比的提高在保证原料与催化剂接触时间的前提下对反应有利;循环量及进料α-MS的浓度可以改变反应速率但是不能改变实际处理能力;催化剂的活性稳定是保证加氢效果的前提;床层设计的处理能力限制是造成目前加氢效果下降生产能力受限的主要原因。     

浆态鼓泡床反应器萘异丙基化合成2,6-二异丙基萘

为研究萘的异丙基化反应,制备了Fe2(SO4)3/膨润土催化剂,并对其结构和酸性等进行了表征. 在浆态鼓泡床反应器中考察了该催化剂对萘的异丙基化催化性能和反应条件的影响,结果表明,适宜的反应条件为：表观气速1.1 cm/s,反应温度240℃,催化剂浓度5.1%(w),反应时间4 h,反应系统压力0.8 MPa. 在该条件下,萘的转化率约为77.7%,2,6-二异丙基萘的收率为8.6%. 同时也说明浆态鼓泡床反应器用于萘的异丙基化反应的可行性.     

滴流床反应器中镍基催化剂催化加氢合成间苯二胺工艺的研究

以Ni／La2O3-SiO2为催化剂,采用滴流床反应器较系统地考察了反应温度、压力、气体和液体空速、溶剂等因素对问二硝基苯液相催化加氢合成间苯二胺反应的影响规律。结果表明,在较佳的温度范围内催化剂具有较好的间二硝基苯转化率及间苯二胺选择性,温度过低间苯二胺选择性较低,而温度过高会使间二硝基苯的转化率下降。反应压力及氢气空速提高、间二硝基苯液时空速降低均有刺于提高间二硝基苯的转化率和间苯二胺的选择性。乙酸乙酯对间二硝基苯有良好溶解性能,以乙酸乙酯作为溶剂可以提高催化剂的反应性能。在实验确定的适宜加氢反应工艺条件下,间二硝基苯转化率和间苯二胺选择性均可以达到99．5％以上。     

小颗粒滴流床反应器的流体力学研究

在内径为０．０４７ｍ，床层高０．７ｍ的滴流床反应器内，采用空气－水－玻璃珠（１．８，３．１８ｍｍ）体系，在常温、常压下进行实验。气、液流速分别在０．０５４－０．２３ｋｇ／（ｍ＾２ｓ）和３．２０－１４．７３ｋｇ／（ｍ＾２ｓ）内，用电导信号脉动法、压降波动法结合目测法测定了滴流床的流动状态及其变化，实验结果可用于确定不同操作条件下的流动状态。本研究还分别是用差计、示踪剂法和体积法对滴流床的压降，总持流     

Development of an in-situ H2 reduction and moderate oxidation method for 3,5-dimethylpyridine hydrogenation in trickle bed reactor

The Ru/C catalyst prepared by impregnation method was used for hydrogenation of 3,5-dimethylpyridine in a trickle bed reactor. Under the same reduction conditions (300 °C in H₂), the catalytic activity of the non-in-situ reduced Ru/C-n catalyst was higher than that of the in-situ reduced Ru/C-y catalyst. Therefore, an in-situ H₂ reduction and moderate oxidation method was developed to increase the catalyst activity. Moreover, the influence of oxidation temperature on the developed method was investigated. The catalysts were characterized by Brunauer–Emmett–Teller method, hydrogen temperature programmed reduction H₂-TPR, hydrogen temperature-programmed dispersion (H₂-TPD), X-ray diffraction, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, O₂ chemisorption and oxygen temperature-programmed dispersion (O₂-TPD) analyses. The results showed that there existed an optimal Ru/RuO_x ratio for the catalyst, and the highest 3,5-dimethylpyridine conversion was obtained for the Ru/C-i1 catalyst prepared by in-situ H₂ reduction and moderate oxidation (oxidized at 100 °C). Excessive oxidation (200 °C) resulted in a significant decrease in the Ru/RuO_x ratio of the in-situ H₂ reduction and moderate oxidized Ru/C-i2 catalyst, the interaction between RuO_x species and the support changed, and the hard-to-reduce RuO_x species was formed, leading to a significant decrease in catalyst activity. The developed in-situ H₂ reduction and moderate oxidation method eliminated the step of the non-in-situ reduction of catalyst outside the trickle bed reactor.     

