Fluidized Bed Polyethylene Reactor Modeling in Condensed Mode Operation

Summary: Modeling of fluidized bed reactor for polyethylene production in the condensed mode operation is proposed in this paper. A two-phase model including the emulsion and bubble phases with the constant bubble size is employed to describe hydrodynamic behavior of the reactor. The kinetics of Ziegler-Natta polymerization is also modeled with a two active site model. The phase behavior and solubility of low molecular weight components in polyethylene are estimated with the Sanchez-Lacombe equation of state. The validation of the model is carried out with industrial data for an ethylene and 1-butene copolymerization with the isopentane as a condensable component. The simulation results are in good agreement with industrial data. The model is also used to study quantitatively the effect of the inlet stream temperature to the reactor and isopentane concentration in the reactor on the production rate. For instance, in a typical process, when the inlet stream temperature changes 10 °C, the production rate will alter about 40%. Furthermore, the change of the isopentane concentration around 1 mole percentage leads to a variation of production rate about 14%.     

Selective dimerization of ethylene to but-1-ene under the conditions of industrial process. I. Influence of temperature and pressure on the rate of the process in a bubbling type reactor

Analysis of mass and heat balance in the reaction node of the process of ethylene dimerization into but-1-ene under the industrial conditions is performed. It is found that ethylene concentration in the reactor liquid phase by a complex way depends on the reactor temperature, pressure and but-1-ene concentration in the liquid phase. Optimal process temperature is 80–90°C, operating pressure in the reactor is 0.6–0.8 MPa. Increase in pressure above 1 MPa practically excludes heat withdraw via but-1-ene evaporation and makes the system of heat withdrawing ineffective.     

Highly selective ethylbenzene production through alkylation of dilute ethylene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene.It comprised of a reactor vessel,vapor phase ethylene feed stream,benzene and transalkylation feed stream.Especially the product stream containing ethylbenzene was used to heat the reactor vessel,which consisted of an alkylation section,an upper heat exchange section,and a bottom heat exchange section.In such a novel reactor,vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section.The process was demonstrated by the thermodynamic analysis and experimental results.In fact,during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction,the ethene conversion was above 95%,and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene plus transalkylation feed).At the same time,the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140-185℃ of temperature,1.6-2.1 MPa of pressure,3.0-5.5 of benzene/ethylene mole ratio,4-6 v% of transalkylation feed/(benzene+transalkylation feed),0.19-0.27 h-1 of ethene space velocity,and 1000 g of 3998 catalyst loaded.Thus,compared with the conventional ethylbenzene synthesis route,the transalkylation reactor could be omitted in this novel Industrial process.     

High selective ethylbenzene obtainment through alkylation of dilute ethene with gas phase-liquid phase benzene and transalkylation feed

A novel industrial process was designed for the highly selective production of ethylbenzene. It comprised of a reactor vessel, vapor phase ethylene feed stream, benzene and transalkylation feed stream. Especially the product stream containing ethylbenzene was used to heat the reactor vessel, which consisted of an alkylation section, an upper heat exchange section, and a bottom heat exchange section. In such a novel reactor, vapor phase benzene and liquid phase benzene were coexisted due to the heat produced by isothermal reaction between the upper heat exchange section and the bottom heat exchange section. The process was demonstrated by the thermodynamic analysis and experimental results. In fact, during the 1010 hour-life-test of gas phase ethene with gas phase-liquid phase benzene alkylation reaction, the ethene conversion was above 95%, and the ethylbenzene selectivity was above 83% (only benzene feed) and even higher than 99% (benzene plus transalkylation feed). At the same time, the xylene content in the ethylbenzene was less than 100 ppm when the reaction was carried out under the reaction conditions of 140–185 °C of temperature, 1.6–2.1 MPa of pressure, 3.0–5.5 of benzene/ethylene mole ratio, 4–6 v% of transalkylation feed/(benzene+transalkylation feed), 0.19–0.27 h^?1 of ethene space velocity, and 1000 g of 3998 catalyst loaded. Thus, compared with the conventional ethylbenzene synthesis route, the transalkylation reactor could be omitted in this novel industrial process.     

