SIMULTANEOUS MEASUREMENTS OF SURFACE INTERMEDIATES AND STEP VELOCITIES DURING THE WATER-GAS-SHIFT REACTION OVER AN IRON OXIDE CATALYST

The kinetics of the water-gas-shift reaction over an iron oxide catalyst has been studied with the transient tracing technique. The transient tracing technique was confirmed to be a new methodology of simultaneous measurements of adsorption and kinetics. The rate of the step, H₂O→ 2H(a) + O(a), was observed to be about ten times larger than that of the step, 2H(a) → H₂. The amount of adsorbed hydrogen obtained was 1.7 × 10²⁰ atoms/g-cat in agreement with that determined by the volumetric method during reaction.     

无梯度反应器中沉淀铁催化剂FT合成反应研究

在转篮式无梯度反应器中对喷雾干燥沉淀铁催化剂进行了 Fischer- Tropsch( FT)合成反应研究 .结果表明 :反应温度对 C1～C2 烷烃生成速率的影响比对 C3 ～ C4烷烃的大 ,对 C3 ～ C4烯烃生成速率的影响比对 C3 ～ C4烷烃的大 ;H2 /CO进料比对 C3 ～ C4烷烃和 C2 ～ C4稀烃的作用是先促进后抑制 ;提高反应压力对 C1～ C4烷烃和 C2 ～ C4烯烃的生成具有促进作用 .产品的烃分布为典型的双α分布 ,交点在 C6,α1为 0 .5 5 ,α2 为 0 .89     

喷雾干燥铁催化剂F-T合成反应的研究

采用转环式无梯度反应器对沉淀 -喷雾干燥技术相结合制备的 Fe- Cu- K- Si O2 催化剂在反应温度 2 5 0℃～ 2 80℃ ,压力 0 .5 MPa～ 1 .5 MPa,H2 /CO比 0 .1 9～ 1 .35和原料气空速 1 0 0 0h-1～ 2 5 0 0 h-1的条件下对 Fisher- Tropsch合成反应性能进行了考察 .结果表明 ,该催化剂具有较高的 F- T反应活性和水煤气交换 ( WGS)反应活性 ,产物烃分布显示出高的烯烃选择性 ,说明该条件有利于初级烯烃的脱附和低碳烃的生成 ,一定程度上减少了烯烃再吸附的链增长反应 .还考察了各种反应条件对产物碳数分布的影响 ,并观察到了运行过程中催化剂较低的失活速率 .     

沉淀铁催化剂上F-T合成反应的研究

制备了物相组成为 Quartz- Si O2 ,Hermatite- Fe2 O3 和 Fe2 O3 - Iron Oxide的沉淀铁催化剂 ,研究了该催化剂作用上固定床积分反应器中费托合成反应特性 .发现 2 .6MPa,80 0 h-1,H2 /CO=2 /3,2 60℃～ 2 90℃时 ,随着温度的升高 ,CO和 H2 的转化率增大 ,CO2 选择性减小 ;40 0 h-1,65 0 h-1,80 0 h-1低空速和 2 4 0 0 h-1,32 0 0 h-1,40 0 0 h-1,640 0 h-1高空速时 ,随着空速的升高 ,H2转化率、CO转化率选择性下降 ,CO2 的选择性升高 ;2 80℃ ,2 .6MPa,H2 /CO进料比 2 /3,1 /1 ,2 /1时 ,随着 H2 /CO进料比的增加 ,CO转化率 ,H2 /CO利用比和 CH4选择性都增加 ,H2 转化率和 CO2选择性减小 .     

沉淀铁挤条F-T合成催化剂WGS反应考察

采用固定床积分反应器, 在工业条件下 （５００ ｈ－ １, １ ＭＰａ～２．６ ＭＰａ）, 对挤条Ｆｅ－Ｃｕ－Ｋ工业催化剂进行了水煤气变换反应性和ＦＴ反应产物分布链增长几率的考察． 在稳态下, 保持一定的轴向温度分布, 求得宏观动力学方程, 与实验数据符合较好．     

浆态相费托合成反应铁基催化剂的磨损研究

在催化剂磨损现象和强度理论的基础上,对浆态相费托合成反应中的铁催化剂的磨损机制进行了描述,侧重对系列雷尼铁催化剂的磨损规律加以研究,结果表明雷尼铁的磨损是因为其发达的孔结构,反应条件下沿狭缝形的孔发生破裂,但是并不致使继续粉化,而且其粒度的变化对浆态相费托合成反应活性影响很小,反应结束后的分离性能也显著优于沉淀铁催化剂。     

