Production of gaseous fuel from refuse plastic fuel via co-pyrolysis using low-quality coal and catalytic steam gasification

In this study, refuse plastic fuel (RPF) was copyrolyzed with low-quality coal and was gasified in the presence of a metal catalyst and steam. Some metal catalysts, such as Ni, NiO, and Mg, and mixtures of these with base promoters such as Al₂O₃ and Fe₂O₃ were employed in the pyrolysis and gasification processes to convert the synthesis gas into more valuable fuel gas. The operating temperatures for the pyrolysis and gasification were between 700° and 1000°C. The experimental parameters were the operating temperature, catalyst type, basic promoter type, and steam injection amount. Solid fuel samples (5 g) were fed into a semibatch-type quartz tube reactor when the reactor reached the designated temperature. The synthesis gas was analyzed by gas chromatography. The use of low-quality coal as fuel in co-pyrolysis with RPF was explored. For the co-pyrolysis of RPF and low-quality coal, the effectiveness of the catalysts for fuel gas production followed the order Mg > NiO > Ni. In catalytic gasification of RPF, the addition of Al₂O₃ seemed to reduce the activity of the corresponding catalysts Ni and Mg. The maximum fuel gas yield (92.6%) was attained when Mg/Fe₂O₃ was used in steam gasification at 1000°C.     

Hydrogen-rich fuel gas production from refuse plastic fuel pyrolysis and steam gasification

In this study, experimental conditions were optimized to maximize the production of hydrogen gas from refuse plastic fuel (RPF) by pyrolysis and steam gasification processes conducted in a laboratory-scale reactor. We carried out gasification using 10-g RPF samples at different temperatures (700°-1000°C) with and without steam. The effect of the amount of steam (0–0.25 g/min) for RPF steam gasification was also studied. The effect of K₂CO₃ as a catalyst on these processes was also investigated. Experimental results showed that the hydrogen gas yield increased with temperature; with respect to the gas composition, the hydrogen content increased mainly at the expense of other gaseous compounds, which highlights the major extension of secondary cracking reactions in the gaseous fraction at higher temperatures.     

Co-gasification of wood and polyethylene with the aim of CO and H2 production

This article describes the gasification of polyethylene–wood mixtures to form syngas (H₂ and CO) with the aim of feedstock recycling via direct fermentation of syngas to ethanol. The aim was to determine the effects of four process parameters on process properties that give insight into the efficiency of gasification in general, and particularly into the optimum gasification conditions for the production of ethanol by fermentation of producer gas. Gasification experiments (fluidized bed, 800°–950°C) were done under different conditions to optimize the composition of syngas suitable for fermentation purposes. The data obtained were used for statistical analysis and modeling. In this way, the effect of each parameter on the process properties was determined and the model was used to predict the optimum gasification conditions. The parameters varied during the experiment were gasification temperature, equivalence ratio, the ratio of plastic to wood in the feed, and the amount of steam added to the process. The response models obtained proved to be statistically significant in the experimental domain. The optimum gasification conditions for maximization of carbon monoxide and hydrogen production were identified. The conditions are: temperature 900°C, equivalence ratio 0.15, amount of plastic in the feed 0.11 g/g feed, and amount of steam added 0.42 g/g feed. These optimum conditions are at the edge of the present experimental domain. The maximum combined CO and H₂ efficiency was 42%, and for the maximum yield of CO and H₂ it is necessary to minimize the polyethylene content, minimize the added steam and the equivalence ratio, and maximize temperature.     

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.     

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.     

Steam gasification of epoxy circuit board in the presence of carbonates

To recover useful metals from end-of-life electronic devices and to convert plastic components from these devices into clean fuel gas, steam gasification of epoxy board samples was carried out at 600–700?°C and 0.1?MPa pressure in the presence of a ternary eutectic carbonate (lithium carbonate, sodium carbonate, and potassium carbonate). Hydrogen and carbon dioxide were the main products, and methane and carbon monoxide were detected as minor products. The gasification proceeded in two steps: an initial rapid pyrolysis followed by secondary steam gasification of char produced from the pyrolysis. The ternary eutectic carbonate accelerated not only the latter steam gasification but also the initial rapid pyrolysis. The activation energy for the steam gasification of epoxy board samples in the presence of the carbonate was 122?kJ/mol.     

Alkaline hydrolysis of photovoltaic backsheet containing PET and PVDF for the recycling of PVDF

Recovering fluorine from end-of-life products is crucial for the sustainable production and consumption of fluorine-containing compounds because fluorspar, an important natural resource for fluorine, is currently at a supply risk. In this study, we investigated the feasibility of chemically recycling a fluorine-containing photovoltaic (PV) backsheet for fluoropolymer recycling. Herein, a PV backsheet consisting of laminated polyethylene terephthalate (PET) and polyvinylidene fluoride (PVDF) was treated with different concentrations of sodium hydroxide (NaOH) to hydrolyze the PET layer to water-soluble sodium terephthalate (Na₂TP) and to separate pure PVDF layer as a solid material. Optimized alkaline conditions (up to 10 M NaOH at 100 °C for 2 h) were determined, under which 87% of the PET layer could be decomposed without any significant deterioration of the PVDF layer. The hydrolysis kinetics of PET layer in NaOH could be explained by the modified shrinking-core model. Considering that the mass of end-of-life PV panels in Japan is estimated to increase to approximately 280,000 tons per year by 2036, PV backsheets are attractive candidates for fluoropolymer recycling, which can be effectively achieved using chemical recycling approach demonstrated in this study.

