Gasification of silicone fluids under external thermal radiation. Part I. Gasification rate and global heat of gasification

Transient gasification rates and fluid temperatures were measured for polydimethylsiloxane fluids ranging in viscosity from 0.65 cS to 60 000 cS in a nitrogen atmosphere at external radiant fluxes from 20 kW/m² to 70 kW/m². A detailed energy balance for each fluid sample was conducted to determine its global heat of vaporization. Two major energy loss corrections were identified and quantified. The absorption of incident radiation by the volatile products from short chain oligomers was measured and found to substantially reduce the incident flux to the sample surface; the energy loss due to re-radiation was determined to be a substantial factor in reducing the net heat flux to the sample for long chain length fluids. Other energy losses, e.g. heat loss to the substrate, were observed but were less significant. The average gasification rate for each fluid increased linearly with increasing external radiant flux. The global heat of gasification increases with an increase in the chain length (molecular weight) for the siloxane oligomers. These agreed well with calculated values. The global heat of gasification for 50 cS fluid is about 1200 kJ/kg and its value remains nearly constant for all higher molecular weight dimethylsiloxanes. Pyrolysis rates for siloxane fluids are very sensitive to trace catalysts. Measurements of the global heat of gasification for ultra-clean polymers resulted in significantly higher values (3000 kJ/kg). The gasification of siloxanes occurs via two modes or combinations thereof: (1) volatilization of molecular species native to the polymer, and (2) volatilization of thermal degradation products. The former process dominates for low molecular weight siloxanes (η<10 cS) and the latter process dominates for high molecular weight siloxanes (η>1000 cS). For the intermediate molecular weight siloxanes, both volatilization and degradation processes occur. © 1998 John Wiley & Sons, Ltd.     

Gasification of pelletized renewable fuel for clean energy production

The main aim of the study was to develop and investigate a small-scale experimental gasification technique for the effective thermal decomposition of pelletized renewable fuels (wood sawdust, wheat straw). The technical solution of the biomass gasifier for gasification of renewable fuels presents a downdraft gasifier with controllable additional heat energy supply to the biomass using the radial propane flame injection into the bottom part of the biomass layer. From the kinetic study of the mass conversion rate of pelletized biomass and variations of the composition of produced gas it is concluded that the process of biomass gasification is strongly influenced by the amount of additional heat energy and air supply into the biomass. The results of experimental measurements of the composition of produced gas have shown that under the conditions of the sub-stoichiometric air supply into the layer of pelletized wood biomass (α < 0.3) increasing additional heat energy supply in a range from 60 kJ up to 130 kJ leads to an enhanced mass loss of pelletized biomass and enhanced formation of volatiles (CO, H₂) in the flaming pyrolysis zone. For the wood biomass the average content of CO in the products can be increased from 73 g/m³ up to 97 g/m³, while the average content of H₂ increases from 4.7 g/m³ up to 6.2 g/m³. Similar variations of the composition of products are observed during the enhanced gasification of the wheat straw. At constant rate of additional heat energy supply and the sub-stoichiometric combustion conditions (α ≈ 0.17 − 0.30), a faster thermal decomposition of the pelletized biomass and larger average amount of the produced volatiles (CO, H₂) can be obtained by increasing the air supply rate from 0.27 to 0.43 g/s, determining the variations of air-to-fuel ratio in a range from 1.3 up to 1.6.     

Industrial-scale fixed-bed coal gasification: modeling,simulation and thermodynamic analysis

We have developed a process model to simulate the behavior of an industrial-scale pressurized Lurgi fixed-bed coal gasifier using Aspen Plus and General Algebraic Modeling System （GAMS）. Reaction characteristics in the fixed-bed gasifier comprising four sequential reaction zones-drying, pyrolysis, combustion and gasification are respectively modeled. A non-linear programming （NLP） model is developed for the pyrolysis zone to estimate the products composition which includes char, coal gases and distillable liquids. A four-stage model with restricted equilibrium temperature is used to study the thermodynamic equilibrium characteristics and calculate the composi-tion of syngas in the combustion and gasification zones. The thermodynamic analysis shows that the exergetic effi-ciency of the fixed-bed gasifier is mainly determined by the oxygen/coal ratio. The exergetic efficiency of the proc-ess will reach an optimum value of 78.3%when the oxygen/coal and steam/coal mass ratios are 0.14 and 0.80, re-spectively.     

