磁稳定床研究进展

介绍了磁稳定床的流体力学特性、传质传热特性及磁稳定床在己内酰胺加氢精制过程中工业应用的进展情况。     

磁性催化剂的研究进展

磁性催化剂是一种有着广泛应用的新型功能催化剂材料。磁性催化剂的载体由磁核和包覆层组成,磁核主要是软磁、硬磁铁的氧化物,包覆层主要有氧化硅,氧化铝,氧化锆等,主要应用于加氢精制、固体酸催化、生物催化等领域,特别是在采用磁稳定床用于己内酰胺加氢精制领域,以非晶镍为代表的磁性催化剂已成功应用到工业生产中,这为磁性催化剂的的大发展带来契机。     

镍基非晶态合金加氢催化剂与磁稳定床反应器的开发与工业应用

报道了开发镍基非晶态合金加氢催化剂的实验室研究、中试研究及工业应用研究结果。向非晶态合金中加入少量原子半径大的其他元素，使非晶态合金的晶化温度由360℃提高到520℃；在含镍非晶态合金中加入铝，然后用碱将铝抽出，使非晶态合金比表面积由1m^2/g增加到100m^2/g以上；在建立30t/a非晶态合金生产示范装置中，自行设计了特殊的喷嘴和选用适宜的坩埚材质，使生产成品率由20％左右提高到95％以上，利用副产的偏铝酸钠，合成NaY分子筛，形成了整体的清洁生产过程；重点介绍了非晶态合金加氢催化剂经在三个工厂工业应用成功，三项工业应用成果每年为企业创造直接效益6700万元。还报道了对磁稳定床反应器的研究开发，经在20kt/a磁稳定床加氢示范装置上3500h试验，其生产效率比釜式加氢过程提高4倍，催化剂消耗减少50％。     

磁性催化剂反应器耦合磁分离装置

反应磁分离耦合装置兼具化学反应和流固相分离的功能,有助于提高反应效率、降低分离能耗、缩短工艺流程和避免催化剂磨损流失。综述近年来反应磁分离耦合装置的研究进展,流化态耦合磁分离装置包括磁稳流化床反应器和流化床耦合旋流磁分离装置,悬浮态耦合磁分离装置包括磁分离耦合悬浮态光催化反应器和釜式反应器耦合磁分离装置。指出磁性催化剂反应器和磁分离耦合装置应用中需要解决的关键问题是:规范生产适用于磁性催化剂反应器耦合磁分离装置的磁性催化剂以及构建磁性催化剂反应器耦合磁分离装置过程中必须引入磁场发生器。     

磁稳定床羰基化合成碳酸二苯酯的冷模实验

以磁性催化剂Pd/La0.5Pb0.5MnO3为固相、N2为气相、纯水为液相在磁稳定床上进行冷模实验,探索磁稳定床的流动特性,为磁稳定床氧化羰基化合成碳酸二苯酯提供数据。考察了不同操作条件对固相催化剂在磁稳定床中流化状态的影响,并通过流体力学软件FLUENT对实验进行计算模拟。结果表明:催化剂可以在流化床中达到完全流化状态,且起始流化速度随液体流速增大、外加磁场强度的增大及分布板开孔率减小而增大,床层高度随气相流速和液相流速减小而减小,随磁场强度的减小而增大,固相分布随床层高度减小而趋于密集,在实验气相流速范围内,床层的平均气相含率与气体流速基本呈直线上升关系。FLUENT软件模拟结果与实验过程完全吻合。     

液固磁稳定床流体力学特性

The hydrodynamic characteristics of liquid-fluidized magnetically stabilized beds (MSB) with commercial amorphous nickel alloy catalyst (SRNA- 4) as solid phase and water as liquid phase in a cold model experimental apparatus of Φ140 mm were investigated. The influence of magnetic field intensity on bed structure, pressure drop, minimum fluidization velocity, transition velocity, and liquid holdup were investigated. Mathematical models for minimum fluidization velocity, transition velocity, liquid holdup were established respectively. The operating phase diagrams of liquid-fluidized MSB with SRNA-4 catalyst of two different sizes were obtained.     

