Chemical-looping gasification of biomass in a 10 kW_(th) interconnected fluidized bed reactor using Fe_2O_3/Al_2O_3 oxygen carrier

Abstract:The aim of this research is to design and operate a 10 kW hot chemical-looping gasification(CLG)unit using Fe2O3/Al2O3as an oxygen carrier and saw dust as a fuel.The effect of the operation temperature on gas composition in the air reactor and the fuel reactor,and the carbon conversion of biomass to CO2and CO in the fuel reactor have been experimentally studied.A total60 h run has been obtained with the same batch of oxygen carrier of iron oxide supported with alumina.The results show that CO and H2concentrations are increased with increasing temperature in the fuel reactor.It is also found that with increasing fuel reactor temperature,both the amount of residual char in the fuel reactor and CO2concentration of the exit gas from the air reactor are degreased.Carbon conversion rate and gasification efficiency are increased by increasing temperature and H2production at 870℃reaches the highest rate.Scanning electron microscopy(SEM),X-ray diffraction(XRD)and BET-surface area tests have been used to characterize fresh and reacted oxygen carrier particles.The results display that the oxygen carrier activity is not declined and the specific surface area of the oxygen carrier particles is not decreased significantly.     

CFD Simulation of a Hydrogen／Argon Plasma Jet Reactor for Coal Pyrolysis

A Computational Fluid Dynamics (CFD) model was formulated for DC arc hydrogen/argon plasma jet re-actors used in the process of the thermal H2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete da-ta, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-ε equations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.     

Low temperature microwave-assisted vs conventional pyrolysis of various biomass feedstocks

A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste residues.Microwave pyrolysis was found to efficiently deliver comparable evolution of bio-gases in the system as compared with conventional pyrolysis at significantly reduced temperatures(120 180 C vs 250 400 C).The gas obtained from microwave-assisted pyrolysis was found to contain CO 2,CH 4 and CO as major components as well as other related chemicals(e.g.acids,aldehydes,alkanes) which were obtained in different proportions depending on the selected feedstock.     

PLASMA POLYMERIZATION OF ACETYLENE/CO_2/H_2

A study has been made on the plasma polymerization of acetylene/CO_2/H_2 in a capacitively coupled RF plasma. The monomer mixture yielded a crosslinked film with light brown color. A kinetic study is reported for the plasma polymer ization of acetylene/CO_2/H_2. The effects of discharge power level and reactor geometry on the rate of polymer formation are reported. The structure of the plasma polymer is investigated by IR study.     

Vapor—phase Nitration of Benzene to Nitrobenzene over Supported Sulfuric Acid Catalyst

Nitrobenzene is an important chemical intermediate for producing dyestuffs. It is also used as a solvent. The industrial synthesis of nitrobenzene has been carried out in liquid phase with a mixture of nitric acid and concentrated sulfuric acid. This conventional nitration process still has some unsolved problems such as treatment of waste sulfuric acid and disposal of wastewater. The vapor-phase nitration of benzene to prepare nitrobenzene over the solid acidic catalysts in diluted nitric…     

Preparation of cassava starch-based superabsorbent polymer using a twin-roll mixer as reactor

Cassava starch-based superabsorbent polymer was successfully synthesized using a new technology that based on modification of a Haake twin-roll mixer as reactor. The cassava starch was first gelatinized then modified by grafting under external shear stress in the reactor. The torque and temperature curves as a function of time can reflect the variations in the reactor and also offer some information about the copolymerization reaction. The advantages of this system include starch modification can be carried out(1) with high starch concentration,(2) under controlled time and(3) smaller amount of sample(60 g) required. The technology provides useful guides for reactive extrusion. The starch grafted composites were characterized by Fourier transform infrared spectroscopy(FTIR), nuclear magnetic resonance(NMR) and thermal gravimetric analysis(TGA). The TGA was also used for determining the percentage of grafting ratio. The results show that the cassava starch has been successfully grafted with acrylamide then crosslinked by N,N′-methylene-bisacrylamide using this reactor. The ultimate water absorbent capacity of the cassava-based superabsorbent polymer impacted by various pH values illustrated that the acid and basic solutions inhibit the ability of imbibing water. Additionally, gel properties of the cassava-based superabsorbent polymer were investigated. It can be concluded that the structure of cassava gel is stable, while the three dimensional network of cassava-based superabsorbent polymer is rigid but its structure could not resist external force effectively and everlastingly since G′ was decreased with increasing amplitude.     

