Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

Downdraft gasification of biomass

The objectives of this research were to investigate the parameters affecting the gasification process within downdraft gasifiers using biomass feedstocks. In addition to investigations with an open-core gasifier, a novel open-topped throated gasifier was designed and used. A sampling system was designed and installed to determine the water, tar and particular content of the raw product gas. This permitted evaluation of the effects of process parameters and reactor design on tar and particular production, although a large variation was found for the particulate measurements due to the capture of large particles. For both gasifiers, the gasification process was studied in order to identify and compare the mechanisms controlling the position and shape of the reaction zones. The stability of the reaction zone was found to be governed by the superficial gas velocity within the reactor. A superficial gas velocity below 0.2 Nms-1 resulted in a rising reaction zone in both gasifiers. Turndown is achieved when the rate of char production by flaming pyrolysis equals the rate of char gasification over a range of throughputs. A turndown ratio of 2:1 was achieved for the hybrid-throated gasifier, compared to 1.3:1 for the open-core. It is hypothesized that pyrolysis is a surface area phenomenon, and that in the hybrid gasifier the pyrolysis front can expand to form a dome-shape. The rate of char gasification is believed to increase as the depth of the gasification zone increases. Vibration of the open-core reactor bed decreased the bed pressure drop, reduced the voidage, aided solids flow and gave a minor improvement in the product gas energy content. Insulation improved the performance of both reactors by reducing heat losses resulting in a reduced air to feed ratio requirement. The hybrid gasifier gave a higher energy conversion efficiency, a higher product gas heating value, and a lower tar content than the open-core gasifier due to efficient gas mixing in a high temperature tar cracking region below the throat and reduced heat losses.

Gasification of rubberwood in a downdraft gasifier

The objectives of this research were to investigate the perforamnce of a rubberwood gasifier and engine with electricity generation and to identify opportunities for the implementation of such a system in Malaysia. The experimental work included the design, fabrication and commissioning of a throated downdraft gasifier in Malaysia. The gasifier was subsequently used to investigate the effect of moisture content, dry wood capacity and particle size of rubberwood on gasifier performance. Additional experiments were also conducted to investigate the influence of two different nozzle numbers and two different throat diameters on tar cracking. A total of 101 runs were completed during the duration of the research. From the experimental data, the average mass balance was found to be 92.65%. The average energy balance over the gasifier to hot raw gas was 98.7%, to cold clean gas was 102.4% and over the complete system was 101.9%. The heat loss from the gasifier was estimated to range from 10-26% of the chemical energy of the feedstock. From the downstream operation, the heat loss was estimated to range from 17-37% of the chemical energy of rubberwood feedstock. The maximum throughput for stable operation was found to be 60-70% of the maximum dry wood capacity. The gasifier was found to have a maximum turndown ratio of 5:1. It is also postulated that the phenomenon of turndown of the gasifier is due to a `bubble theory' occurring at the gasification zone, and this hypothesis is explained. For stable power output, the working range of the engine was found to be 5-33.5 kWe. The thermal efficiency and diesel displacement of the engine was found to be 17-18% and 65-70% respectively. The research also showed that rubberwood gasification in Malaysia is feasible if the price of diesel is above MR35/l and the price of wood is below MR120/tonne.