非晶态合金催化剂和磁稳定床反应工艺

2006年1月9日，在北京召开的全国科学技术大会上，中国石化石油化工科学研究院历经二十年研制开发的“非晶态合金催化剂和磁稳定床反应工艺的创新与集成”项目，荣获国家科学技术发明一等奖。     

液固磁稳定床研究进展

鉴于液固磁稳定床在石油化工、生化工程及环境工程等领域具有广阔的应用前景,本文从流体力学特性、传质过程、返混与扩散等几个方面,对液固磁稳定床的研究进展进行了综述。     

液固两相磁稳定床中试冷模研究

在磁稳定床冷模中以水为液相,非晶态合金催化剂(SRNA-4)为固相,探索磁稳定床反应器流动特性,并考察电磁线圈的放大效应,为工业磁稳定床反应器的设计提供数据。     

非晶态合金催化剂和磁稳定床反应工艺获国家奖

2006年1月9日，在北京召开的全国科学技术大会上，中石化石科院历经二十年研制开发的“晶态合金催化剂和磁稳定床反应工艺的创新与集成”项目，荣获国家科学技术发明一等奖。     

磁稳流化床研究与应用进展

磁稳流化床（MSFB）作为一种新型反应器,兼具固定床和流化床的众多优点,具有巨大的应用前景。本文综述了MSFB近年来在基础研究和应用上取得的进展。基础研究方面主要介绍了磁场强度和液相流速对床层结构的影响,以及床层空隙率、操作稳定性和传递特性等研究情况;应用方面介绍了MSFB在生物化工、能源和环境工程等领域的应用。最后分析了MSFB目前存在的不足,如对于一定的反应体系未找到相应合适的磁性催化剂、操作温度高于磁性载体的居里温度时,MSFB将无法操作、磁场发生装置释放出大量的热量对磁性载体和反应过程产生影响、难以确定稳定操作区域。并指出其今后的主要研究方向为磁性载体催化剂的研究与开发及对MSFB的稳定性判据、传热、传质、强化反应过程机理、反应器放大规律、工业化应用装置设计等方面的研究。     

Light FCC gasoline olefin oligomerization over a magnetic NiSo4/γ‐Al2o3 catalyst in a magnetically stabilized bed

Magnetic NiSO₄/γ‐Al₂O₃ catalysts were prepared by impregnating NiSO₄ solutions onto the γ‐Al₂O₃ support containing a magnetic material of Fe₃O₄. Characterization by XRD, NH₃‐TPD, and thermal analysis showed that the magnetic NiSO₄/γ‐Al₂O₃ catalyst with a nickel content of 7.0% by weight had a monolayer dispersion of NiSO₄ and the largest number of moderate strength acid sites, and a high specific saturation magnetization. The magnetic catalyst was evaluated for light FCC gasoline olefin oligomerization in both fixed‐bed and magnetically stabilized bed (MSB) reactors. Comparing with that in the fixed‐bed reactor, the optimal reaction temperature in the MSB lowered to 443 K, and its space velocity ranged broadly from 2.0 to 6.0 h^?1. The sulfur‐free diesel distillate produced by operation of the MSB for 100 h had higher cetane number and good low‐temperature flow property, which illuminates a promising application of the MSB to manufacture clean diesel fuels with high productivity and flexibility. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Integration of magnetically stabilized bed and amorphous nickel alloy catalyst for CO methanation

A novel process for the methanation of CO, involving an amorphous nickel alloy (ANA) catalyst incorporated in a magnetically stabilized bed (MSB), has been developed. The effects of varying the operating conditions on the reaction yield and catalyst lifetime have been investigated. The new process was shown to be markedly superior to existing processes for CO methanation in that the concentration of CO in an H₂-rich gas mixture could be reduced from 2000 ppm to less than 1 ppm at a temperature of 433 K, a pressure of 3.0 MPa, a gas hourly space velocity of , and a magnetic field intensity of 40 kA/m. Compared with conventional fixed bed processes, the operating temperature of the ANA/MSB process can be decreased by about 100 K and the gas velocity can be increased by a factor of 5-10. In durability tests, the ANA catalyst does not undergo any significant structural change and retains its initial high activity. These preliminary results indicate that the novel process has good prospects for application in the petrochemical industry.     