乙烯在煤焦及石英砂床层上裂解实验研究

以石油炼制过程中产生的炼厂气与煤共转化利用为背景,采用小型石英管固定床反应装置,在850℃～1000℃下,对乙烯在空床、彬县煤焦以及石英砂床层上的裂解反应进行了研究。结果表明,乙烯裂解产物包括氢气、甲烷、乙烷及裂解炭,反应温度越高,裂解越彻底,生成的氢气越多;850℃～950℃时,乙烯在彬县焦上初始转化率最高,随着反应的进行逐渐降低到一个较低的平衡值,并且与在石英砂上裂解结果接近。这说明新鲜彬县煤焦对乙烯裂解呈现良好的催化作用,但随着反应进行其催化活性由于裂解生成的炭沉积在煤焦表面而逐渐丧失。1000℃时乙烯在石英砂上和空床裂解转化率均可达到94％,即在此温度下乙烯无需催化剂通过热作用即可接近完全裂解。     

Thermal Effects on Hydrothermal Biomass Liquefaction

Batch pressure vessels commonly used for hydrothermal liquefaction have typical heating times in the range of 30 to 60 min. Thermodynamically, the complex set of reactions are path dependent, so that the heating rate can possibly affect yields and the composition of the resultant liquid products. It is postulated that the mode of heat transfer becomes an uncontrolled variable in kinetic studies and can seriously impact scale-up. To confirm this hypothesis and minimize these heat-transfer-related artifacts, we designed a batch pressure vessel equipped with an induction heating system, which allows the reduction of heat-up times by about two orders of magnitude to several seconds, compared to tens of minutes with standard pressure reactors. This system was used to study the direct liquefaction of corn stover and aspen wood with a pretreatment. The heating rate was found to have no significant effect on the composition of the liquid products. However, the liquid yields are dependent on the heating rate. Varying the cooling rate does not show obvious effects. The results confirm that the heating rate, as governed by the mode of heat transfer, is an important factor that needs to be considered during scale-up.     

Sampling system for mass spectrometric monitoring of a stream of reaction liquid

Reaction liquid is continuously circulated between the reactor and an automated Bendix liquid injection valve. A well defined volume of liquid is injected into a hot zone. The liquid injected is then vaporized and the resulting sample gas is swept with a stream of helium into a series of dilution chambers. The analyte concentration-time profile at the exit of the last chamber was mathematically modelled. It was found that the degree of symmetry of the profile increases when the number of chambers increases. The design and performance of the system are discussed together with results of a kinetic study of a chemical reaction.     

乙烷脱氢制乙烯技术研究进展及趋势

在碳中和及全球能源供需版图调整的背景下,乙烯生产原料轻质化成为主流趋势。乙烷脱氢制乙烯技术具有低能耗、低碳排、流程短、收率高、成本低等优势,但目前工业上主要通过乙烷蒸汽裂解法生产乙烯,其他方法工业化生产相对不成熟。本文简述了近年来乙烷脱氢制乙烯技术(包括直接催化脱氢、O₂辅助氧化脱氢、CO₂辅助氧化脱氢、化学链氧化脱氢、催化膜反应器脱氢等)工艺及催化剂的研究现状,同时介绍了其他新兴工艺及催化剂。乙烷脱氢制乙烯技术现阶段面临的挑战不仅在于开发更高效的催化剂及更低能耗的技术,更需要突破乙烷脱氢热力学平衡的限制设计合适的反应路径,其中催化膜反应器脱氢、化学链氧化脱氢工艺都具有非常广阔的市场和工业化发展前景。     

Synthesis of Functional Oxide Nanoparticles Through RF Thermal Plasma Processing

A method of synthesizing functional nanostructured powders through reactive thermal plasma processing has been developed. Nano-sized oxide powders, including titanium dioxide and some functional oxides, were synthesized by the oxidation of liquid precursors. Oxides with the prescribed cation ratio of the liquid precursor can be synthesized with this technique, and it is possible to precisely adjust the chemical composition, which is linked to the appropriate functions of ceramic materials. Quench gases, either injected from the shoulder of the reactor or injected counter to the plasma plume from the bottom of the reactor, were used to vary the quench rate; therefore, the particle size of the resultant powders. The experimental results are well supported by numerical analysis on the effects of quench gases on the flow pattern and temperature field of thermal plasma as well as on the trajectory and temperature history of particles. Plasma-synthesized TiO₂ nanoparticles showed phase preferences different from those synthesized by conventional wet-chemical processes. Nano-sized particles of high crystallinity and nonequilibrium chemical composition were formed in one step via reactive thermal plasma processing. The plasma-synthesized nanoparticles were spherical and hardly agglomerated, and high dispersion properties were observed, i.e., the plasma-synthesized TiO₂ nanoparticles were individually dispersed in water.     

Thermodynamic Effects on Grade Transition of Polyethylene Polymerization in Fluidized Bed Reactors

An off‐line dynamic optimization procedure is employed to optimize the transition between different grades of linear low density polyethylene in a fluidized bed reactor. This type of reactor is frequently operated under condensed mode, which consists of injecting induced condensing agents (ICA) to absorb part of the reaction heat. However, the presence of ICA affects the solubility of monomers in the polymer, so it is important to account for this effect in a grade transition optimization strategy. A kinetic model is combined with a thermodynamic model based on the Sanchez–Lacombe equation of state to describe the grade transitions. Simplified correlations are then suggested to predict the impact of ICA on ethylene and comonomer solubility in a quaternary system. The results highlight the importance of the thermodynamic model during grade transition.     

