Hydrogen-rich synthesis gas production from waste wood via gasification and reforming technology for fuel cell application

The purpose of this study was to establish a fuel process for an advanced power generation system in which hydrogen-rich synthesis gas, as the fuel for the molten carbonate fuel cell (MCFC), can be extracted from biomass via gasification and reforming technologies. Experiments on waste wood gasification were performed using a bench-scale gasification system. The main factors influencing hydrogen generation in the noncatalytic process and in the catalytic process were investigated, and temperature was identified as the most important factor. At 950°C, without employing a catalyst, hydrogen-rich synthesis gas containing about 54 vol% hydrogen was extracted from feedstock with appropriately designed operation parameters for the steam/carbon ratio and the equivalence ratio. However, by employing a commercial steam reforming catalyst in the reforming process, similar results were obtained at 750°C.     

Energy from Waste – Clean,efficient, renewable: Transitions in combustion efficiency and NOx control

Traditionally EfW (Energy from Waste) plants apply a reciprocating grate to combust waste fuel. An integrated steam generator recovers the heat of combustion and converts it to steam for use in a steam turbine/generator set. This is followed by an array of flue gas cleaning technologies to meet regulatory limitations.Modern combustion applies a two-step method using primary air to fuel the combustion process on the grate. This generates a complex mixture of pyrolysis gases, combustion gases and unused combustion air. The post-combustion step in the first pass of the boiler above the grate is intended to “clean up” this mixture by oxidizing unburned gases with secondary air.This paper describes modifications to the combustion process to minimize exhaust gas volumes and the generation of noxious gases and thus improving the overall thermal efficiency of the EfW plant. The resulting process can be coupled with an innovative SNCR (Selective Non-Catalytic Reduction) technology to form a clean and efficient solid waste combustion system.Measurements immediately above the grate show that gas compositions along the grate vary from 10% CO, 5% H₂ and 0% O₂ to essentially unused “pure” air, in good agreement with results from a mathematical model. Introducing these diverse gas compositions to the post combustion process will overwhelm its ability to process all these gas fractions in an optimal manner. Inserting an intermediate step aimed at homogenizing the mixture above the grate has shown to significantly improve the quality of combustion, allowing for optimized process parameters. These measures also resulted in reduced formation of NO_x (nitrogenous oxides) due to a lower oxygen level at which the combustion process was run (2.6 vol% O_2, wet instead of 6.0 vol% O_2, wet).This reduction establishes optimal conditions for the DyNOR? (Dynamic NO_x Reduction) NO_x reduction process. This innovative SNCR technology is adapted to situations typically encountered in solid fuel combustion. DyNOR? measures temperature in small furnace segments and delivers the reducing reagent to the exact location where it is most effective. The DyNOR? distributor reacts precisely and dynamically to rapid changes in combustion conditions, resulting in very low NO_x emissions from the stack.     

Carbon materials-catalyzed hydroliquefaction of flame-retardant plastics in organic solvents

Flame-retardant plastics, such as desktop and laptop personal computer bodies, could be completely liquefied by carbon materials-catalyzed hydroliquefaction in tetralin without using H₂ as a hydrogen source. Active carbons with larger surface areas (1450–3450 m²/g) acted as superior catalysts in transferring tetralin hydrogens to plastics. On the other hand, carbon blacks and fullerene-rich soot were less active catalysts. Graphite and mesocarbon microbeads did not show any catalytic effects. Benzene, toluene, and ethylbenzene were obtained as recyclable hydrocarbons; their total amounts varied from 4 wt% to 12 wt% depending on the types of plastics and the carbon materials used. Organic bromides such as polybromodioxins were not contained in the gases and oils of the product. Received: July 19, 2000 / Accepted: September 17, 2000     

Characterization of products obtained from pyrolysis and steam gasification of wood waste,RDF, and RPF