The role of NiFe2O4 nanoparticle in the anaerobic digestion（AD） of waste activated sludge（WAS）

Anaerobic digestion（AD） is a promising technology for the treatment of waste activated sludge（WAS）with energy recovery. However, the low methane yield and slow methanogenesis limit its broad application. In this study, the NiFe₂O₄ nanoparticles（NPs） were fabricated and applied as a conductive material to enhance the AD via promoting the direct interspecies electron transfer（DIET）. The crystal structure,specific surface area, morphology and elemental composition of the as-pr...     

DEACTIVATION OF P_2O_5-MgO/RE_2O_3 CATALYST FOR OXIDATIVE COUPLING OF METHANE

Techniques including TPD,XPS,XRD and spectrophotometry have been applied to theinvestigation of the deactivation of a highly active P_2O_5-MgO/RE_2O_2 catalyst during a 100-h test.The results of the studies have shown that there is little difference in various properties between thefresh and the deactivated catalyst except for the surface acid-base property which is demonstrated to becontrolled by the presence of phosphorus on the catalyst surface.The deactivation of the catalyst ismainly due to the heavy loss of phosphorus on the surface that causes an increase of the surface basiccenters and a decrease of the surface acid centers,and the coordination between the acid and basiccenters is considerably weakened with a subsequence of the drop of the C_2 selectivity.     

Studies on the Adsorption of Asymmetrical Triblock Copolymers by Scheutjens-Fleer Theory and Monte Carlo Simulation

The adsorption of asymmetrical triblock copolymers from a non-selective solvent on solid surface has been studied by using Scheutjens-Fleer mean-field theory and Monte Carlo simulation method on lattice model. The main aim of this paper is to provide detailed computer simulation data, taking A8-kB20Ak as a key example, to study the influence of the structure of copolymer on adsorption behavior and make a comparison between MC and SF results. The simulated results show that the size distribution of various configurations and density-profile are dependent on molecular structure and adsorption energy. The molecular structure will lead to diversity of adsorption behavior. This discrepancy between different structures would be enlarged for the surface coverage and adsorption amount with increasing of the adsorption energy. The surface coverage and the adsorption amount as well as the bound fraction will become larger as symmetry of the molecular structure becomes gradually worse. The adsorption layer becomes thicker with increasing of symmetry of the molecule when adsorption energy is smaller but it becomes thinner when adsorption energy is higher. It is shown that SF theory can reproduce the adsorption behavior of asymmetrical triblock copolymers. However, systematic discrepancy between the theory and simulation still exists.The approximations inherited in the mean-filed theory such as random mixing and the allowance of direct back folding may be responsible for those deviations.     

LAMINATION OF POLYMER FILMS BY BULK SURFACE PHOTOGRAFTING PROCESS AND PROPERTIES

A new process for lamination of polymer films by "bulk surface photografting" has been developed. The chemicalcomponent of the invention is that the curing of reactive solution between two substrates is initiated by the surface freeradicals produced by aromatic ketones and surface-hydrogen of substrates. Using the new approach, two or more polymerfilms are bonded together by a grafted polymer network which is grafted to adjacent substrate surfaces. The technique hasbeen applied to film substrates of different polymers such as polyolefins, polyesters. and polyamides which have abstractablehydrogens at the surface. The photolaminated film composites containing carrier films and an intermediate functional film of low permeability give strong laminates with high barrier properties, e.g. for oxygen and air.     

Pyrolysis of used automobile tires and residual char utilization

In the present study the rubber portion of used car tires was transformed by atmospheric pyrolysis into oil, gas and char. The experiments have been performed in a captive sample reactor at atmospheric pressure, under helium atmosphere. The effect of temperature on the products yield was investigated. In a second step, alternative uses of pyrolysis char such as combustion, gasification and active carbons preparation were examined, in order to produce fuels and high added value materials. First, pyrolysis char was burned and its reactivity was measured in function with pyrolysis temperature. Second, char was gasified with Steam and CO₂ to produce fuel gases, in a tubular stainless steel reactor. It was also activated to produce high added value materials. It was shown that tire chars present higher reactivity with steam than with CO₂ and also active carbons produced from tire chars possess surface areas, comparable with those of commercially available active carbons.     

