氟化钕制备的新工艺

氟化钕是制备Ｎｄ和ＮｄＦｅ合金的主要原料。针对传统方法制备氟化钕中存在的反应速率慢，转化率低及产品中含有结晶水等问题进行了探讨，提出了制备氟化钕的新工艺，摸索出了最佳工艺条件，获得了反应速率快、转化率高、不含结晶水的满意结果。     

气相氟化法合成3，3，3-三氟丙烯

在固定床反应器中,以1,1,1,3-四氯丙烷（TCP）为原料,氟化氢为氟化剂,采用自制的改性氧氟铬催化剂,合成了3,3,3-三氟丙烯（TFP）,考察了反应条件对气相氟化合成TFP的影响。结果表明,催化剂具有良好的催化性能。适用于TFP的气相氟化合成工艺;适宜的操作条件为：温度230℃,HF与TCP摩尔比为20：1、空速1000h^-1。在此条件下。TCP的转化率可达到100％。TFP的收率可达到95％以上。     

过热蒸汽流化床流化特性的实验研究

在底部直径为120 mm的锥型流化床中,以玻璃珠为流化颗粒,过热蒸汽为流化介质,研究了固体颗粒在过热蒸汽流化床中的流化特性,考察了操作温度和压力对临界流化速度(umf)的影响.结果表明,过热蒸汽流化床的流化行为与热空气相似,临界流化速度(umf)随床层温度的升高而减小,随床内压力的增大而减小;在相同温度条件下,过热蒸汽流化床的临界流化速度比热空气大.     

流化床甲烷化有关工程技术问题的探讨

镍系催化剂流化床甲烷化技术的关键问题为原料气的预处理、流化床反应器流体力学条件的确定、反应热量的导出及反应温度的控制及夹带催化剂的回收与返尘等。原料气预处理采用氧化铁脱硫剂先脱去大部分无机硫和部分有机硫,然后用氧化锌脱硫剂脱至总硫为1mg/m~3以下。由于甲烷化催化剂颗粒分布较好,流化速度范围较宽,在流化数为50～70的情况下,仍能较好地操作。反应热采用内置盘管换热经取热介质(水)带出,并产生中压蒸汽,反应器温度可用下降水量方便地控制。夹带的催化剂采用多级旋风分离器回收并经料腿返回床层。     

响应面法优化氟化铝合成实验

在单因素实验基础上,以氟化铵制得的氟化氢和固体氢氧化铝为原料,采用工业干法制备氟化铝.利用响应面法优化工艺并建立数学模型,探讨氟化铵分解温度、流化床床层温度和流化反应时间各因素间相互作用对合成氟化铝的影响.确定了较优的工艺条件：氟化铵分解温度为259.70℃、流化床床层温度为553.54℃、流化反应时间为1.13 h.在此条件下,制得的产品w（A1F3）可达到90.26％.     

固定流化床反应器内气体分布方式的优化

传统小型固定流化床反应器采用烧结板作为气体分布装置,利用中控螺栓将分布器压紧固定在流化床反应器底部。在较高的操作温度条件下,由于密封垫与反应器材质的不同而产生不同程度的膨胀,导致密封部分或者环隙出现气流短路的问题,造成流化状态的不稳定,导致部分催化剂未参与实际反应,影响了催化剂评价数据结果的准确性。为了解决这一难题,文中采用堆砌的不锈钢珠作为分散介质,利用规则不锈钢珠气阻小、易于安装和拆卸的特点,降低了密封要求。文中通过流化床冷模实验比较了烧结板气体分布器和规则填料气体分布器的阻力大小和流化状态,通过流化床热模比较了烧结板气体分布器和规则填料气体分布器的温度分布。实验表明本文的方法大大改善了流化床流化状态,获得了良好的固定流化床评价结果。     

制备二氯氟乙酰卤的工艺

制备二氯氟乙酰氟（CFCl2COF)的工艺步骤包括：（1）在填充有氟化催化剂的固定床或管状流化床反应器内,在介于反应原料进口温度（175℃）与反应产物出口温度（275℃）之间的温度下,用氢氟酸（HF）氟化三氯乙酰卤;（2）蒸馏反应产物,循环回用三氯乙酰氟,回收HF和CFCl2COF的混合物;（3）在低于－10℃的温度下对HF／CFCl2COF进行冷却分离,对HF进行循环回用。     

液固提升管-流化床组合反应器中流化床径向固含率分布的实验研究

在一套新型液固提升管-流化床组合反应器中，以水-玻璃珠为液-固体系，对f500 mm′4000 mm的液固流化床反应器内不同高度颗粒固含率的径向分布进行了实验，考察了表观液速和颗粒循环速率操作条件对颗粒固含率径向分布的影响. 实验表明，液固流化床内流动区域在轴向上可以划分为分布器影响区、过渡区和均匀流化区，径向上可以划分为中心区和环隙区. 这种分布特征主要取决于分布器的结构、尺寸及其流化介质. 本工作还对液固流化床与气固喷动床的三区流动结构进行了比较.     