Numerical solution of nonlinear and non-isothermal general rate model of reactive liquid chromatography

Abstract

A nonlinear general rate model (GRM) of liquid chromatography is formulated to analyze the influence of temperature variations on the dynamics of multi-component mixtures in a thermally insulated liquid chromatographic reactor. The mathematical model is formed by a system of nonlinear convection–diffusion reaction partial differential equations (PDEs) coupled with nonlinear algebraic equations for reactions and isotherms. The model equations are solved numerically by applying a semi-discrete high-resolution finite volume scheme (HR-FVS). Several numerical case studies are conducted for two different types of reactions to demonstrate the influence of heat transfer on the retention time, separation, and reaction. It was found that the enthalpies of adsorption and reaction significantly influence the reactor performance. The ratio of density time heat capacity of solid and liquid phases significantly influences the magnitude and velocity of concentration and thermal waves. The results obtained could be very helpful for further developments in non-isothermal reactive chromatography and provide a deeper insight into the sensitivity of chromatographic reactor operating under non-isothermal conditions.     

乙烯装置裂解炉管焦炭燃烧特性的研究

齐鲁石化公司乙烯厂是我国最先引进计算机控制下蒸汽 空气在线烧焦技术的乙烯厂 ,在线烧焦使其过程自动化程度大大提高 ,裂解炉没有升降温过程 ,延长了裂解炉管的使用年限[1～ 5] 。但裂解气盘管管径较小 ,易于堵塞 ,烧焦时间稍短 ,管壁上的焦炭就燃烧不完全 ,目前在线烧焦时间还需 70ｈ～ 80ｈ。为了进一步缩短烧焦时间 ,节约能源 ,提高炉子运行周期 ,必须对乙烯装置裂解炉管焦炭的微观结构及燃烧过程进行深入研究 ,以提出进一步加快烧焦速度的办法 ,满足工业生产的需要。本研究采用国内某乙烯厂裂解炉管焦炭为实验原料 ,研究了焦炭的微观…     

Syngas Production from Propane Using Atmospheric Non-thermal Plasma

Propane steam reforming using a sliding discharge reactor was investigated under atmospheric pressure and low temperature (420 K). Non-thermal plasma steam reforming proceeded efficiently and hydrogen was formed as a main product (H₂ concentration up to 50%). By-products (C₂-hydrocarbons, methane, carbon dioxide) were measured with concentrations lower than 6%. The mean electrical power injected in the discharge is less than 2 kW. The process efficiency is described in terms of propane conversion rate, steam reforming and cracking selectivity, as well as by-products production. Chemical processes modelling based on classical thermodynamic equilibrium reactor is also proposed. Calculated data fit quiet well experimental results and indicate that the improvement of C₃H₈ conversion and then H₂ production can be achieved by increasing the gas fraction through the discharge. By improving the reactor design, the non-thermal plasma has a potential for being an effective way for supplying hydrogen or synthesis gas.     

Polymerization of ethylene with the (C5H5)4Zr-methylaluminoxane soluble catalytic system

The effects of catalyst concentration, Al-to-Ti molar ratio, hydrogen additives, and time of aging of catalyst components on the kinetic features of ethylene polymerization in the presence of the (C₅H₅)₄Zr-methylaluminoxane soluble catalytic system in toluene and hexane at 60°C and an ethylene pressure of 0.6 MPa have been studied. It has been demonstrated that the highest activity and productivity of the title system is achieved in the presence of 0.9% H₂ in the gas phase of a reactor (2180 kg PE/(g Zr h)). When polymerization is carried out in hexane, the rate constant of chain propagation is lower by a factor of ～1.5 than that in the case of toluene and the catalytic system is characterized by a long lifetime.     

Ethylene Conversion to Higher Hydrocarbon over Copper Loaded BZSM-5 in the Presence of Oxygen

The successful production of higher hydrocarbons from methane depends on the stability or the oxidation rate of the intermediate products. The performances of the BZSM-5 and the modified BZSM-5 catalysts were tested for ethylene conversion into higher hydrocarbons. The catalytic experiments were carried out in a fixed-bed micro reactor at atmospheric pressure. The catalysts were characterized using XRD, NH3-TPD, and IR for their structure and acidity. The result suggests that BZSM-5 is a weak acid. The introduction of copper into BZSM-5 improved the acidity of BZSM-5. The conversion of ethylene toward higher hydrocarbons is dependent on the acidity of the catalyst. Only weaker acid site is required to convert ethylene to higher hydrocarbons. The loading of Cu on BZSM-5 improved the selectivity for higher hydrocarbons especially at low percentage. The reactivity of ethylene is dependent on the amount of acidity as well as the presence of metal on the catalyst surface. Cu1%BZSM-5 is capable of converting ethylene to higher hydrocarbons. The balances between the metal and acid sites influence the performance of ethylene conversion and higher hydrocarbon selectivity. Higher loading of Cu leads to the formation of COx.     