基于Aspen Plus的气流床煤气化炉三段平衡模型(英文)

A three stage equilibrium model is developed for coal gasification in the Texaco type coal gasifiers based on Aspen Plus to calculate the composition of product gas, carbon conversion, and gasification temperature. The model is divided into three stages including pyrolysis and combustion stage, char gas reaction stage, and gas phase reaction stage. Part of the water produced in the pyrolysis and combustion stage is assumed to be involved in the second stage to react with the unburned carbon. Carbon conversion is then estimated in the second stage by steam participation ratio expressed as a function of temperature. And the gas product compositions are calculated from gas phase reactions in the third stage. The simulation results are consistent with published experimental data.     

Gasification of wood char and effects of intraparticle transport

Kinetic parameters for gasification of hybrid poplar spp. char have been measured. A differential reactor was used to obtain rate data for catalytic and non-catalytic reactions of small wood char particles (1–2 mm in size) at 100 kPa for temperatures in the range 400–700 °C, steam partial pressures between 45–100 kPa, and space velocities in the range 2.0–7.3 s^?1 During pyrolysis of wood without the addition of either K₂CO₃ or Na₂CO₃, the cellular structure of the wood was preserved. Additionally, this cellular structure remained intact during most of the gasification process. Addition of K₂CO₃ and Na₂CO₃ before pyrolysis caused a degradation of the regular cellular structure and an increase in the rate of gasification of the resulting char. Effectiveness factor calculations were made for particles of various sizes and results indicate that diffusion control of the gasification reaction becomes important for particles larger than 0.5 CM.     

典型气流床煤气化炉气化过程的建模

利用Aspen Plus、基于热力学平衡模型对GSP煤粉气化炉、GE水煤浆气化炉及四喷嘴对置式水煤浆气化炉的气化过程建模。根据煤颗粒热转化的历程,将煤气化过程划分为热解、挥发分燃烧、半焦裂解及气化反应4个阶段,利用David Merrick模型计算热解过程,采用Beath模型校正压力对热解过程的影响,选用化学计量反应器模拟挥发分燃烧反应,编制Fortran程序计算半焦裂解产物收率,最后基于Gibbs自由能最小化方法计算气化反应。结果表明,采用建立的气流床气化过程模型模拟工业气化过程的结果与生产数据基本吻合,对GSP煤粉气化炉、GE水煤浆气化炉及四喷嘴对置式水煤浆气化炉等3种气化炉有效气成分（CO+H₂）体积分数模拟结果的误差均不超过2%,建立模型的可靠性得到验证。     

Effect of Chemical Compositions on Ash Fusibility Characterization of a Jincheng Anthracite during Combustion and Gasification

The ash melting temperature of coal ash has an important effect during the fluidized bed combustion and gasification process, which affects the slagging and deposition characteristics of the boiler. Experiments on the effects of chemical components on the ash fusion behaviors have been completed on the ash fusion temperatures (AFTs) analyzer under typical gasification and combustion atmospheres. Meanwhile, calculations on the variation of minerals in ash with ash composition were conducted using the FactSage software. The results indicated that the AFTs under gasification were a little higher than those under the combustion atmosphere. On increasing the Fe₂O₃, CaO, and Na₂O contents under the combustion and gasification atmospheres, the four temperatures deformation temperature (DT), softening temperature (ST), hemispherical temperature (HT), and flow temperature (FT) decreased dramatically and the generation and transformation of minerals occurred. The iron-containing minerals, such as hercynite and fayalite, formed with increase in the content of Fe₂O₃; the Ca-bearing feldspar minerals, like gehlenite and anorthite, started appearing on increasing the CaO content, and the Na-containing feldspar minerals, like carnegieite, were detected as the Na₂O was increased. These three minerals can form low-temperature eutectics, decreasing the fusion temperature.     