电化学氟化技术及其应用

电化学氟化(ECF)技术是用镍作阳极,在无水氟化氢中电解制备全氟化合物的一种方法.围绕ECF的原理,介绍了其反应机理.讨论了底物、反应介质、电极电压、电流密度等因素对ECF的影响.在不同电解氟化条件下,探讨了合成的相应氟化产物的稳定性和电化学性能.讨论了多种有机物的ECF的特点及应用.     

氟气在制备含氟有机物中的应用

重点介绍了近年来氟气直接氟化法在制备含氟的脂肪族、芳香族、杂环化合物以及在聚合物表面改性中的应用进展,同时介绍了微反应器技术在直接氟化反应中的应用情况。     

流化床在甲烷临氧CO2重整反应中的作用研究

在流化床反应器中进行甲烷临氧CO₂重整制合成气反应。通过计算分析了催化剂颗粒在床层内的流化特性。对比实验表明,流化床反应器在催化剂活性、稳定性、自热过程以及催化剂积炭等方面均体现出比固定床反应器的优越性。在流化床反应器中进行的甲烷自热重整反应,甲烷的转化率接近热力学平衡值,床层温度梯度小于10 ℃, 反应20 h后,催化剂表面无积炭。     

A simplified mathematical modeling for thermo-catalytic decomposition of methane over carbon black catalyst in a fluidized bed reactor

A mathematical model for thermo-catalytic decomposition of methane over carbon black catalysts in a fluidized bed was proposed. The simplified isothermal, uniform flow model was considered and implemented into a computer code to predict the reactor performance. The experiment of methane decomposition into hydrogen and carbon was carried out in a fluidized bed of I.D of 0.055 m and height of 1.0 m. The range of reaction temperature was 850–900 °C, gas velocity was 1.0–3.0 U _mf , and catalyst loading was 50–200 g. The reaction parameters for model equation were determined from the curve fittings and the comparison of experimental data with simulation results showed good agreement for fluidized bed reactor system. From the simulation results, the fluidized bed performance with different operating conditions were obtained, and this simple model can be used to predict the performance of a larger scale fluidized bed reactor and also in determining the optimum operating conditions.     

High temperature fluidized bed reactor: measurements,hydrodynamics and simulation

This paper was made possible through the development of a novel high temperature optical fiber probe to study the hydrodynamics of a high temperature fluidized bed reactor. The experimental results show that the hydrodynamic parameters considerably change with bed temperature when fluidizing FCC particles. For a given superficial gas velocity, the average local particle concentration, the dense phase fraction and the particle concentration in the dense phase decrease with increasing bed temperature. As a result of an increase in temperature, the fluidized behavior of the FCC particles progressively shifts from typical Geldart A towards B. Consequently, a modified two-phase model, based on the simple two-phase model, integrating the effects of temperature and superficial gas velocity on the hydrodynamics, is proposed. Simulation of a reactive catalytic system using a conventional simple two-phase model and the modified model is achieved. The predicted reactor performances strongly differ for each model. In the present case, the simple two-phase model underestimates the reactor performance by inadequately accounting for the solid fractions in the bubble and dense phases and their dependence on temperature and superficial gas velocity. This suggests that the hydrodynamic models should take into account the effects of temperature and superficial gas velocity when simulating the performance of a high temperature fluidized bed reactor.     

多段流化床技术用于多相催化与纳米材料合成过程

简要回顾了清华大学十余年来开发多段流化床技术与工业应用历程,包括利用冷态实验确定多段流化床的操作域,不同段中催化剂密相高度随气速变化以及与外置溢流管尺寸的关系,并且将其运用于硝基苯气相加氢制备苯胺、间苯二腈氨氧化、甲醇合成、乙炔法制备氯乙烯以及化学气相沉积法制备碳纳米管过程,并实现了工业化应用。多段流化床结构灵活,可以根据不同过程的工艺要求（如对变温或变气氛及高转化率与长催化剂寿命的要求等）进行调节。相关技术开发拓展了流化床的应用领域。     

丙烯催化氧化制丙烯酸的两段流化床工艺

分别在一段和两段流化床反应器中对丙烯催化氧化制备丙烯酸过程进行了研究. 主要考察了温度、丙烯空速和氧/烯比等操作条件对丙烯氧化制备丙烯醛的第一步反应中丙烯转化率和液相收率的影响. 结果表明,在两段流化床反应器中,由于能够有效抑制气体和固体的返混及催化剂床层中气泡的增长,第一步反应中丙烯转化率和液相收率可以分别大幅度提高到94.2%和74.4%. 得到第一步反应的优化条件为：丙烯空速20~21 L/(h·kg),操作温度360~365℃,氧/烯摩尔比1.6~1.8,在此条件下,考察了连续两步反应中的丙烯转化率和液相收率.     