Pyrolysis and steam gasification of woody biomass chip (WBC) obtained from construction and demolition wastes, refuse-derived fuel (RDF), and refuse paper and plastic fuel (RPF) were performed at various temperatures using a lab-scale instrument. The gas, liquid, and solid products were examined to determine their generation amounts, properties, and the carbon balance between raw material and products.The amount of product gas and its hydrogen concentration showed a considerable difference depending on pyrolysis and steam gasification at higher temperature. The reaction of steam and solid product, char, contributed to an increase in gas amount and hydrogen concentration. The amount of liquid products generated greatly depended on temperature rather than pyrolysis or steam gasification. The compositions of liquid product varied relying on raw materials used at 500 °C but the polycyclic aromatic hydrocarbons became the major compounds at 900 °C irrespective of the raw materials used. Almost fixed carbon (FC) of raw materials remained as solid products under pyrolysis condition whereas FC started to decompose at 700 °C under steam gasification condition.For WBC, both char utilization by pyrolysis at low temperature (500 °C) and syngas recovery by steam gasification at higher temperature (900 °C) might be practical options. From the results of carbon balance of RDF and RPF, it was confirmed that the carbon conversion to liquid products conspicuously increased as the amount of plastic increased in the raw material. To recover feedstock from RPF, pyrolysis for oil recovery at low temperature (500 °C) might be one of viable options. Steam gasification at 900 °C could be an option but the method of tar reforming (e.g. catalyst utilization) should be considered.     

Carbon dioxide utilization with carbonation using industrial waste-desulfurization gypsum and waste concrete

In this study, we propose a process making calcium carbonate and calcium sulfate and recovering absorbent using ammonia absorbent, carbon dioxide, and industrial waste. The main objective of this study is to confirm the possibility of carbon capture and utilization based on waste materials. We assumed desulfurization gypsum and construction waste (ready mixed concrete washing water, waste concrete, etc.) are CaSO₄, Ca(OH)₂, respectively. And concentration of simulated carbon dioxide gas was 15 vol% similar to flue gas. Calcium carbonate was produced by combination reaction between ionic CO₂ in absorbent and metal ion in the solid waste. Experiments were conducted at normal temperature and pressure. Furthermore, the generated products were characterized by X-ray diffraction, and scanning electron microscope.     

Pyrolysis and dehalogenation of plastics from waste electrical and electronic equipment (WEEE): A review

Plastics from waste electrical and electronic equipment (WEEE) have been an important environmental problem because these plastics commonly contain toxic halogenated flame retardants which may cause serious environmental pollution, especially the formation of carcinogenic substances polybrominated dibenzo dioxins/furans (PBDD/Fs), during treat process of these plastics. Pyrolysis has been proposed as a viable processing route for recycling the organic compounds in WEEE plastics into fuels and chemical feedstock. However, dehalogenation procedures are also necessary during treat process, because the oils collected in single pyrolysis process may contain numerous halogenated organic compounds, which would detrimentally impact the reuse of these pyrolysis oils. Currently, dehalogenation has become a significant topic in recycling of WEEE plastics by pyrolysis. In order to fulfill the better resource utilization of the WEEE plastics, the compositions, characteristics and dehalogenation methods during the pyrolysis recycling process of WEEE plastics were reviewed in this paper. Dehalogenation and the decomposition or pyrolysis of WEEE plastics can be carried out simultaneously or successively. It could be ‘dehalogenating prior to pyrolysing plastics’, ‘performing dehalogenation and pyrolysis at the same time’ or ‘pyrolysing plastics first then upgrading pyrolysis oils’. The first strategy essentially is the two-stage pyrolysis with the release of halogen hydrides at low pyrolysis temperature region which is separate from the decomposition of polymer matrixes, thus obtaining halogenated free oil products. The second strategy is the most common method. Zeolite or other type of catalyst can be used in the pyrolysis process for removing organohalogens. The third strategy separate pyrolysis and dehalogenation of WEEE plastics, which can, to some degree, avoid the problem of oil value decline due to the use of catalyst, but obviously, this strategy may increase the cost of whole recycling process.     

Biomass Carbon Ratio of Polymer Composites Measured by Accelerator Mass Spectrometry

The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO₃) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO₃ powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO₃, are omitted. Biomass carbon ratio was evaluated by ratio of ¹⁴C to ¹²C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO₃ content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.     

Thermal cracking of oils from waste plastics

Thermal cracking of decomposed waste plastic oil produces a good yield of olefins. The solvent extraction of such waste plastic oil seems to be efficient for increasing gas yields and recycling monomers. To assess the potential of monomer recovery from municipal waste plastics, the oils were cracked using a laboratory-scale quartz-tube reactor. The waste plastic oils were provided by two commercial plants of the Sapporo Plastic Recycle Co. and the Dohoh Recycle Center Co. in Japan. A model waste plastic oil made in a laboratory was also examined. Yields of ethene, propene, and other products were measured at different temperatures. Two-step pyrolysis reduces coking compared with the direct thermal degradation of plastics. The raffinates from waste plastic oils extracted by sulfolane were also cracked. The primary products were almost the same as those from nontreated oils. The maximum total gas yield was 78wt%–85wt% at 750°C, an increase of about 20wt% compared with that of nonextracted oil. Solvent extraction removes stable aromatic hydrocarbons such as styrene, which is more coked than cracked.     