Some process fundamentals of biomass gasification in dual fluidized bed

The dual fluidised bed gasification technology is prospective because it produces high caloric product gas free of N₂ dilution even when air is used to generate the gasification-required endothermic heat via in situ combustion. This study is devoted to providing the necessary process fundamentals for development of a bubbling fluidized bed (BFB) biomass gasifier coupled to a pneumatic transported riser (PTR) char combustor. In a steam-blown fluidized bed of silica sand, gasification of 1.0 g biomass, a kind of dried coffee grounds containing about 10 wt.% water, in batch format clarified first the characteristics of fuel pyrolysis (at 1073 K) under the conditions simulating that prevailing in the gasifier intended to develop. The result shown that via pyrolysis more than 60% of fuel carbon and up to 75% of fuel mass could be converted into product gas, while the simultaneously formed char was about 22% of fuel mass. With all of these data as the known input, a process simulation using the software package ASPEN then revealed that the considered dual bed gasification plant, i.e. a BFB gasifier + a PTR combustor, is able to sustain its independent heat and mass balances to allow cold gas efficiencies higher than 75%, given that the fuel has suitable water contents and the heat carried with the product gas from the gasifier and with the flue gas from the char combustor is efficiently recovered inside the plant. In a dual fluidized bed pilot gasification facility simulating the gasification plant for development, the article finally demonstrated experimentally that the necessary reaction time for fuel, i.e. the explicit residence time of fuel particles inside the BFB gasifier computed according to a plug granular flow assumption, can be lower than 160 s. The results shown that varying the residence time from 160 to 1200 s only slightly increased the gasification efficiency, but the reaction time available in the PTR, say, about 3 s in our case, was too short to assure the finish even of fuel pyrolysis.     

生物质气化与催化剂的研究进展

生物质气化是一种在高温氧化性介质作用下将生物质热分解为可燃性气体的热解技术。为了提高生物质气化过程中气化效率、调整可燃性气体组分的含量和去除焦油,通常需要采用不同气化介质、改变气化条件或添加不同的催化剂。本文重点综述了生物质气化所使用的介质和催化剂种类以及气化条件对气化气组分,主要是H₂和CO的影响规律。最后对未来生物质气化研究进行了展望,提出了几个待研究解决的问题。     

生物质气化与催化剂的研究进展

生物质气化是一种在高温氧化性介质作用下将生物质热分解为可燃性气体的热解技术。为了提高生物质气化过程中气化效率、调整可燃性气体组分的含量和去除焦油,通常需要采用不同气化介质、改变气化条件或添加不同的催化剂。本文重点综述了生物质气化所使用的介质和催化剂种类以及气化条件对气化气组分,主要是H2和CO的影响规律。最后对未来生物质气化研究进行了展望,提出了几个待研究解决的问题。     

葡萄树枝烟气气氛下热解气化特性研究

以葡萄树枝为研究对象,采用热重-傅里叶变换红外光谱（TG-FTIR）联用技术,研究了反应气氛和升温速率对其热解特性的影响。结果表明：在烟气气氛（80% N₂、15% CO₂、5% O₂）下,DTG曲线在80、350和800℃温度附近存在3个明显失重峰,而在氮气气氛下仅存在80和350℃左右2个失重峰;升温速率为30℃/min时,氮气气氛下样品失重率达80%左右,而烟气气氛下达到95%。说明烟气气氛可提高葡萄树枝转化率,促进热解气化反应的进行。升温速率对生物质热解气化过程有双重影响,提高升温速率有利于葡萄树枝挥发分析出,促进热解气化反应进行,但容易引起葡萄树枝炭结焦,进而影响热失重的进程。热解析出产物采用FTIR分析,结果表明：不同热解阶段气体析出产物及析出量差别很大,且不同热解产物的析出特性由葡萄树枝样品内部官能团的重组、断裂引起。360℃时热解析出的气相产物种类最多,主要包括CO、CO₂、H₂O和CH₄等小分子气体,以及醛类、烃类、羧酸类等大分子物质。     