用磁性催化剂 Pd/La1-xPbxMnO3（x=0.20.6）合成碳酸二苯酯（英文）

The magnetic perovskite-supported palladium catalysts Pd/La1-xPbxMnO3 (x=0.2-0.7) were prepared and used for the oxidative carbonylation of phenol to diphenyl carbonate. The synthesized catalysts were characterized by the X-ray diffraction (XRD), surface area measurement BET, vibration sample magnetometer (VSM) and tem-perature-programmed reduction (TPR). The experimental results demonstrated that the magnetic Pd/La1-xPbxMnO3 (x=0.4-0.5) obtain relative better catalytic activity. It can be explained by higher concentration of oxygen vacan-cies, larger amount and better mobility of lattice oxygen of their support. Furthermore, these samples possess suffi-cient saturated magnetization. Thus, Pd/La1-xPbxMnO3 (x=0.4-0.5) may be suitable for operation in the magneti-cally stabilized bed reactor.     

Synthesis of Diphenyl Carbonate over the Magnetic Catalysts Pd/La1-xPbxMnO3 (x=0.2-0.7)

The magnetic perovskite-supported palladium catalysts Pd/La_1-xPb_xMnO₃ (x=0.2-0.7) were prepared and used for the oxidative carbonylation of phenol to diphenyl carbonate. The synthesized catalysts were characterized by the X-ray diffraction (XRD), surface area measurement BET, vibration sample magnetometer (VSM) and temperature-programmed reduction (TPR). The experimental results demonstrated that the magnetic Pd/La_1-xPb_xMnO₃ (x=0.4-0.5) obtain relative better catalytic activity. It can be explained by higher concentration of oxygen vacancies, larger amount and better mobility of lattice oxygen of their support. Furthermore, these samples possess sufficient saturated magnetization. Thus, Pd/La_1-xPb_xMnO₃ (x=0.4-0.5) may be suitable for operation in the magnetically stabilized bed reactor.     

Hydrodynamic characteristics of magnetically stabilized fluidized admixture beds of iron and copper particles

Hydrodynamic characteristics of fluidized beds of pure iron (1416 μm), copper (934 μ) and their admixture (25, 50 and 75 mass %) particles when exposed to a uniform magnetic field collinear with the gas flow are investigated. Bed pressure-drop data taken as a function of increasing and decreasing gas velocities (up to about 8 m/s) for different values of magnetic-field intensity over a wide range (0 to 17 272 A/m) are employed to determine the superficial minimum bubbling and fluidization gas velocities at ambient temperature and pressure. The minimum bubbling velocity is found to increase with an increase in the value of the magnetic-field intensity, as well as with the mass fraction of magnetizable particles in the bed. These data are correlated with an empirical relation, as well as with a semi-theoretical expression. The bed voidage data are also generated and analyzed, as also the bed quality fluidization in terms of interparticle magnetic forces. These hydrodynamic properties of magnetically stabilized fluidized-bed reactors are useful in their design and operation for a variety of chemical and biochemical applications.     

A110-5Q 型氨合成催化剂在双层并流合成塔中的使用

介绍了A 11025Q 型氨合成催化剂的装填、升温还原及使用情况。装填该催化剂后, 在合成塔有缺陷的情况下仍创出了合成氨产量记录, 表明该催化剂性能优良、活性好、生产强度大,在双层并流合成塔的应用是成功的。     

铜基催化剂结构对烯醛滴流床和固定鼓泡床加氢效果的影响

采用共沉淀法制备了不同组成的铜硅、铜铬和铜锌复合氧化物催化剂。利用X射线衍射（XRD）、氢气程序升温还原（H2-TPR）、氮气物理吸附（BET）和正丁胺电位滴定法等测试手段对制备的铜基复合氧化物催化剂的物化性质和孔结构进行了表征。考察了3种不同组成的铜基复合氧化物催化剂在滴流床和固定鼓泡床反应器中催化2-丙基-2-庚烯醛加氢的效果。结果表明：3种铜基复合氧化物催化剂的铜晶粒大小、表面酸碱性差异与催化2-丙基-2-庚烯醛加氢性能未呈现任何正向相关关系;具有丰富大孔的催化剂采用固定鼓泡床反应器催化烯醛加氢的效果优于采用滴流床反应器。