Synthesis and Properties of Polyesters from Waste Grapeseed Oil: Comparison with Soybean and Rapeseed Oils

The aim of this study was to investigate the application of grapeseed oil, a waste product from the wine industry, as a renewable feedstock to make polyesters and to compare the properties of these materials with those derived from soybean and rapeseed oils. All three oils were epoxidized to give renewable epoxy monomers containing between 3.8 and 4.7 epoxides per molecule. Polymerisation was achieved with cyclic anhydrides catalysed by 4-methyl imidazole at 170 and 210 °C. Polymers produced from methyl tetrahydrophthalic anhydride (Aradur917^®) had greater tensile strength and Young’s Modulus (tensile strength = 12.8 MPa, Young’s Modulus = 1005 MPa for grapeseed) than methyl nadic anhydride (MNA) derived materials (5.6 and 468 MPa for grapeseed) due to increased volume of MNA decreasing crosslink density. Soybean and grapeseed oils produced materials with higher tensile strength (5.6–29.3 MPa) than rapeseed derived polyesters (2.5–3.9 MPa) due to a higher epoxide functionality increasing crosslinking. T _g’s of the polyesters ranged from ?36 to 62 °C and mirrored the trend in epoxide functionality with grapeseed producing higher T _g polymers (?17 to 17 °C) than soybean (?25 to 6 °C) and rapeseed (?36 to ?27 °C). Grapeseed oil showed similar properties to soybean oil in terms of T _g, thermal degradation and Young’s Modulus but produced polymers of lower tensile strength. Therefore grapeseed oil would only be a viable substitute for soybean for low stress applications or where thermal properties are more important.     

Influence of mixed molten carbonate composition on hydrogen formation by steam gasification

Steam gasification in the presence of carbonate compounds is an effective method to recover useful materials from electronic waste streams by converting plastics into gaseous products that can be used for energy production and avoiding the expensive manual disassembly process. We investigated steam gasification of activated carbon in the presence of various mixtures of lithium carbonate, sodium carbonate, and potassium carbonate. The activated carbon was almost completely converted into hydrogen and carbon dioxide at 700°C under 0.1 MPa pressure in the presence of carbonate mixtures. Carbon dioxide was also derived from partial decomposition of lithium carbonate. Steam gasification was accelerated in the presence of various carbonate mixtures and at increasing steam partial pressures. These experimental results show that fluidity of carbonates, the potassium content of the carbonate, and the steam partial pressure are important factors in accelerating steam gasification.     

Study on the conversion of waste plastics/petroleum resid mixtures to transportation fuels

Catalytic coprocessing of model and waste plastics with light Arabian crude oil residue was investigated using NiMo/Al₂O₃, ZSM-5, FCC, and hydrocracking catalysts. Reaction systems that were studied included low density polyethylene (LDPE), high density polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plastic/catalyst) and binary (plastic/resid/catalyst) reactions were carried out in a 25-cm³ micro autoclave reactor under different conditions of weight and type of catalyst, duration, pressure, and temperature. The optimum conditions selected for our work were: 1% catalyst by weight of total feedstock weight, 60min reaction time, 8.3Mpa of H₂, and 430°C. The product distribution for the binary system using plastic and petroleum residue provided some encouraging results. High yields of liquid fuels in the boiling range of 100°–480°C and gases were obtained along with a small amount of heavy oils and insoluble material such as gums and coke. In general, this study helps to demonstrate the technical feasibility of upgrading both waste plastics and petroleum resid, as well as an alternative approach to feedstock recycling.     