Low temperature gasification using lattice oxygen

Low temperature pyrolysis and gasification has been investigated based on the chemical looping combustion (CLC), where insufficient amount of lattice oxygen was reacted with hydrocarbons. Metal oxides such as nickel oxide, iron oxide and titanium oxide were used as lattice oxygen source and were coated on silica gel or porous aluminum. Single column reactor was used for experiments and 36.1 mmol of polyethylene was dropped to the column whose temperature was ranged from 693 to 1073 K. For the pyrolysis, hydrogen yield was 100% of polyethylene contained hydrogen, while methane, CO and CO₂ were minor products and almost half of the supplied carbon was deposited on the particle surface. On the other hand, for the steam gasification, 2-3 mol of the hydrogen was generated from 1 mol of carbon and almost no carbon deposition was observed. It is found that no wax and heavy tar was observed in the exhaust. Therefore, the lattice oxygen was able to be applied to the low temperature gasification of hydrocarbons.     

Prospects of Using Boron Powders As Fuel. III. Influence of Polymer Binders on the Composition of Condensed Gasification Products of Model Boron-Containing Compositions

Combustion, Explosion, and Shock Waves - The effect of polymer binders on the thermal behavior, combustion, and composition of condensed gasification products of model boron-containing compositions...     

Thermochemical Conversion of Sewage Sludge by TGA-FTIR Analysis: Influence of Mineral Matter Added

Thermal treatments, such as combustion, gasification, and pyrolysis, have been proven to be a convenient alternative to conventional sludge disposal technologies. Today, process development implies scaling up and so improving the reactor's design. In continuously operated reactors, fresh sewage sludge is in contact with solid residues (reacted material rich in mineral matter and char). Mineral matter has been reported to catalyze the thermo-chemical reactions involved but few works focus on this aspect. In this work, sewage sludge residues were added to fresh sewage sludge. Non-isothermal thermo-gravimetric analysis (TGA) coupled with infrared spectrometry (FTIR) showed that added residues reduce the characteristic reaction temperatures during char combustion and gasification (air, air-N₂, and CO₂ atmospheres). However, any considerable influence of residues was observed during pyrolysis experiments (N₂ atmosphere). The analysis of gas produced during those experiments revealed further details about the solid decomposition, showing considerable differences between different atmospheres.     

Model of Vapor—Air Gasification of a Solid Fuel in a Filtration Mode

A two-temperature mathematical model of steady filtration combustion of a solid fuel in open systems is proposed. Air or a mixture of air with water vapors is considered as a gaseous oxidizer. The model takes into account that the heat capacities of the phases depend on temperature and composition and that the reactor length is finite and allows obtaining the composition of gaseous combustion products. Calculated results on gasification of a mixture of carbon with an inert component are presented. It is demonstrated that thermodynamic calculations are important for obtaining the upper estimate of gasification efficiency. Even a sufficiently long reactor becomes “short” in the regime of transient combustion waves, which results in more intense entrainment of heat by combustion products and, as a consequence, in lower efficiency of the process. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 1, pp. 65–72, January–February, 2006.     

丙炔基双酚A醚硼聚合物热解过程的ReaxFF分子动力学模拟

聚合物的热解过程涉及的化学反应较为复杂,难以通过测试表征的手段深入探究其机理。本研究在实验表征的基础上,结合ReaxFF分子动力学(ReaxFF-MD)模拟方法,研究了丙炔基双酚A醚硼聚合物(PB)的热解过程。通过观察升温过程中PB的结构变化,可得到其热解过程中的断键顺序。此外,采用ReaxFF-MD模拟,其研究结果不仅验证了实验中热重-红外光谱联用(TG-FTIR)分析所得的PB热解生成小分子的主要组成为CH₄、H₂O、H₂ 和 CO,并且通过追踪上述小分子的生成过程可得到其主要的生成途径。以上研究结果表明,ReaxFF-MD模拟方法不仅有助于理解PB聚合物的热解机理,直观地反映出其热解产物生成途径,而且对聚合物耐热性能的研究有所借鉴。     

Carbon-negative syngas production: A comprehensive assessment of biomass pyrolysis coupling chemical looping reforming