Gasification of biomass in a downdraft reactor

The objective of this study was to design, construct, commission and operate a laboratory scale gasifier system that could be used to investigate the parameters that influence the gasification process. The gasifier is of the open-core variety and is fabricated from 7.5 cm bore quartz glass tubing. Gas cleaning is by a centrifugal contacting scrubber, with the product gas being flared. The system employs an on-line dedicated gas analysis system, monitoring the levels of H2, CO, CO2 and CH4 in the product gas. The gas composition data, as well as the gas flowrate, temperatures throughout the system and pressure data is recorded using a BBC microcomputer based data-logging system. Ten runs have been performed using the system of which six were predominantly commissioning runs. The main emphasis in the commissioning runs was placed on the gas clean-up, the product gas cleaning and the reactor bed temperature measurement. The reaction was observed to occur in a narrow band, of about 3 to 5 particle diameters thick. Initially the fuel was pyrolysed, with the volatiles produced being combusted and providing the energy to drive the process, and then the char product was gasified by reaction with the pyrolysis gases. Normally, the gasifier is operated with reaction zone supported on a bed of char, although it has been operated for short periods without a char bed. At steady state the depth of char remains constant, but by adjusting the air inlet rate it has been shown that the depth of char can be increased or decreased. It has been shown that increasing the depth of the char bed effects some improvement in the product gas quality.

Fluidized bed gasification of biomass

A fluidized bed process development unit of 0.8 m internal diameter was designed on basis of results obtained from a bench scale laboratory unit. For the scaling up empirical models from the literature were used. The process development unit and peripheral equipment were constructed, assembled and commissioned, and instruments were provided for data acquisition. The fluidization characteristics of the reactor were determined and were compared to the design data. An experimental programme was then carried out and mass and energy balances were made for all the runs. The results showed that the most important independent experimental parameter was the air factor, with an optimum at 0.3. The optimum higher heating value of the gas produced was 6.5 MJ/Nm3, while the thermal efficiency was 70%. Reasonably good agreement was found between the experimental results, theoretical results from a thermodynamic model and data from the literature. It was found that the attainment of steady state was very sensitive to a continuous and constant feedstock flowrate, since the slightest variation in feed flow resulted in fluctuations of the gas quality. On the basis of the results a set of empirical relationships was developed, which constitutes an empirical model for the prediction of the performance of fluidized bed gasifiers. This empirical model was supplemented by a design procedure by which fluidized bed gasifiers can be designed and constructed. The design procedure was then extended to cover feedstock feeding and gas cleaning in a conceptual design of a fluidized bed gasification facility. The conceptual design was finally used to perform an economic evaluation of a proposed gasification facility. The economics of this plant (retrofit application) were favourable.

HTHP syngas cleaning concept of two stage biomass gasification for FT synthesis

The EU intends to increase the fraction of fuels from biogenic energy sources from 2% in 2005 to 8% in 2020. This means a minimum of 30 million TOE/a of fuels from biomass. This makes technical-scale generation of syngas from high-grade biomass, e.g. straw, hay, bark, or paper/cardboard waste, and the production of synthetic fuels by Fischer-Tropsch (FT) synthesis highly attractive. The BTL concept (Biomass to Liquids) of the Karlsruhe Research Center, labeled bioliq, focuses on this challenge by locally concentrating the biomass energy content by fast pyrolysis in a coke/oil slurry followed by slurry conversion to syngas in a central entrained flow gasifier at 1200C and pressures above 4MPa. FT synthesis generates intermediate products for synthetic fuels. To prevent the sensitive catalysts from being poisoned the syngas must be free of tar and particulates. Trace concentrations of H2S, COS, CS2, HCl, NH3, and HCN must be on the order of a few ppb. Moreover, maximum conversion efficiency will be achieved by cleaning the gas above the synthesis conditions. (T>350C, P>4MPa). The concept of an innovative dry HTHP syngas cleaning process is presented. Based on HT particle filtration and suitable sorption and catalysis processes for the relevant contaminants, an overall concept will be derived, which leads to a syngas quality required for FT synthesis in only two combined stages. Results of filtration experiments on a pilot scale are presented. The influence of temperature on the separation and conversion, respectively, of particulates and gaseous contaminants is discussed on the basis of experimental results obtained on a laboratory and pilot scale. Extensive studies of this concept are performed in a scientific network comprising the Karlsruhe Research Center and five universities; funding is provided by the Helmholtz Association of National Research Centers in Germany.