Performance of catalytic reactors for the hydrogenation of CO2 to hydrocarbons

Fluidized bed and slurry reactors were employed to increase the CO₂ conversion and desirable product selectivity in the direct hydrogenation of CO₂ to hydrocarbons over K-promoted iron catalysts, as it is beneficial for the removal of heat generated due to highly exothermic nature of the reaction. The iron catalysts (Fe-K/Al₂O₃ and Fe-Cu-Al-K) were characterized by BET surface area, CO₂ and H₂ chemisorption, temperature-programmed reduction (TPR), X-ray diffraction (XRD) and temperature-programmed hydrogenation (TPH). The results of TPR and TPH study clearly indicated that co-precipitated Fe-Cu-Al-K catalyst has much higher reducibility and catalytic activity of CO₂ hydrogenation at low temperature than Fe-K/Al₂O₃. The performance of fluidized bed or slurry reactors was superior to that of fixed bed reactor for the CO₂ hydrogenation over Fe-Cu-Al-K catalyst in terms of CO₂ conversion and hydrocarbon productivity. Moreover, light olefins and heavy hydrocarbons were selectively synthesized in fluidized bed and slurry reactors, respectively. The optimum operation conditions and the effects of operating variables on the CO₂ conversion and its product distribution in these catalytic reactors were also discussed.     

镍对Pt/γ-Al2O3催化剂稠环芳烃选择性加氢性能的影响

分别以氯铂酸和硝酸镍为铂和镍前驱体,通过等体积浸渍法制备了系列镍修饰的Pt/γ-Al₂O₃催化剂,并采用电感耦合等离子体原子发射光谱（ICP-AES）、氨程序升温脱附（NH₃-TPD）、氢气程序升温还原（H₂-TPR）、氢气程序升温脱附（H₂-TPD）及氢氧滴定法（H₂-O₂）等手段进行表征。以重整C₁₀⁺重芳烃为原料,在30 mL固定床装置上考察镍引入对Pt/γ-Al₂O₃催化剂稠环芳烃（PAHs）选择性加氢性能的影响。固定床评价结果表明,随镍含量增加,稠环芳烃加氢活性和单环芳烃选择性呈现先增加后降低的趋势,当0.1Pt/γ-Al₂O₃催化剂中引入0.5%（质量分数）的镍时,催化剂稠环芳烃加氢活性和选择性最佳,此时稠环芳烃转化率为75%左右,单环芳烃选择性为98%以上。结合H₂-TPR、H₂-TPD及H₂-O₂滴定等表征结果,分析主要原因在于一定量镍的引入提高了铂的分散度,同时由于铂的加氢活化能较低,铂通过溢流活化的氢迁移至非贵金属镍上,提高了金属镍的加氢性能。此外,铂的存在还可避免镍形成尖晶石结构等非活性相,促进镍氧化物的还原,进而提高了催化剂的稠环芳烃加氢活性、选择性和稳定性。     

镍/氧化铝加氢催化剂的制备及性能研究

羟基新戊醛（HPA）的加氢多采用贵金属和铜系催化剂,为了更好地降低催化剂生产成本和操作成本,分别对比了共沉淀法和浸渍法制备的镍/氧化铝催化剂,并以HPA为原料,在固定床装置上考察了系列催化剂加氢合成新戊二醇（NPG）的催化性能。采用X射线衍射（XRD）、氮气物理吸附（BET）、一氧化碳脉冲吸附等方法进行表征,结果表明,浸渍法制备的20%镍/氧化铝催化剂,比表面积较大,金属分散性好,且催化剂中的镍物种易被还原,其反应性能良好。在相对较温和的反应条件下,即反应温度为103 ℃、反应压力为3 MPa、液时空速为1 h^-1、氢醛物质的量比为10时,HPA转化率为100%,NPG选择性为99.3%。在1 000 h的长周期评价过程中,该催化剂保持了较好的活性,具有更好的工业化前景。     

Syngas production from methane reforming with CO2/H2O and O2 over NiO–MgO solid solution catalyst in fluidized bed reactors

Catalyst performance of NiO–MgO solid solution catalysts for methane reforming with CO₂ and H₂O in the presence of oxygen using fluidized and fixed bed reactors under atmospheric and pressurized conditions was investigated. Especially, methane and CO₂ conversion in the fluidized bed reactor in methane reforming with CO₂ and O₂ was higher than those in the fixed bed reactor over Ni_0.15Mg_0.85O catalyst under 1.0 MPa. In contrast, conversion levels in the fluidized and fixed bed reactor were almost the same over MgO-supported Ni and Pt catalysts. It is suggested that the promoting effect of catalyst fluidization on the activity is related to the catalyst reducibility. On a catalyst with suitable reducibility, the oxidized and deactivated catalyst can be reduced with the produced syngas and the reforming activity regenerates in the fluidized bed reactor during the catalyst fluidization. In addition, the catalyst fluidization inhibited the carbon deposition.     