循环流化床内废轮胎的热解油化

介绍了以循环流化床反应器为主体的废轮胎热解油化装置,实验过程,实验结果及分析。通过评价热解条件对气体成分及油、碳和气产物产率的影响,以及热解油品的成分分析,得出如下结论：（１）较高的温度和较好的停贸时间会生成过多的不凝气（主要成分为ＣＨ４、Ｈ２,Ｃ２ＨＶ和ＣＯ等）,降低油的产率,过低的温度和加热速率导致严重的碳化,同样会降低油产率。（２）热解油品的组成成分非常复杂,芳烃占了很大比例,其次是烷烃和非     

An experimental investigation into the gasification reactivity and structure of agricultural waste chars

The gasification reactivity as well as physical and chemical structure of chars generated from two kinds of agricultural waste (i.e. corn straw and wheat straw) were studied to better understand the role of lower pyrolysis temperatures and lower heating rates on the gasification characteristics of agricultural waste chars. Char samples were generated in a one-stage quartz fixed-bed reactor. The carbon dioxide (CO₂) gasification reactivity of chars was measured by thermogravimetric (TGA) analysis. Scanning electron microscopy (SEM) analysis, surface area (BET) analysis, Fourier transform infrared spectroscopy (FTIR) analysis and X-ray diffractometry (XRD) analysis were employed to determine the effect of operating conditions on the char structure. Char gasification reactivities decreased with increasing pyrolysis temperatures. The char particles generated under high pyrolysis temperatures had many smaller pores with thinner cell walls, larger surface areas, and some melting. Results indicated that many functional groups’ bands decreased and even disappeared with an increasing pyrolysis temperature. The chars’ microcrystalline became larger at high pyrolysis temperatures. The reactivity of wheat straw char is higher than corn straw char. The difference in the gasification reactivity of agricultural waste chars generated at different pyrolysis temperatures correlated well with the effect of pyrolysis temperatures on the agricultural waste char structure.     

Sulphur distribution in the products of waste tire pyrolysis

The aim of the presented work was to investigate the distribution of sulphur in tire pyrolysis products as well as the influence of process parameters (temperature and residence time) on sulphur distribution due to environmental concerns. Among modern methods used for waste tire recycling, pyrolysis is one of the most reasonable alternatives meeting current environmental standards. However, waste tire sulphur content can be a potential drawback for pyrolysis products utilisation as fuels. Sulphur is present in tires in different concentrations, depending on the type and age of the tires. Typical sulphur content in tires is about 1.6 mass %. In this paper, the distribution of sulphur in tire pyrolysis products was investigated. Tire pyrolysis yields three different products: liquid, gaseous, and solid residue composed mostly of carbon black (chars). Temperature and residence time are the two most important parameters affecting the yield and composition of the volatile fraction and they are therefore expected to affect the sulphur content in residues. Pyrolysis experiments were carried out in a laboratory pyrolysis reaction unit in the temperature range of 650°C to 750°C at different residence times: 88.6 s, 80.2 s, and 73.9 s. Liquid and solid products were analysed by elemental analysis and the distribution of total sulphur in tire pyrolysis products was calculated.     

Recycling of carbon fibre reinforced polymeric waste for the production of activated carbon fibres

Composite waste composed of carbon fibres and polybenzoxazines resin has been pyrolysed in a fixed bed reactor at temperatures of 350, 400, 450, 500 and 700 °C. Solid residues of between 70 and 83.6 wt%, liquid yields 14 and 24.6 wt% and gas yields 0.7 and 3.8 wt% were obtained depending on pyrolysis temperature. The derived pyrolysis liquids contained aniline in high concentration together with oxygenated and nitrogenated aromatic compounds. The pyrolysis gases consisted mainly of CO₂, CO, CH₄, H₂ and other hydrocarbons. The carbon fibres used in the composite waste were separated from the char of the solid residue via oxidation of the char at two different temperatures and investigated for their mechanical strength properties. The carbon fibres recovered from the sample pyrolysed at 500 °C and oxidised at 500 °C exhibited mechanical properties which were 90% of that of the original virgin carbon fibres. Steam activation of the recovered carbon fibres was carried out at 850 °C at different times of activation. The effect of activation time on BET surface area, activated carbon fibres yield, porosity and the morphological structure of activated carbon fibres was evaluated. A maximum BET surface area of over 800 m² g⁻¹ was obtained for the activated carbon fibres produced at 850 °C for 5 h of activation. Nitrogen adsorption-desorption isotherms showed that the adsorption capacity increased as the activation time increased up to 5 h of activation and then after that decreased.     