Fixed bed downdraft gasification of paper industry wastes

The two main wastes generated from secondary fibre paper mills are rejects (composed mainly of plastics and fibres) and de-inking sludge, both of which are evolved from the pulping process during paper manufacture. The current practice for the disposal of these wastes is either by land-spreading or land-filling. This work explores the gasification of blends of pre-conditioned rejects and de-inking sludge pellets with mixed wood chips in an Imbert type fixed bed downdraft gasifier with a maximum feeding capacity of 10kg/h. The producer gases evolved would generate combined heat and power (CHP) in an internal combustion engine. The results show that as much as 80wt.% of a brown paper mill's rejects (consisting of 20wt.% mixed plastics and 80wt.% paper fibres) could be successfully gasified in a blend with 20wt.% mixed wood chips. The producer gas composition was 16.24% H, 23.34% CO, 12.71% CO 5.21% CH and 42.49% N (v/v%) with a higher heating value of 7.3MJ/Nm. After the removal of tar and water condensate the producer gas was of sufficient calorific value and flow rate to power a 10kWe gas engine. Some blends using rejects from other mill types were not successful, and the limiting factor was usually the agglomeration of plastics present within the fuel.

Pyrolysis and gasification of biomass and acid hydrolysis residues

This research was carried for an EC supported project that aimed to produce ethyl levulinate as a diesel miscible biofuel from biomass by acid hydrolysis. The objective of this research was to explore thermal conversion technologies to recover further diesel miscible biofuels and/or other valuable products from the remaining solid acid hydrolysis residues (AHR). AHR consists of mainly lignin and humins and contains up to 80% of the original energy in the biomass. Fast pyrolysis and pyrolytic gasification of this low volatile content AHR was unsuccessful. However, successful air gasification of AHR gave a low heating value gas for use in engines for power or heat with the aim of producing all the utility requirements in any commercial implementation of the ethyl levulinate production process. In addition, successful fast pyrolysis of the original biomass gave organic liquid yields of up to 63.9 wt.% (dry feed basis) comparable to results achieved using a standard hardwood. The fast pyrolysis liquid can be used as a fuel or upgraded to biofuels. A novel molybdenum carbide catalyst was tested in fast pyrolysis to explore the potential for upgrading. Although there was no deoxygenation, some bio-oil properties were improved including viscosity, pH and homogeneity through decreasing sugars and increasing furanics and phenolics. AHR gasification was explored in a batch gasifier with a comparison with the original biomass. Refractory and low volatile content AHR gave relatively low gas yields (74.21 wt.%), low tar yields (5.27 wt.%) and high solid yields (20.52 wt.%). Air gasification gave gas heating values of around 5MJ/NM3, which is a typical value, but limitations of the equipment available restricted the extent of process and product analysis. In order to improve robustness of AHR powder for screw feeding into gasifiers, a new densification technique was developed based on mixing powder with bio-oil and curing the mixture at 150°C to polymerise the bio-oil.

Evaluation of options for energy recovery from municipal solid waste in India using the hierarchical analytical network process

In this paper a Hierarchical Analytical Network Process (HANP) model is demonstrated for evaluating alternative technologies for generating electricity from MSW in India. The technological alternatives and evaluation criteria for the HANP study are characterised by reviewing the literature and consulting experts in the field of waste management. Technologies reviewed in the context of India include landfill, anaerobic digestion, incineration, pelletisation and gasification. To investigate the sensitivity of the result, we examine variations in expert opinions and carry out an Analytical Hierarchy Process (AHP) analysis for comparison. We find that anaerobic digestion is the preferred technology for generating electricity from MSW in India. Gasification is indicated as the preferred technology in an AHP model due to the exclusion of criteria dependencies and in an HANP analysis when placing a high priority on net output and retention time. We conclude that HANP successfully provides a structured framework for recommending which technologies to pursue in India, and the adoption of such tools is critical at a time when key investments in infrastructure are being made. Therefore the presented methodology is thought to have a wider potential for investors, policy makers, researchers and plant developers in India and elsewhere. © 2013 Elsevier Ltd. All rights reserved.