Catalytic pyrolysis of car tire waste using expanded perlite

In this study, the non-catalytic and catalytic pyrolysis experiments were conducted on the sample of tire waste using expanded perlite as an additive material to determine especially the effect of temperature and catalyst-to-tire ratio on the products yields and the compositions and qualities of pyrolytic oils (NCPO and CPO). Non-catalytic studies, which were carried out under the certain conditions (a nitrogen flow of 100 mL/min and a heating rate of 10 °C/min), showed that the highest yield of pyrolytic oil (NCPO) was 60.02 wt.% at 425 °C. Then, the catalytic pyrolysis studies were carried out at catalyst-to-tire ratio range of 0.05-0.25 and the highest catalytic pyrolytic oil (CPO) yield was 65.11 wt.% at the ratio of 0.10 with the yield increase of 8.48 wt.% compared with the non-catalytic pyrolysis. Lastly, the pyrolytic oils were characterized with applying a various techniques such as elemental analyses and various chromatographic and spectroscopic techniques (GC-MS, ¹H NMR, FT-IR, etc.). The characterization results revealed that the pyrolytic oils which were complex mixtures of C₅-C₁₅ organic compounds (predominantly aromatic compounds) and also the CPO compared to the NCPO was more similar to conventional fuels in view of the certain fuel properties.     

The important role of microwave receptors in bio-fuel production by microwave-induced pyrolysis of sewage sludge

Microwave receptor plays an important role in the microwave pyrolysis of sewage sludge in view of its significant influence on the yield and property of bio-fuel products. The yield and the chemical compositions of bio-fuels (gases and oils) obtained from sewage sludge mixed with different receptors (graphite, residue char, active carbon or silicon carbide) were investigated in this study by Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), and Fourier Transform Infrared Spectroscopy (FTIR). The results showed that the use of silicon carbide gave rise to the highest final temperature of 1130 °C, resulting in the highest yield of gas fraction (up to 63.2 wt.%). The low heating rate (200 °C/min) which was attributed to the addition of residue char promoted condensation reactions and resulted in an increase in solid yield. The existence of active carbon could prolong the resistance time of volatiles in the hot zone owing to its porous structure, generating the maximum concentration of H₂ + CO (60%) in the pyrolysis gas. When graphite was used, the final low temperature favoured the cyclization of the alkenes, giving rise to a higher concentration of mononuclear aromatics in the pyrolysis oils. The model established in this study revealed that the quantity and quality of the products obtained from the microwave pyrolysis highly depended on the process conditions, which were influenced by the receptor significantly.     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

Novel Polymeric Materials from Biological Oils

A variety of novel polymeric materials ranging from elastomers to tough, rigid plastics have been prepared by the cationic copolymerization of regular soybean oil, low-saturation soybean oil, or conjugated low-saturation soybean oil with various alkene commonomers. Using appropriate compositions and reaction conditions, 70–100% of the soybean oil is covalently incorporated into the cross-linked polymer networks, contributing significantly to cross-linking during copolymerization. The resulting thermosets exhibit thermophysical and mechanical properties that are competitive with those of their petroleum-based counterparts. In addition, good damping and shape memory properties have been obtained by controlling the degree of cross-linking and the rigidity of the polymer backbone. New materials with similar characteristics have also been produced from other biological oils, including tung, and fish oils using the same technique. The new, more valuable properties of these bioplastics suggest numerous promising applications of these novel polymeric materials.     

Characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil

An attempted has been made to recover high-calorific fuel gas and useful carbonaceous residue by the electric arc pyrolysis of waste lubricating oil. The characteristics of gas and residues produced from electric arc pyrolysis of waste lubricating oil were investigated in this study. The produced gas was mainly composed of hydrogen (35–40%), acetylene (13–20%), ethylene (3–4%) and other hydrocarbons, whereas the concentration of CO was very low. Calorific values of gas ranged from 11,000 to 13,000 kcal kg^?1 and the concentrations of toxic gases, such as NO_x, HCl and HF, were below the regulatory emissions limit. Gas chromatography–mass spectrometry (GC/MS) analysis of liquid-phase residues showed that high molecular-weight hydrocarbons in waste lubricating oil were pyrolyzed into low molecular-weight hydrocarbons and hydrogen. Dehydrogenation was found to be the main pyrolysis mechanism due to the high reaction temperature induced by electric arc. The average particle size of soot as carbonaceous residue was about 10 μm. The carbon content and heavy metals in soot were above 60% and below 0.01 ppm, respectively. The utilization of soot as industrial material resources such as carbon black seems to be feasible after refining and grinding.     