褐煤热解过程中半焦重整催化剂性质的变化

为降低焦油产率,提高褐煤气化效率,采用胜利褐煤热解所得的半焦作为催化剂,在二阶石英反应器中对煤热解的焦油进行原位催化重整,分析和讨论了反应前后半焦催化剂的性质变化。结果表明,反应后半焦质量较反应前普遍有所下降,半焦是一种消耗性催化剂;反应后半焦的比表面积由422 m~2/g降到231.8 m~2/g;Raman分析结果表明,反应后半焦含氧官能团、小环(3-5个缩合芳环)与大环(大于5个缩合芳环)体系之比均有所降低。在半焦-挥发分作用过程中,快速热解制得半焦主要将挥发分裂解为小分子气体,慢速热解制得的半焦则主要使挥发分缩聚结焦脱除。     

废轮胎快速热解实验研究

介绍了废轮快速热解的试验装置和结果。重点考察了反应器温度在５００～１０００℃时,热分解气体产率和组分的变化规律,热分解产物分布以及延长气相停留时间对热分解气体产率和组分的影响。结果表明,热分解速率随温度呈线性变化,热分解温度升高,产气率增加,液体和固体产物减少。１０００℃时气体产率为５００℃的４倍。废轮胎热解气热值较高（２０～３７ＭＪ／Ｎｍ＾３）,在７００～８００℃间达到最大值。７００℃以上延长气     

催化热解废轮胎制衍生油

催化热解废轮胎对于资源利用及环境保护具有重要意义,近年来引起人们关注.在废轮胎胶粉热解反应中加入催化剂,不仅会加速胶粉裂解速率,缩短反应时间,而且可以通过催化剂择形催化改变产物分布,从而提高目的产物衍生油的收率和性能.国内外对废轮胎催化热解已做了大量研究,以期提高衍生油中高附加值单环芳烃的含量,同时降低S, N和Cl含量,虽然已取得较大进展,但衍生油收率较低,大大降低了该技术的可行性.
　　本文采用带搅拌器的1000 mL不锈钢反应器,在常压条件下研究了反应温度和催化剂类型对废轮胎胶粉热解反应及产物衍生油性能的影响,通过元素分析、馏程模拟和色谱-质谱等表征手段检测了衍生油的理化性能.结果表明,在废轮胎胶粉热解反应过程中,随反应温度上升,出油速率先增加后降低.至500 oC时,热解衍生油收率最高达55.65 wt%,所得衍生油呈黑棕色,具有轻质油含量低、S和N含量高、粘度低和流动性好的特点,其轻质芳烃含量低,却含有大量可以转变为芳烃的脂肪烃类.因此,为了提高衍生油中轻质油和轻质芳烃收率,降低S和N含量,尽量维持较高的衍生油收率,在热解反应过程中引入少量ZSM-5, USY,β, SAPO-11和ZSM-22等常见催化剂,利用催化剂独特的孔道结构和酸分布,达到定向催化和转化的目的,提高轻质芳烃含量.同时,为了克服催化剂与胶粉难以接触进行反应的问题,在反应温度升至200 oC时,维持一定时间保证胶粉发生溶胀和液化反应形成液体烃类,使得催化剂不仅能够均匀分散于液体烃中与其接触进行反应,而且有效提高了反应物料与催化剂之间传质传热效率,使得裂解反应在均相中进行,降低因传热不均匀而造成的结焦和过度裂化反应.在催化热解过程中,1.0 wt%催化剂的加入可明显缩短反应时间,在保证衍生油收率基本不变的情况下,获得的衍生油呈黄棕色,轻质油收率较高为70–75 wt%, S和N含量分别降至0.3–0.58wt%和0.78–1.0 wt%.以具有较高酸性和孔径分布的ZSM-5, USY,β和SAPO-11为催化剂时,衍生油中总芳烃含量可达到50 wt%,其中单环芳烃含量高达45 wt%.     

Processing methods,characteristics and adsorption behavior of tire derived carbons: A review

The remarkable increase in the number of vehicles worldwide; and the lack of both technical and economical mechanisms of disposal make waste tires to be a serious source of pollution. One potential recycling process is pyrolysis followed by chemical activation process to produce porous activated carbons.     

聚乙烯类废弃塑料延迟焦化方法制取燃料油的研究

通过对比废弃塑料（PE）和渣油的热重曲线（TG/DTG）,研究了两者的热解特性,论证了利用延迟焦化方法处理聚乙烯类废弃塑料的理论可行性;同时通过模拟延迟焦化实验,针对性地考察了废弃聚乙烯延迟焦化及废弃聚乙烯与渣油共延迟焦化的反应特性,采用模拟蒸馏方法分析了燃料油产物的成分组成,探讨了废弃聚乙烯延迟焦化方法制取燃料油的生产可行性。结果表明,PE的主要热解温区为350℃~480℃,渣油的为250℃~460℃,两者的热解特性有很大的相似性。PE热解的液体产物中汽油和柴油馏分达到62％,蜡油馏分为38％;PE热解的气相产物为小分子的烃类和氢气。PE与渣油共延迟焦化的液体产物中汽油馏分明显比渣油单独焦化的增加。