Assessing economically viable carbon reductions for the production of ammonia from biomass gasification

Greenhouse gas emissions from fertiliser production are set to increase before stabilising due to the increasing demand to secure sustainable food supplies for a growing global population. However, avoiding the impacts of climate change requires all sectors to decarbonise by a very high level within several decades. Economically viable carbon reductions of substituting natural gas reforming with biomass gasification for ammonia production are assessed using techno-economic and life cycle assessment. Greenhouse gas savings of 65% are achieved for the biomass gasification system and the internal rate of return is 9.8% at base-line biomass feedstock and ammonia prices. Uncertainties in the assumptions have been tested by performing sensitivity analysis, which show, for example with a ±50% change in feedstock price, the rate of return ranges between -0.1% and 18%. It would achieve its target rate of return of 20% at a carbon price of £32/t CO, making it cost competitive compared to using biomass for heat or electricity. However, the ability to remain competitive to investors will depend on the volatility of ammonia prices, whereby a significant decrease would require high carbon prices to compensate. Moreover, since no such project has been constructed previously, there is high technology risk associated with capital investment. With limited incentives for industrial intensive energy users to reduce their greenhouse gas emissions, a sensible policy mechanism could target the support of commercial demonstration plants to help ensure this risk barrier is resolved. © 2013 The Authors.

Modelling and simulation of biomass gasification in a circulating fluidized bed reactor

Computational Fluid Dynamics (CFD) has found great acceptance among the engineering community as a tool for research and design of processes that are practically difficult or expensive to study experimentally. One of these processes is the biomass gasification in a Circulating Fluidized Bed (CFB). Biomass gasification is the thermo-chemical conversion of biomass at a high temperature and a controlled oxygen amount into fuel gas, also sometime referred to as syngas. Circulating fluidized bed is a type of reactor in which it is possible to maintain a stable and continuous circulation of solids in a gas-solid system. The main objectives of this thesis are four folds: (i) Develop a three-dimensional predictive model of biomass gasification in a CFB riser using advanced Computational Fluid Dynamic (CFD) (ii) Experimentally validate the developed hydrodynamic model using conventional and advanced measuring techniques (iii) Study the complex hydrodynamics, heat transfer and reaction kinetics through modelling and simulation (iv) Study the CFB gasifier performance through parametric analysis and identify the optimum operating condition to maximize the product gas quality. Two different and complimentary experimental techniques were used to validate the hydrodynamic model, namely pressure measurement and particle tracking. The pressure measurement is a very common and widely used technique in fluidized bed studies, while, particle tracking using PEPT, which was originally developed for medical imaging, is a relatively new technique in the engineering field. It is relatively expensive and only available at few research centres around the world. This study started with a simple poly-dispersed single solid phase then moved to binary solid phases. The single solid phase was used for primary validations and eliminating unnecessary options and steps in building the hydrodynamic model. Then the outcomes from the primary validations were applied to the secondary validations of the binary mixture to avoid time consuming computations. Studies on binary solid mixture hydrodynamics is rarely reported in the literature. In this study the binary solid mixture was modelled and validated using experimental data from the both techniques mentioned above. Good agreement was achieved with the both techniques. According to the general gasification steps the developed model has been separated into three main gasification stages; drying, devolatilization and tar cracking, and partial combustion and gasification. The drying was modelled as a mass transfer from the solid phase to the gas phase. The devolatilization and tar cracking model consist of two steps; the devolatilization of the biomass which is used as a single reaction to generate the biomass gases from the volatile materials and tar cracking. The latter is also modelled as one reaction to generate gases with fixed mass fractions. The first reaction was classified as a heterogeneous reaction while the second reaction was classified as homogenous reaction. The partial combustion and gasification model consisted of carbon combustion reactions and carbon and gas phase reactions. The partial combustion considered was for C, CO, H2 and CH4. The carbon gasification reactions used in this study is the Boudouard reaction with CO2, the reaction with H2O and Methanation (Methane forming reaction) reaction to generate methane. The other gas phase reactions considered in this study are the water gas shift reaction, which is modelled as a reversible reaction and the methane steam reforming reaction. The developed gasification model was validated using different experimental data from the literature and for a wide range of operating conditions. Good agreement was observed, thus confirming the capability of the model in predicting biomass gasification in a CFB to a great accuracy. The developed model has been successfully used to carry out sensitivity and parametric analysis. The sensitivity analysis included: study of the effect of inclusion of various combustion reaction; and the effect of radiation in the gasification reaction. The developed model was also used to carry out parametric analysis by changing the following gasifier operating conditions: fuel/air ratio; biomass flow rates; sand (heat carrier) temperatures; sand flow rates; sand and biomass particle sizes; gasifying agent (pure air or pure steam); pyrolysis models used; steam/biomass ratio. Finally, based on these parametric and sensitivity analysis a final model was recommended for the simulation of biomass gasification in a CFB riser.

