Production of H2 and medium heating value gas via steam gasification of lignins in fixed‐bed reactors

In this work, steam gasification of Alcell and Kraft lignins were carried out in a fixed‐bed reactor in order to produce H₂ and medium heating value gas. The conversion of lignins increased from a low of 64 wt% for Alceil lignin to a high of 88 wt% for Kraft lignin with increasing steam flow rate and temperature. Maximum H₂ production of 60.7 mol% was obtained at 800°C and at a steam flow rate of 15 g/h/g of Kraft lignin, whereas maximum heating value of 18000 kl/m³ of the product gas was obtained at 650°C and at 5 g/h/g of Alcell lignin. Also, the performance of a Ni‐based steam reforming catalyst for the production of H₂ was studied for both types of lignin in a dual fixed‐bed reaction system. A maximum H₂ production of 63 mol% was obtained at a catalyst bed temperature of 750°C and at a catalyst loading of 0.3 g for Alcell lignin. The sulfur present in Kraft lignin had detrimental effect on the catalyst performance.     

Kinetic study of crude oil-to-chemicals via steam-enhanced catalytic cracking in a fixed-bed reactor

This study presents new experimental results on the direct conversion of crude oil to chemicals via steam-enhanced catalytic cracking. We have organized the experimental results with a kinetics model using crude oil and steam co-feed in a fixed-bed flow reactor at reaction temperatures of 625, 650, and 675°C over the Ce-Fe/ZSM-5 catalyst. The model let us find optimum conditions for crude oil conversion, and the order of the steam cracking reaction was 2.0 for heavy oil fractions and 1.0 for light oil fractions. The estimated activation energies for the steam cracking reactions ranged between 20 and 200 kJ/mol. Interestingly, the results from kinetic modelling helped in identifying a maximum yield of light olefins at an optimized residence time in the reactor at each temperature level. An equal propylene and ethylene yield was observed between 650 and 670°C, indicating a transition from dominating catalytic cracking at a lower temperature to a dominating thermal cracking at a higher temperature. The results illustrate that steam-enhanced catalytic cracking can be utilized to effectively convert crude oil into basic chemicals (52.1% C2-C4 light olefins and naphtha) at a moderate severity (650°C) as compared to the conventional high-temperature steam cracking process.     

Suppressing secondary reactions of coal pyrolysis by reducing pressure and mounting internals in fixed-bed reactor

Pyrolysis of Shenmu coal was performed in fixed-bed reactors indirectly heated by reducing operating pressure and mounting internals in the reactor to explore their synergetic effects on coal pyrolysis. Mounting internals particularly designed greatly improved the heat transfer inside coal bed and raised the yield of tar production.Reducing pressure further facilitated the production of tar through its suppression of secondary reactions occurring in the reactor. The absolute increase in tar yield reached 3.33 wt% in comparison with the pyrolysis in the reactor without internals under atmospheric pressure. The obtained tar yield in the reactor with internals under reduced pressure was even higher than the yield of Gray–King assay. Through experiments in a laboratory fixed bed reactor, it was also clarified that the effect of reducing pressure is related to volatile release rate in pyrolysis. It did not obviously vary tar yield at pyrolysis temperatures below 600 °C, while the effect was evident at 650 and 700 °C but became limited again above 800 °C. Under reduced pressure the produced tar contained more aliphatics and phenols but less aromatics.     

Production of fatty acid methyl esters over a limestone-derived heterogeneous catalyst in a fixed-bed reactor

Production of fatty acid methyl esters (FAME) via the transesterification of different vegetable oils and methanol with a limestone-derived heterogeneous catalyst was investigated in a fixed-bed reactor at 65 °C and ambient pressure. This heterogeneous catalyst, as a 1 or 2 mm cross-sectional diameter extrudate, was prepared via a wet mixing of thermally treated limestone with Mg and Al compounds as binders and with or without hydroxyethyl cellulose (HEC) as a plasticizer, followed by calcination at 800 °C. The physicochemical properties of the prepared catalysts were characterized by various techniques. Palm kernel oil, palm oil, palm olein oil and waste cooking oil could be used as the feedstocks but the FFA and water content must be limited. The extrudate catalyst prepared with the HEC addition exhibited an enhanced formation of FAME due to an increased porosity and basicity of the catalyst. The FAME yield was increased with the methanol/oil molar ratio. The effect of addition of methyl esters as co-solvents on the FAME production was investigated. The structural and compositional change of the catalysts spent in different reaction conditions indicated that deactivation was mainly due to a deposition of glycerol and FFA (if present). The FAME yield of 94.1 wt.% was stably achieved over 1500 min by using the present fixed-bed system.     