CO＋H2两段法合成汽油（MFT）过程开发

经过程分析,认为一段反应器的选型与放大是本过程开发的中心环节。通过三种规格及两种气氛下的一段工业单管模试,表明高速固定床反应器能解决强放热反应的移热问题。经100t油/年中试,1600小时运行汽油收率达90～100g/Nm~3(CO+H_2),油品辛烷值(马达法)≥80,并为进一步放大提供了设计依据。     

A PROBABILISTIC MODEL OF THE FISCHER-TROPSCH SYNTHESIS IN A FLOW REACTOR

The Fischer-Tropsch synthesis is usually carried out in flow reactors, such as fluidized-bed and bubble column slurry reactors. The nature of multiphase flow together with the well-known random nature of chemical reactions renders the performances of such flow reactors stochastic. In this work, stochastic processes, more specifically continuous time Markov chains, are employed for analyzing and modeling both the dispersive mixing and chemical kinetics in a flow reactor for the Fischer-Tropsch synthesis. The model predicts the distributions of products inside as well as outside the reactor at any time Under a steady state operation, the model gives rise to the Flory equation. Other results include expressions for predicting the mole fraction of chains with j carbon atoms inside and outside the reactor. This approach can be applied to both time homogeneous and heterogeneous processes.     

DME DIRECT SYNTHESIS FROM SYNGAS IN A LARGE-SCALE THREE-PHASE SLURRY BUBBLE COLUMN REACTOR: TRANSIENT MODELING

In this research, a new transient mathematical model based upon tanks-in-series configuration was developed to simulate the direct synthesis of dimethyl ether (DME) from syngas in a commercial-scale slurry bubble column reactor. A comparison between the simulation results and experimental data showed that the applied model might acceptably describe the behavior of the slurry reactor. Furthermore, simulation results in the heterogeneous bubble flow regime indicated that the proposed model with 10 tanks-in-series provided the optimum condition. Utilizing this transient model and considering catalyst deactivation, the effect of operating conditions on DME productivity and CO conversion were investigated. In addition, the dynamic behavior of the reactor was studied after implementing a step change in the reactor's coolant fluid temperature.     

用程序升温表面反应研究铁系催化剂丁烯氧化脱氢性能

本文利用TPR法研究了丁烯氧化脱氢铁系催化剂的表面性能。三种类型氧吸附中心被检测。结果表明，催化剂活性与氧吸附中心类型有关。CO2生成量取决于不同氧中心位的密度和反应温度，并对温度的影响进行了讨论。     

沉淀型Fe-Mn工业催化剂的F-T反应性能

在积分固定床反应器中系统考察了用于Fischer-Tropsch(F-T)合成的沉淀型Fe-Mn工业催化剂的性能.首先对催化剂进行了2000h的稳定性测试,然后在不同反应温度、原料气H₂/CO比、空速和总压下考察其反应性能.结果表明,在2000h的运行过程中,该催化剂活性和选择性较平稳,失活速率较小,且在较高的反应温度下失活速率更小,显示出该催化剂具有良好的长期稳定性;经2000h的运行后,该催化剂仍表现出较高的反应活性和稳定性,同时,还保持着较高的低碳烯烃和C₅₊选择性.此外,当反应条件在一定范围内发生变化时,低碳烯烃和C₅₊选择性变化不大,说明该催化剂具有良好的可操作性.     

低温液相甲醇合成鼓泡浆态反应器数学模拟

建立了经由甲酸甲酯的低温液相甲醇合成鼓泡浆态反应器的数学模型 ,模拟了实验室鼓泡浆态反应器的行为 ,并利用模型考察了工艺参数如表观气速、催化剂浓度对反应的影响 ,对改进和提高低温液相浆态床反应器甲醇合成提供了信息 ,以便对开发低温甲醇合成工艺提供参考和指导     

SYNTHESIS OF MONODISPERSED IRON OXIDE PARTICLES BY A LARGE-SCALE MICROWAVE REACTOR

Well-defined mondispersed iron oxide particles can be synthesized in conventional hydrolysis approaches, but the synthesis generally takes two to seven days. Microwave hydrothermal approaches offer the possibility of significantly reducing synthesis time. This work demonstrates the feasibility of microwave synthesis in large scale. The batch size was 5 L, and the holding time was two hours. The crystallinity of the powders and the morphology and the monodispersity of the synthesized particles were comparable to those produced from conventional approaches. The particle size was in the nanosize range. The results indicated that for synthesis of monodispersed Fe₂O₃ nanopowders, it is possible to achieve the production rate of a 2.1 m³ conventional reactor with a 5 L microwave accelerated reactor.     