Downdraft gasification of biomass and opportunities in Chile

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Assessing economically viable carbon reductions for the production of ammonia from biomass gasification

Greenhouse gas emissions from fertiliser production are set to increase before stabilising due to the increasing demand to secure sustainable food supplies for a growing global population. However, avoiding the impacts of climate change requires all sectors to decarbonise by a very high level within several decades. Economically viable carbon reductions of substituting natural gas reforming with biomass gasification for ammonia production are assessed using techno-economic and life cycle assessment. Greenhouse gas savings of 65% are achieved for the biomass gasification system and the internal rate of return is 9.8% at base-line biomass feedstock and ammonia prices. Uncertainties in the assumptions have been tested by performing sensitivity analysis, which show, for example with a ±50% change in feedstock price, the rate of return ranges between -0.1% and 18%. It would achieve its target rate of return of 20% at a carbon price of £32/t CO, making it cost competitive compared to using biomass for heat or electricity. However, the ability to remain competitive to investors will depend on the volatility of ammonia prices, whereby a significant decrease would require high carbon prices to compensate. Moreover, since no such project has been constructed previously, there is high technology risk associated with capital investment. With limited incentives for industrial intensive energy users to reduce their greenhouse gas emissions, a sensible policy mechanism could target the support of commercial demonstration plants to help ensure this risk barrier is resolved. © 2013 The Authors.

A techno-economic comparison of power production by biomass fast pyrolysis with gasification and combustion