间热径向流反应器料层厚度对煤热解特性的影响

考察了方形径向流固定床煤热解反应器中变化煤层厚度对料层升温速度及煤热解产物分布特性的影响。随着料层厚度增加,导致煤热解反应要求的时间增长,热解水和气的产率相应增加,焦油和半焦收率逐渐降低,但焦油中轻质组分(沸点低于360℃组分)含量呈升高趋势,半焦和煤气热值稍许降低。如,加热壁温度900℃、从45 mm至105 mm增加煤料层厚度时,焦油产率从7.17%(质量,下同)下降到6.26% (相对干基煤),但焦油中的轻焦油组分含量则从67%升至72.7%,半焦产率由80.0%降至77.0%,热解水和煤气产率分别由6.96%和5.91%增至8.85%和7.90%,煤气热值则由24348.5 kJ·m^-3下降至20649.2 kJ·m^-3。所得半焦的热值径向上由高温侧向低温侧逐渐降低,煤料层越厚、热值降幅越大,而相同煤料层厚度处与加热壁平行的同一轴向平面上的半焦热值基本相同。针对研究的反应器,气相热解产物在反应器内沿径向(横向)由高温料层区向低温料层区流动。在该过程中伴随着热解产物对远离加热壁的低温煤料的传热、热解生成重质组分的冷凝和在煤/半焦颗粒表面的吸附截留,进而在低温料层进一步升高温度时发生二次裂解等物理化学过程。反应器内煤层厚度越大,上述各种伴随的物化作用越显著,从而明显影响煤料层的升温及热解特性。     

Production of hydrogen and syngas via gasification of the corn and wheat dry distiller grains (DDGS) in a fixed-bed micro reactor

Production of hydrogen and syngas via gasification of the corn and wheat dry distiller grains (DDGS) with oxygen in a continuous downflow fixed bed micro reactor are studied in this paper. A series of experiments have been performed to investigate the effects of reaction time (15–45 min), reactor temperature (700–900 °C) and oxygen to nitrogen ratio (0.08–0.2 vol./vol.) on product gas composition, gas yield, low heating value (LHV) and carbon conversion efficiency. Over the ranges of the experimental conditions used, the results obtained seemed to suggest that for both biomasses the operating conditions were optimized for a gasification temperature around 900 °C, an oxygen to nitrogen ratio of 0.08 and a reaction time of 30 min, because a gas richer in hydrogen and carbon monoxide and poorer in carbon dioxide and hydrocarbons. The results showed that the product gas of corn DDGS gasification has higher H₂ and CO concentrations (11 and 56.5%) than that of wheat DDGS gasification (10.5 and 51.5%). In addition gasification of corn DDGS resulted to higher gas yield (0.42 m³/kg), LHV (10.65 MJ/m³) and carbon conversion efficiency (44.2%).     

OCM in a fixed-bed reactor: limits and perspectives

The oxidative coupling of methane (OCM) over a La₂O₃/CaO catalyst was studied in a poly tropic fixed-bed reactor (I.D. = 15 mm, W/F= 0.15 g · s/ml). Reaction conditions for stable operation were determined. (1) A minimum inlet temperature of 580°C was necessary to initiate the reaction. (2) The maximum hot-spot temperature of 1000°C limited the highest oxygen inlet concentration to 20%. The temperature gradients in the bed amounted to 250 K. The influence of the reaction conditions on the C₂₊ selectivity was investigated by testing the effects of temperature (T_inlet = 580–860°C), oxygen concentration (C_O2 = 5–20%) and particle diameter (d_p = 250–350 μm, and pellets of h_p = 4 mm and d_p = 4 mm). The C₂₊ selectivity ran through a maximum with increasing temperature and decreased with rising inlet oxygen concentration. Mass-transfer limitations, which occurred when applying pellets, resulted in a drop of C₂₊ selectivity. Highest C₂₊ yields amounted to 15.5% (X_CH4 = 31%, S ₂₊ = 51%). Distributed feed of oxygen was tested as a means to cope with the high temperature gradients and to increase C₂₊. selectivity. Upon applying this mode of operation, oxygen concentrations up to 30% could be converted. However, no improvement of C₂₊ selectivity and yield compared to cofeed operation was achieved.     

Experimental investigation of controller-induced bifurcation in a fixed-bed autothermal reactor

“Snap-through” Hopf bifurcations are induced in a laboratory autothermal reactor by the destabilizing effects of a single proportional controller. These unexpected and dramatic phenomena are predicted a priori by a bifurcation analysis of the model equations with the controller gain as the bifurcation parameter. The experimental bifurcation data are used in a parameter estimation study which yields an extremely accurate dynamic model for the nonlinear system.     