催化、动力学与反应器Pt/Y催化剂催化FCC柴油加氢制备BTX

利用Pt/Y催化剂,在固定床反应器中,温度380℃、压力3 MPa、氢油体积比1000及质量空速1.0 h^-1条件下,分别采用加氢处理的全馏分和轻馏分催柴为原料制备苯、甲苯和二甲苯（BTX）,获得（C₆+C₇+C₈）芳烃的总选择性分别为9.4%和33.9%。对原料和液体产物进行的气相色谱和质谱分析表明,BTX主要经过重芳烃的加氢饱和、裂解等反应生成,中间物质为烷基苯、四氢萘、茚满及茚类等单环芳烃。通过对反应原料以及对反应前后催化剂的N₂吸脱附、NH₃-TPD、XRD衍射图谱、TG等物化性质的表征,分析催化剂失活的主要原因。即全馏分催柴原料中高含量的S、N化合物快速吸附造成了催化剂中毒,而轻馏分原料中S、N化合物在催化剂表面的缓慢积累覆盖活性位,造成催化剂逐渐失活。     

Si含量对CO_2加氢制烃铁基催化剂的影响

以湿固相研磨法制备不同硅含量的铁基催化剂,采用X射线衍射、H2程序升温还原和傅里叶红外光谱对催化剂进行表征,在V(H_2)∶V(CO_2)∶V(N_2)=16∶8∶1、反应压力1.6 MPa、反应温度230℃、反应时间48 h和空速6 000 m L·(h·g-cat)-1条件下,在固定床反应器中考察催化剂的CO_2加氢制烃反应活性和烃类选择性。结果表明,随着Si O_2掺入量增加,催化剂的还原性能降低,结晶度呈下降趋势,CO_2转化率下降,但C5+烃类产物选择性在硅含量为10%时达到最大,为38.6%。     

Trickle bed reactor diluted with fine particles and coiled tubular flow-type reactor for kinetic measurements without external effects

Gas and liquid velocities in laboratory scale trickle bed reactors are one or two orders of magnitude lower than those in commercial reactors. Then, the kinetic data may include the external effects. This shortcoming of laboratory scale trickle bed reactor can be resolved by diluting the catalyst bed with fine inert particles. The catalyst bed dilution increases dynamic liquid holdup, pressure drop, gas–liquid mass transfer coefficient. Hydrogenation of 2-phenylpropene on Pd/Al₂O₃ was performed with the trickle bed reactor diluted with fine inert particles and the coiled tubular flow-type reactor to compare the kinetics with that of the basket type batch reactor. The trickle bed reactor diluted with fine inert particles is suitable to obtain the reaction rate without external effects even if the liquid velocity is low. The coiled tubular flow-type reactor should be used at high gas velocities.     

Intensification of Deep Hydrodesulfurization Through a Two-stage Combination of Monolith and Trickle Bed Reactors

Deep hydrodesulfurization (HDS) is an important process to produce high quality liquid fuels with ultra-low sul-fur. Process intensification for deep HDS could be implemented by developing new active c...     

催化剂形貌对沸腾床渣油加氢Ni-Mo/Al2O3催化剂活性位的影响机制

随着原油供应趋于劣质化和严格的环保法规出台,沸腾床渣油加氢技术引起了广泛关注。采用挤压成型法和STRONG沸腾床的特殊成型法分别制备了圆柱形和球形Ni-Mo/Al₂O₃催化剂,系统地研究了催化剂的颗粒形貌对活性相和渣油加氢性能的影响。采用XRD、N₂物理吸脱附、H₂-TPR、HRTEM、XPS和电子微探针分析等手段对催化剂进行了表征。结果表明,球形催化剂具有活性更强的Type Ⅱ类型活性位点、更优异的孔道结构性质和更好的流化性能,这使得其具有更高的渣油加氢活性。球形催化剂中的金属和载体之间相互作用较弱,这有利于形成更高硫化程度和堆垛层数的Ni-Mo-S Ⅱ型活性相,这种活性相在渣油加氢中具有更高的活性。此外,球形催化剂具有比圆柱形催化剂更大的孔径和孔体积,这有利于大分子杂质在孔道中的扩散和活性位点上的吸附,并且使得金属沉积物均匀分布在球形催化剂中,而不是集中分布在孔口。而且球形催化剂尺寸更小,可能更易于流化,这增强了催化剂的传质性能。