Dehydration of Ethanol to Ethylene on Ring- and Trilobe-Shaped Catalysts

The indicators of ethanol to ethylene catalytic dehydration process on trilobe- and ring-shaped samples of an alumina catalyst were compared at the fixed parameters: thermal agent temperature and catalyst load. Experiments were performed in a flow-through reactor of a laboratory setup and in a tubular reactor of a pilot installation. The use of the less active ring-shaped catalyst ensures higher values of ethanol conversion, ethylene yield, and catalyst performance and significantly lower hydraulic resistance, compared to the more active trilobe-shaped catalyst. This is caused by lower intensity of the heat absorption on the less active catalyst and, correspondingly, to the higher temperature in the ring bed due to higher bed porosity.     

Tandem use of carboxypeptidase Y reactor and displacement chromatograph for peptide synthesis

A packed-bed enzyme reactor with immobilized carboxypeptidase Y was used in tandem with a displacement chromatograph for the preparation of N-benzoyl-L-arginyl-L-methioninamide, from N-benzoyl-L-arginine and L-methioninamide. The pumps and valves of the coupled enzyme reactor and displacement chromatograph were controlled by a microprocessor. The enzyme was immobilized on microparticulate amino-silica by glutaraldehyde and packed into a 60 X 4.6 mm I.D. column. The packed-bed reactor was used in the recirculating mode and components of the reaction mixture were subsequently separated by displacement chromatography on a 250 X 4.6 mm octadecyl-silica column using butoxyethoxyethanol as the displacer. Unreacted L-methioninamide was returned to the reaction mixture. Both the progress of the reaction and the extent of separation by displacement chromatography were monitored by high-performance liquid chromatographic analysis. The system was designed so that enzymatic peptide synthesis, separation by displacement chromatography, and column regeneration were carried out simultaneously by using two identical columns in parallel. An amount of 460 mg of N-benzoyl-L-arginyl-L-methioninamide having purity greater than 99% could be obtained in 24 h with this system. The tandem operation of the enzyme reactor and liquid chromatograph operated in the displacement mode offers a means for the synthesis and purification of peptides.     

Modelling of the thermal effects involved in the determination of heat of mixing,using an ITC operating in continuous mode

A simplified RC model which simulates the operation mode of an isothermal titration calorimeter (ITC), when it is used in a continuous mode to determine heat of mixing, is proposed. The model takes into account several thermal effects that are evident in the mixing process and it must be identified and quantified to determine reliable values of heat of mixing. The main effects considered in the development of the model were those caused by: (i) the difference between the temperatures of the injected liquid and the mixture, (ii) the increase in heat capacity of the mixture and the thermal conductance of the couplings between the mixture and its surroundings and (iii) the changes in the power dissipated by stirring after injection. A good agreement between model and experimental results is observed.     

Trichloroethylene Combustion in a Submerged Thermal Plasma: Results and Chemical Kinetics Model

This work deals with incineration of organic liquid wastes using an oxygen thermal plasma jet, submerged in water. The results presented here concern incineration of trichloroethylene (TCE). During a trial run, the CO₂ and CO content in the exhaust gas is continuously measured; samples taken periodically from the solution are analyzed by appropriate methods: total organic carbon and chlorine content are measured. Process efficiency during tests with a few L/h of TCE is given by the mineralization rate. The trapping rate of chlorine as HCl is near 100 %. The TCE destruction and removal efficiency, measured by MS/GC, is better than 99.9999 %. A simplified kinetic model of gas quenching was constructed from a single-phase plug-flow reactor model taking into account 14 species and 34 reactions. It satisfies the requirements of heat balance and major components analysis, and reveals the major role of the OH radical on the concentrations of CO as well as HCl and/or Cl₂ in the off-gas stream.     

Mathematical simulation of the formation of liquid products from catalytic cracking gases over a zeolite-containing catalyst modified with Group VI and VIII metals

The kinetics of the formation of liquid products from catalytic cracking gases over a zeolite-containing catalyst in a flow reactor in the temperature range from 260 to 420°C at GHSV = 30–264 h^–1 and an on-stream time of 5–25 s has been investigated. A kinetic model for the process proceeding according to a likely scheme is proposed. The rate constants and activation energies of certain reactions involved in the process have been determined. A mathematical model of the process taking into account the mass and heat balances, as well as hydrodynamic conditions, has been developed. The concentration and temperature fields and the pressure over the catalyst bed height have been calculated. The target product yield on has been plotted as a function of the on-stream time.