Modeling of methanol synthesis in a 3-phase fixed-bed reactor

The authors propose a new reactor concept for Methanol Synthesis from CO + CO₂ + H₂ mixtures : a down-flow, liquid-continuous, fixed-bed reactor operating at high liquid circulating rate. The two reversible reactions for methanol and water production are modeled simultaneously to provide information for reactor sizing and scaling up. A method for derivating expressions to easily calculate the concentration profiles of the five reacting species inside the catalyst pellets is introduced.     

Dynamic modelling of a gas phase catalytic fixed-bed reactor—II: Results from dynamic experiments

The dynamic experiments on the fixed bed reactor consist of periodic changes in inlet conditions as well as start-up and step disturbances. The experimental results are compared with simulations using a simple one dimensional homogeneous model.The model parameters are determined in mutually independent groups. One group is the kinetic parameters which have been estimated in Ref.[1]. Another group is the heat transport parameters found from heat regenerator experiments. The experiments and the estimation method are described in this paper. The results show that the thermal residence time should be augmented 10% in order to account for the combined effect of radial velocity profile, nonadiabaticy and dynamic heat exchange with the reactor insulation. The estimated total heat transport Peclet number is high indicating that no dispersion phenomena apart from those characteristic for a packed bed are present.The agreement between simulations and experiments is fine for all types of experiments.The effect of radial velocity profile has been investigated separately. This involves solution of a model with two spatial dimensions. Through using a double collocation method combined with Runge-Kutta integration of the ordinary differential equations reasonable calculation times have been obtained.     

Experimental investigation of the dynamics of a fixed-bed reactor

The transient behavior of an adiabatic pilot-plant chemical reactor during start-up is studied. The reaction between oxygen and hydrogen over an alumina supported platinum catalyst is used, and it is demonstrated that the adsorption of water has a pronounced effect on the transient behavior of the reactor. The reactor is modeled by three partial differential equations, and excellent agreement is achieved between the observed temperature profiles and the model.     

Investigation of a fixed-bed pilot plant reactor by dynamic experimentation. Part 2. Simulation of reactor behaviour

Data collected with forced uncorrelated sinusoidal changes of the process variables are used to simulate the behaviour of a non-isothermal non-adiabatic pilot plant fixed-bed reactor. The test reaction applied is the hydrogenation of toluene to methylcyclohexane on an industrial nickel catalyst. A pseudo-homogeneous two-dimensional model as well as a one-dimensional model are applied to describe the reactor behaviour. The model parameters are estimated by defining an objective function based upon residuals of the discretized differential equations instead of upon deviation from the observed variables. This procedure leads to a drastic reduction of computer expenditure. Measured and simulated temperature and concentration profiles are compared on the basis of a number of plots and fitting quality criteria. The model parameters estimated from data collected during dynamic runs are comparable to those obtained from a series of stationary experiments (2₃ experimental design). However, with the dynamic experiments the data necessary for modelling can be collected much more efficiently.     

Production of aromatics by catalytic fast pyrolysis of cellulose in a bubbling fluidized bed reactor

Catalytic fast pyrolysis of cellulose was studied at 500°C using a ZSM‐5 catalyst in a bubbling fluidized bed reactor constructed from a 4.92‐cm ID pipe. Inert gas was fed from below through the distributor plate and from above through a vertical feed tube along with cellulose. Flowing 34% of the total fluidization gas through the feed tube led to the optimal mixing of the pyrolysis vapors into the catalyst bed, which experimentally corresponded to 29.5% carbon aromatic yield. Aromatic yield reached a maximum of 31.6% carbon with increasing gas residence time by changing the catalyst bed height. Increasing the hole‐spacing in the distributor plate was shown to have negligible effect on average bubble diameter and hence did not change the product distribution. Aromatic yields of up to 39.5% carbon were obtained when all studied parameters were optimized. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1320–1335, 2014     

Modeling, simulation and control of a methanol synthesis fixed-bed reactor

In this paper, the dynamic behavior and control of the low pressure methanol synthesis fixed bed reactor have been investigated. For simulation purpose, a heterogeneous one-dimensional model has been developed. First, the reactor simulation is carried out under steady-state condition and the effects of several parameters such as shell temperature, feed composition (especially CO₂ concentration) and recycle ratio on the methanol productivity and reactor temperature profile are investigated. Using the steady state model and a trained feedforward neural network that calculates the effectiveness factor, an optimizer which maximizes the reactor yield has been developed. Through the dynamic simulation, the system open loop response has been obtained and the process dynamic is approximated by a simple model. This model is used for the PID controller tuning and the performances of fixed and adaptive PID controllers are compared for load rejection and set point tracking. Finally the proposed optimizer is coupled with a controller for online optimization and hot spot temperature protection.     