Gasification of the char derived from distillation of granulated scrap tyres

This work reports the effect of pressure on the steam/oxygen gasification at 1000 °C of the char derived from low temperature-pressure distillation of granulated scrap tyres (GST). The study was based on the analysis of gas production, carbon conversion, cold gas efficiency and the high heating value (HHV) of the product. For comparison, similar analyses were carried out for the gasification of coals with different rank.In spite of the relatively high ash (≈12 wt.%) and sulphur (≈3 wt.%) contents, the char produced in GST distillation can be regarded as a reasonable solid fuel with a calorific value of 34 MJ kg⁻¹. The combustion properties of the char (E_A ≈ 50 kJ mol⁻¹), its temperature of self-heating (≈264 °C), ignition temperature (≈459 °C) and burn-out temperature (≈676 °C) were found to be similar to those of a semi-anthracite.It is observed that the yield, H₂ and CO contents and HHV of the syngas produced from char gasification increase with pressure. At 0.1 MPa, 4.6 Nm³ kg_char⁻¹ of syngas was produced, containing 28% v/v of H₂ and CO and with a HHV around 3.7 MJ Nm⁻³. At 1.5 MPa, the syngas yield achieved 4.9 Nm³ kg_char⁻¹ with 30% v/v of H₂-CO and HHV of 4.1 MJ Nm⁻³. Carbon conversion significantly increased from 87% at 0.1 MPa to 98% at 1.5 MPa.It is shown that the char derived from distillation of granulated scrap tyres can be further gasified to render a gas of considerable heating value, especially when gasification proceeds at high pressure.     

Decomposition of mixed plastics consisting of polypropylene and polyethylene terephthalate into oils over titania/silica catalysts

The catalytic decomposition of mixed plastics consisting of polypropylene (PP) and polyethylene terephthalate (PET) has been investigated over titania/silica catalysts at 698 K. The yield of oil produced was about 70%, and the large amounts of C₁₈₊ hydrocarbons this contained was from the aromatics in PET. Gas was also produced, including C₃–C₅ hydrocarbons. The carbon-number fractions in the oil was influenced by the PET/(PP + PET) ratios and the catalyst weight. The titania/silica catalysts could be used repeatedly, and after they had been fouled, could be regenerated. From the Fourier Transform Infrared (FT–IR) spectroscopic data of adsorbed pyridine on the catalyst surface, most of the acid sites of the titania/silica catalysts were found to be Lewis sites where the hydride abstracted from PP pyrolysates react with PET pyrolysates to form oil and gas. Received: July 19, 2000 / Accepted: October 20, 2000     

Effect of heating rate on the pyrolysis of high-impact polystyrene containing brominated flame retardants: fate of brominated flame retardants

In the case of plastics containing brominated flame retardants, various brominated organic compounds, including polybrominated dibenzodioxins and dibenzofurans, are yielded when they are degraded. In order to reduce the hazard that might be generated during after-live treatment, the behaviour of flame retarded high-impact polystyrene containing decabromo diphenylether and antimony oxide (Sb₂O₃), was investigated using several heating programs. It was found that the separation of the thermal process into two steps divided at 330?°C makes it possible to obtain an oil fraction rich in brominated compounds at low temperatures and an oil fraction depleted in brominated compounds at high temperatures. The low temperature oil contained a high concentration of SbBr₃ and dibromodibenzofurans. Various brominated compounds with a low volatility and 1-bromo-1-phenylethane from the reaction of HBr with styrene were among the substances in the high temperature oil. The concentration of brominated compounds was reduced from 6?wt% for degradation in a single step to below 1?wt% in the high temperature oil in the two step process.     

From Natural Oils to Epoxy Resins: A New Paradigm in Renewable Performance Materials

The direct conversion of natural products to useful engineering materials is desirable from both economic and environmental considerations. We describe the synthesis and properties of 100?% oil-based epoxy resins generated from three epoxidized oils. The catalyst, tris(pentafluorophenyl)borane (B(C₆F₅)₃) in toluene, allowed for controlled cationic polymerization at a very low concentration. Epoxidized oils (derived from triolein, soybean, and linseed oil) had varying epoxy content, rendering resins of different cross-link density. The polymerization was carried out at room temperature followed by post-curing at elevated temperature to speed up conversion. Epoxy resins were amorphous transparent glasses below glass transitions and hard rubbers above. Despite their high cross-link density, these materials show relatively low T_g’s reflecting the aliphatic nature of fatty acids and the presence of plasticizing “dangling” chains. The structure of the triglyceride starting oils influenced the properties of the resulting materials: the more regular structure of triolein compared to the very heterogeneous structures of soybean and linseed oils seemed to have enhanced some properties of the polymer networks. These epoxy polymers are potentially useful as encapsulating and potting compounds for electronic applications.