This paper presents an assessment of the technical and economic performance of thermal processes to generate electricity from a wood chip feedstock by combustion, gasification and fast pyrolysis. The scope of the work begins with the delivery of a wood chip feedstock at a conversion plant and ends with the supply of electricity to the grid, incorporating wood chip preparation, thermal conversion, and electricity generation in dual fuel diesel engines. Net generating capacities of 1–20 MWe are evaluated. The techno-economic assessment is achieved through the development of a suite of models that are combined to give cost and performance data for the integrated system. The models include feed pretreatment, combustion, atmospheric and pressure gasification, fast pyrolysis with pyrolysis liquid storage and transport (an optional step in de-coupled systems) and diesel engine or turbine power generation. The models calculate system efficiencies, capital costs and production costs. An identical methodology is applied in the development of all the models so that all of the results are directly comparable. The electricity production costs have been calculated for 10th plant systems, indicating the costs that are achievable in the medium term after the high initial costs associated with novel technologies have reduced. The costs converge at the larger scale with the mean electricity price paid in the EU by a large consumer, and there is therefore potential for fast pyrolysis and diesel engine systems to sell electricity directly to large consumers or for on-site generation. However, competition will be fierce at all capacities since electricity production costs vary only slightly between the four biomass to electricity systems that are evaluated. Systems de-coupling is one way that the fast pyrolysis and diesel engine system can distinguish itself from the other conversion technologies. Evaluations in this work show that situations requiring several remote generators are much better served by a large fast pyrolysis plant that supplies fuel to de-coupled diesel engines than by constructing an entire close-coupled system at each generating site. Another advantage of de-coupling is that the fast pyrolysis conversion step and the diesel engine generation step can operate independently, with intermediate storage of the fast pyrolysis liquid fuel, increasing overall reliability. Peak load or seasonal power requirements would also benefit from de-coupling since a small fast pyrolysis plant could operate continuously to produce fuel that is stored for use in the engine on demand. Current electricity production costs for a fast pyrolysis and diesel engine system are 0.091/kWh at 1 MWe when learning effects are included. These systems are handicapped by the typical characteristics of a novel technology: high capital cost, high labour, and low reliability. As such the more established combustion and steam cycle produces lower cost electricity under current conditions. The fast pyrolysis and diesel engine system is a low capital cost option but it also suffers from relatively low system efficiency particularly at high capacities. This low efficiency is the result of a low conversion efficiency of feed energy into the pyrolysis liquid, because of the energy in the char by-product. A sensitivity analysis has highlighted the high impact on electricity production costs of the fast pyrolysis liquids yield. The liquids yield should be set realistically during design, and it should be maintained in practice by careful attention to plant operation and feed quality. Another problem is the high power consumption during feedstock grinding. Efficiencies may be enhanced in ablative fast pyrolysis which can tolerate a chipped feedstock. This has yet to be demonstrated at commercial scale. In summary, the fast pyrolysis and diesel engine system has great potential to generate electricity at a profit in the long term, and at a lower cost than any other biomass to electricity system at small scale. This future viability can only be achieved through the construction of early plant that could, in the short term, be more expensive than the combustion alternative. Profitability in the short term can best be achieved by exploiting niches in the market place and specific features of fast pyrolysis. These include: •countries or regions with fiscal incentives for renewable energy such as premium electricity prices or capital grants; •locations with high electricity prices so that electricity can be sold direct to large consumers or generated on-site by companies who wish to reduce their consumption from the grid; •waste disposal opportunities where feedstocks can attract a gate fee rather than incur a cost; •the ability to store fast pyrolysis liquids as a buffer against shutdowns or as a fuel for peak-load generating plant; •de-coupling opportunities where a large, single pyrolysis plant supplies fuel to several small and remote generators; •small-scale combined heat and power opportunities; •sales of the excess char, although a market has yet to be established for this by-product; and •potential co-production of speciality chemicals and fuel for power generation in fast pyrolysis systems.

Novel Ni-Mg-Al-Ca catalyst for enhanced hydrogen production for the pyrolysis-gasification of a biomass/plastic mixture

A Ni-Mg-Al-Ca catalyst was prepared by a co-precipitation method for hydrogen production from polymeric materials. The prepared catalyst was designed for both the steam cracking of hydrocarbons and for the in situ absorption of CO2 via enhancement of the water-gas shift reaction. The influence of Ca content in the catalyst and catalyst calcination temperature in relation to the pyrolysis-gasification of a wood sawdust/polypropylene mixture was investigated. The highest hydrogen yield of 39.6molH2/g Ni with H2/CO ratio of 1.90 was obtained in the presence of the Ca containing catalyst of molar ratio Ni:Mg:Al:Ca=1:1:1:4, calcined at 500°C. In addition, thermogravimetric and morphology analyses of the reacted catalysts revealed that Ca introduction into the Ni-Mg-Al catalyst prevented the deposition of filamentous carbon on the catalyst surface. Furthermore, all metals were well dispersed in the catalyst after the pyrolysis-gasification process with 20-30nm of NiO sized particles observed after the gasification without significant aggregation.