Effect of particle size on lignite devolatilization in a fixed-bed reactor

A fixed-bed coal gasification reactor was set up which specifically simulated the devolatilization zone in a gasifier. Samples (100 g) of lignite coal in three size ranges; ?2+1 mm, ?3+2 mm and ?4+3 mm, were devolatilized in the temperature range 350–550 °C with a steam-oxygen mixture, at 1 atm. The effect of these operating variables on tar yield and composition, melting point, viscosity, specific gravity, and molecular weight distribution was determined. A first-order reaction model was fitted to the experimentally observed total loss in weight of the lignite.     

Multiple steady states and transitional regimes in a cylindrical fixed-bed catalytic reactor

Heterogeneous catalytic reactions in a cylindrical axial-flow fixed-bed reactor have been investigated using a two-phase mathematical model. Regions of multiple steady states have been mapped for basic process parameters, namely, the flow velocity and coolant temperature. Transitions from one steady state to another and possible pathways of the establishment of various steady states have been examined.     

Dynamic modelling of a gas phase catalytic fixed-bed reactor—I: Experimental apparatus and determination of reaction kinetics

A large scale fixed bed pilot reactor for performing dynamic experiments is described. The reactor system is especially designed to suppress secondary dispersion effects not characteristic for the packed bed itself.As a model reaction the reaction between oxygen (<1%) and hydrogen on a platinum catalyst supported by alumina has been used.Differential reactor experiments disclosed a hysteresis phenomenon in the catalyst activity. The catalyst is generally more active when going from high to low temperatures than vice versa.A global first order reaction rate expression with Arrhenius temperature dependency fits the fixed-bed reactor profiles well but the static gains badly. However by simultaneous estimation of frequency factor and activation energy in several axial segments a much better approximation to the static gains was obtained. This result indicates that the reaction kinetics is more complicated than first assumed. However for dynamic modelling the exact reaction mechanism is not needed.     

Experimental investigation of the optimal control of a fixed-bed reactor

A computer program is developed for the control of a chemical fixed-bed reactor. The program employs the conventional procedures of Kalman filtering and optimal control in which the reactor is modeled in state-space form through orthogonal collocation in space. The program package is applied successfully to the on-line control of an existing pilot-plant reactor for which a detailed and accurate model is available.     

Flash pyrolysis of wood in a cyclone reactor

This paper reports the first results of an experimental study of the continuous flash pyrolysis of wood sawdust in a cyclone reactor between 893 and 1330 K. The reaction produces low fractions of char (4%) and the gasification yield increases from 0% at about 800 K to 90% at around 1330 K with a constant volume fraction of CO and H₂ (≈73%) and an increasing fraction of light hydrocarbons (up to 50% mass fraction). The heating value of the gas reaches 19 000 kJ m⁻³ STP for the highest temperatures. The wood particles mainly heated by radiation and solid convection react in less than 1 s while the carrier gas (residence time of the order of 0.05 s) seems to be only weakly heated. The 46.2 × 10⁻⁶ m³ cyclone reactor can operate with excellent stability for wood flow rates up to 0.35 kg h⁻¹ at a wall temperature of 1330 K. The cyclone seems to be very efficient for carrying out reactions of the solid → fluids type but more accurate determination of process parameters such as gas and solid residence times and heat transfer efficiencies are required to gain a better understanding of the behaviour of such a high temperature reactor.     

Simulation of hydrocarbons pyrolysis in a fast-mixing reactor

Currently, thermal decomposition of hydrocarbons for the production of basic petrochemicals (ethylene, propyl-ene) is carried out in steam-cracking processes. Aside from the conventional method, under consideration are alternative ways purposed for process intensification. In the context of these activities, the method of high-temperature pyrolysis of hydrocarbons in a heat-carrier flow is studied, which differs from previous ones and is based on the ability of an ultra-short time of feedstock/heat-carrier mixing. This enables to study the pyrolysis process at high temperature (up to 1500 K) at the reactor inlet. A set of model experiments is conducted on the lab scale facility. Liquefied petroleum gas (LPG) and naphtha are used as a feedstock. The detailed data are obtain-ed on temperature and product distributions within a wide range of the residence time. A theoretical model based on the detailed kinetics of the process is developed, too. The effect of governing parameters on the pyrolysis process is analyzed by the results of the simulation and experiments. In particular, the optimal temperature is detected which corresponds to the maximum ethylene yield. Product yields in our experiments are compared with the similar ones in the conventional pyrolysis method. In both cases (LPG and naphtha), ethylene selectivity in the fast-mixing reactor is substantial y higher than in current technology.