流化床甲烷化基础与应用最新进展

由于CO甲烷化的快速表面反应、强放热特性,相比固定床,采用小颗粒催化剂的流化床甲烷化技术在反应活性和催化剂稳定性方面具有明显的技术优势。从高耐磨催化剂、流化床反应器及其创新、短流程两段甲烷化技术构建及其验证等方面总结了流化床甲烷化技术开发的最新进展。优化催化剂前体制备方法、调变催化剂组成可获得具有较高骨架强度和均匀性的催化剂一次微粒,进而通过优化的喷雾造粒工艺和填充黏结剂,制备出具有可调变粒度分布、高强度和高球形度的流化床用粉末催化剂,但其黏结剂的添加明显影响催化剂的低温活性。通过改性如Al₂O₃和FCC催化剂的球形颗粒,进而负载活性组分,开发了制备高活性、磨损指数小于1.5的流化床甲烷化Ni基催化剂的另一种技术方法。实验室研究证实了流化床甲烷化反应速率极快,在分布板上数毫米处即可实现可能的最高转化率,且在转化率和催化剂稳定性方面明显优于固定床,不仅由于流态化催化剂床层温度均匀,而且催化剂在床层内不停循环,加快了颗粒表面的更新。增大空速和表观气速,流化床的催化剂床层膨胀,反应气体与催化剂颗粒表面间的有效接触面积增加,使得流化床甲烷化对空速和表观气速的可调范围大。操作在更高气速条件的输送床甲烷化避免了操作气速的上限限制,可大幅降低反应器尺寸,有效提高单位截面的原料气负荷能力。输送床甲烷化可采用高热导率的催化剂颗粒传递反应热,相对于气体移热效率高、能力大。流化床甲烷化已在生物废弃物利用和焦炉煤气甲烷化方面开展了侧线示范,形成了相对多段绝热固定床工艺更简单的短流程两段甲烷化新工艺。     

Optimization fluidization characteristics conditions of nickel oxide for hydrogen reduction by fluidized bed reactor

We evaluated the optimal conditions for fluidization of nickel oxide (NiO) and its reduction into high-purity Ni during hydrogen reduction in a laboratory-scale fluidized bed reactor. A comparative study was performed through structural shape analysis using scanning electron microscopy (SEM); variance in pressure drop, minimum fluidization velocity, terminal velocity, reduction rate, and mass loss were assessed at temperatures ranging from 400 to 600 °C and at 20, 40, and 60 min in reaction time. We estimated the sample weight with most active fluidization to be 200 g based on the bed diameter of the fluidized bed reactor and height of the stocked material. The optimal conditions for NiO hydrogen reduction were found to be height of sample H to the internal fluidized bed reactor diameter D was H/D=1, reaction temperature of 550 °C, reaction time of 60 min, superficial gas velocity of 0.011 m/s, and pressure drop of 77 Pa during fluidization. We determined the best operating conditions for the NiO hydrogen reduction process based on these findings.     

大颗粒三相环隙气升式环流反应器流体力学行为

研究了大颗粒体系气升式环流反应器的流体力学行为,考察了表观气速和颗粒质量分数对床层膨胀高度、循环液速和固含率分布的影响。实验结果表明,按颗粒的运动状态不同可以将反应器内的流动分为3个区域,即固定床区域、膨胀床区域和循环床区域,各流动区域内的流动行为存在显著差异。随着颗粒质量浓度的增大,起始流化气速和最小循环气速均显著增大。基于三相流化床的流化模型和环流反应器的特点建立了相应的数学模型,对大颗粒三相气升式环流反应器的起始流化气速和最小循环气速进行了预测,模型预测值与实验测量值吻合良好。     

Hydrodynamic study of a toroidal fluidized bed reactor

Hydrodynamic behavior of a newly developed toroidal fluidized bed reactor is studied in this work. The reactor has a gas distributor consisting of angled blades in an annular ring at the reactor bottom. The driving force for particles to move over the distributing blades comes from the velocity head of gas jets accelerated upon entering the blade spacing. Relevant hydrodynamic behaviors are measured with various inert materials in a pilot scale 400-mm toroidal fluidized bed reactor. The observed hydrodynamic behavior is found to be essentially predictable at ambient temperature by conventional hydrodynamic models. Fine particle tracking on the reactor wall is clearly observed through oxidation of zinc dross at a bed temperature of around 1120°C, and is simulated on the basis of a simplified mathematical model. Hydrodynamic issues, such as particle flying trajectory and retention time in the reactor, are discussed based on the developed model.