列管式固定床F-T合成反应器的模拟及优化

针对列管式固定床F-T合成反应器的特点建立了一维拟均相数学模型。通过对模型计算与试验结果进行对比分析,表明该模型可以较好的描述反应过程。并从固定床反应器的操作热稳定性出发,对列管式固定床F-T合成反应器的最大允许管径和最大传热温差进行了计算。结合模型计算结果得出了合适的反应管直径与冷却介质温度范围,可以优化列管式固定床F-T合成反应器的设计。     

SYNTHESIS OF MONODISPERSED IRON OXIDE PARTICLES BY A LARGE-SCALE MICROWAVE REACTOR

Well-defined mondispersed iron oxide particles can be synthesized in conventional hydrolysis approaches, but the synthesis generally takes two to seven days. Microwave hydrothermal approaches offer the possibility of significantly reducing synthesis time. This work demonstrates the feasibility of microwave synthesis in large scale. The batch size was 5 L, and the holding time was two hours. The crystallinity of the powders and the morphology and the monodispersity of the synthesized particles were comparable to those produced from conventional approaches. The particle size was in the nanosize range. The results indicated that for synthesis of monodispersed Fe₂O₃ nanopowders, it is possible to achieve the production rate of a 2.1 m³ conventional reactor with a 5 L microwave accelerated reactor.     

EFFECT OF FINE SOLID PARTICLES ON GAS-LIQUID MASS TRANSFER RATE IN A SLURRY REACTOR

The influence of suspended fine particles of differing adsorbing capacity (activated carbon, avicell cellulose, SiO₂, and molecular sieves) on the liquid-film mass transfer coefficient κ_L, was examined experimentally in a stirred cell of well-defined gas-liquid interfacial area by chemical methods. The greatest effect on κ_L was observed with the activated carbon (about a threefold increase). An addition of glycerine in excess of 2.5 × 10^-3 k mol/m³, which was adsorbed on the particles preferentially, removed this increase in κ_L totally. Amongst other particles, only avicell cellulose showed measureable effects. The increase in κ_L values was inversely proportional to the temperature and the stirring speed, and the particle loading was found to be immaterial after a certain value. When the reaction rate increased (hence, when the thickness of dissolved gas-rich layer decreased) by gradual addition of a homogeneous catalyst (i.e. Co⁺⁺ for sulphite oxidation), the effect of particles on κ_L decreased and eventually it disappeared.     

氨合成催化剂母体相组成对还原性能的影响

采用Shimadzu DT-40型热分析仪,研究了不同原始铁氧化物组成对氨合成熔铁催化剂的还原性能的影响。发现催化剂的还原性能和活性与母体相组成的关系具有相似的规律性。当母体中两种物相共存时,催化剂的还原过程是按物相分阶段依次进行的,其结果使还原速度变慢,还原温度升高,亦使还原后催化剂的活性降低。氨合成催化剂的还原性能与其活性具有一致性,愈易还原的催化剂,其活性亦愈高。研究结果表明,在熔铁催化剂中,Fe_(1-x)O基氨合成催化剂还原速度最快、还原温度最低,其活性亦最高。     

三相鼓泡淤浆床环氧乙烷合成反应器数学模拟及工程分析

建立了加压三相鼓泡淤浆床环氧乙烷合成反应器的数学模型 ,计入了催化剂颗粒在床层中沉降形成沿床高浓度分布对反应的影响以及由于惰性液相载体部分返混对传递的影响 ,进一步利用经实验验证的上述数学模型模拟不同表观气速、床高、反应器直径 (扣除传热元件截面积 )、进口乙烯摩尔分数等参数对床层中催化剂浓度随床高的分布、出口环氧乙烷摩尔分数、环氧乙烷选择率以及单位质量催化剂环氧乙烷年产量的影响 .通过模拟分析预示了工业三相床环氧乙烷反应器的合理尺寸、表观气速、环氧乙烷选择率以及时空产率 ,为工业化提供必要的设计依据     

温度敏感型铁催化剂上F-T合成本征动力学

针对F-T合成铁催化剂对温度敏感的特点,提出了使催化剂活性在高温条件下先“钝化”,用集总法处理F-T合成动力学数据的新的研究方法及数学模型。采用固定床反应器对共沉淀型Fe-Cu-K工业催化剂F-T合成本征动力学进行了研究,求得本征动力学方程,为工业催化剂的进一步放大以及反应器的设计提供了理论依据。     

渣油催化裂化提升管反应器性能的数值模拟--喷嘴射流速度与角度对流动反应的影响

应用三维数值模拟的研究方法,考察了喷嘴射流速度与角度对提升管反应器内流动、传热及反应的影响。从数值模拟结果来看,同一角度下、一定范围内的射流速度对提升管内流动形态改变不大,对催化剂和油气浓度分布、气相组成浓度分布有一定影响,而角度变化对流动、反应都有较大影响,从本研究的范围来看,可以得出对不同的操作条件和装置存在最优喷嘴射流速度和角度的结论,射流角度应不超过45°,且45°时60m·s~(-1)的射流速度为优。