This article introduces a pyrolysis chemical looping reforming (PCLR) process that produces carbon-negative syngas in autothermal operation. To enhance the system's carbon negativity, a process configuration with oxygen carrier two-stage regeneration is adopted, enabling internal CO₂ utilization. The PCLR process is systematically evaluated and compared to chemical looping gasification and steam gasification processes in the process performance, energy efficiency, and environmental impact using a process model. Results reveal significant improvements over chemical looping gasification, including 69%, 45%, and 4% improvement in syngas yield, energy efficiency, and environmental benefit. Process analysis demonstrates that decoupling volatile reforming from pyrolysis and combustion enhances syngas quality, energy efficiency, and process flexibility. While the two-stage regeneration sacrifices syngas production, it contributes to a 4% increase in carbon negativity and a 15% reduction in carbon emissions. Thus, the PCLR process effectively overcomes the limitations of chemical looping gasification systems and exhibits excellent process intensification performance.     

Verwertung von Klärschlamm

Gasification and pyrolysis of sewage sludges. Gasification and pyrolysis of sewage sludge were examined as alternatives to sewage sludge combustion. For this purpose, experimental gasification and pyrolysis tests were carried out with primary sewage sludge of Emschergenossenschaft. Main objective of these tests was the evaluation of yields and qualitites for products gained via sludge gasification or pyrolysis and an assessment of the environmentally relevant properties of the related residues. Both process alternatives enable the utilization of sewage sludge without any negative impact on the environment. Due to the total use of the organic components out of the sewage sludge in combination with an almost complete utilization resulting from the valuable hydrogen produced, gasification is an attractive alternative compared to the burning of sewage sludge, both from an environmental and an economic point of view. In the case of sewage sludge pyrolysis a portion of the organic components, however, will remain in the pyrolysis residue. Therefore, pyrolysis allows only a minor reduction of the residual product.     

流化床煤燃烧过程不同气氛下的气态氮释放特征

利用微型流化床反应装置,结合快速过程质谱仪,在850~940℃操作温度下,研究了三种不同粒度分布烟煤和无烟煤在热解、气化和燃烧反应条件下四种主要气态氮产物HCN、NH₃、NO和NO₂的释放规律。结果表明,微型流化床可以实时检测挥发分氮和焦炭氮的动态释放序和类型,热解、气化和燃烧反应气氛的改变主要影响HCN和NH₃的释放量。热解产物的气态氮主要是来自于挥发分,燃烧反应的HCN和NH₃的释放量与温度有明显关系,而气化反应的各类气态氮释放量随温度变化波动不大。煤颗粒尺寸和温度变化对烟煤和无烟煤中各类气态氮释放量产生影响比较复杂,其中NH₃的释放特性是区分挥发分N释放和半焦N释放的重要特征。     

High Ash Char Gasification in Thermo-Gravimetric Analyzer and Prediction of Gasification Performance Parameters Using Computational Intelligence Formalisms

The coal gasification is a cleaner and more efficient process than the coal combustion. Although high ash coals are commonly utilized in the energy generation, systematic gasification kinetic studies using chars derived from these coals are scarce. Accordingly, this paper reports the development of the data-driven models for the gasification of chars derived from the high ash coals. Specifically, the models predict two important gasification performance parameters, viz. gasification rate constant and reactivity index. These models have been constructed using three computational intelligence (CI) methods, namely genetic programming (GP), multilayer perceptron (MLP) neural network (NN), and support vector regression (SVR). The inputs to the CI-based models consist of seven parameters representing the gasification reaction conditions and properties of high ash coals and chars. The data used in the modeling were collected by performing extensive gasification experiments in the CO₂ atmosphere in a thermo-gravimetric analyzer (TGA) using char samples derived from the Indian coals containing high ash content. Values of the two gasification performance parameters were obtained by fitting the experimental data to the shrinking unreacted core (SUC) model. It has been observed that all the CI-based models possess an excellent prediction accuracy and generalization capability. Accordingly, these models can be gainfully employed in the design and operation of the fixed and fluidized bed gasifiers using high ash coals.