     

Gasification and its emission characteristics for dried sewage sludge utilizing a fluidized bed gasifier

Various research has attempted to determine the proper treatment of sewage sludge, including thermal technologies. Efficient thermal technologies have been focused on because of their energy saving/energy recovery. Gasification technology can be considered one of these approaches. In this study, the characteristics of gasification reactions were investigated with the aim of finding fundamental data for utilizing sewage sludge as an energy source. For the experiments on sewage sludge gasification reaction characteristics, a laboratory-scale experimental apparatus was set up with a fluidizing bed reactor of 70-mm inner diameter and 600-mm total height using an electric muffle furnace. The experimental materials were prepared from a sewage treatment plant located in Seoul. The reaction temperature was varied from 630 to 860°C, and the equivalence ratio from 0.1 to 0.3. The gas yields, compositions of product gas, and cold gas efficiencies of product gas were analyzed by GC/TCD and GC/FID installed with a carboxen-1000 column. The experimental results indicated that 800°C, ER 0.2 was an optimum condition for sewage sludge gasification. The maximum yield of product gas was about 44%. Producer gas from experiments was mainly composed of hydrogen, carbon monoxide, carbon dioxide, and methane. The cold gas efficiency of sewage sludge gasification was about 68%. The H₂/CO ratio and CO/CO₂ ratio were about 1.1 and 1.4, respectively, in optimum reaction conditions. Gaseous pollutants such as SO₂, HCl, NH₃, H₂S, and NO₂ were also analyzed at various gasification/combustion conditions, and their gaseous products were compared, showing significantly different oxidized product distributions.     

钙基固定剂对制氢和污染性气体减排的影响

在未来相当长的一段时间内,煤气化仍是大规模制取氢气的主要途径。目前,常规煤气化过程得到的是H2、CO和CO2为主的混合气,需要通过净化、变换和分离工艺才能得到洁净的氢气,工艺过程复杂。采用连续式超临界水反应装置,以质量分数为20%的水煤浆为反应原料,考察了Ca/C摩尔比和温度对褐煤制氢系统的影响。试验结果表明：Ca（OH）2不仅可以很好地固定气相中的CO2和硫化物,而且对煤气化过程也表现出较好的催化作用。反应温度600℃,压力为25MPa的条件下,与未加Ca（OH）2相比,Ca/C摩尔比为0.45时,气体中CO2的体积分数由50.7%降至1.0%,趋于完全固定;硫化物浓度由10 878mg/m3降至807mg/m3;H2的体积分数由32.4%增至73.3%。Ca（OH）2对煤气化的催化作用在高温下更加明显。     

Gasification of waste plastics by steam reforming in a fluidized bed

The process of producing synthetic gas from waste plastics by steam reforming was investigated. To evaluate this process, the steam reforming of the oils derived from low-density polyethylene and polystyrene were carried out using a laboratory-scale fluidized bed of Ni-Al₂O₃ catalysts. The performance of gasification in terms of carbon conversion, gas yield, and gas compositions was examined. Although oils derived from plastics contain many kinds of heavy hydrocarbons and aromatics, they were well gasified at temperatures above 1023 K with a steam/carbon ratio of 3.5 and a weight hourly space velocity of 1 h⁻¹. The hydrogen content of the product gas was very high at approximately 72 vol% for polyethylene-derived oil and 68 vol% for polystyrene-derived oil. These compositions agreed well with the values calculated from chemical equilibrium.     

Gasification characteristics of sewage sludge combined with wood biomass

The gas products from gasification processes have been considered to have some limitations in gas composition and heating value from the previous studies. Gasification characteristics of sewage sludge and wood mixture were investigated using different mixing ratios with the purpose of better quality of gas product suitable for energy/power generation. The gasification experiment was performed by an indirectly heated fluidized bed reactor. As reaction temperature increased from 600 to 900 °C, the yield of gas product increased with higher generation of CO, H₂ and CH₄ by more activated gas conversion reactions. As the equivalence ratio increased from 0.2 to 0.4, composition ratio of CO₂ increased while CO, CH₄, H₂ decreased as expected. Several operating variables including mixing ratio of wood with dried sludge were also tested. From this initial stage of experiment, optimal operating conditions for the bubbling fluidized bed gasifier, could be considered 900 °C in temperature; 0.2 in equivalence ratio and 40 % in wood mixing ratio within test variables range. These results will be more thoroughly investigated for the application to the larger scale pilot system.     

Treatment of discarded oil in supercritical carbon dioxide for preparation of carbon microspheres

Carbon microspheres with diameter of 1–10 μm were prepared by treatment of waste oil in a supercritical carbon dioxide (scCO₂) system. The structure and morphology of the products were characterized by X-ray diffraction, field-emission scanning electron microscopy, and Raman spectrometry. It is shown that the products consist of graphite microspheres with relatively low graphitization. The yield of solid products increased from 26.8 wt% to 42.2 wt% as the reaction temperature was raised from 530°C to 600°C. Spheres with multilayer structure could be obtained by means of subsequent vacuum annealing of the carbon microspheres at 1500°C. The formation mechanisms of carbon microspheres in the scCO₂ system and the influence of vacuum annealing on the structure are discussed in detail.     

Reduction of tar using cheap catalysts during sewage sludge gasification

Solid-fuel conversion or gasification study of sewage sludge and energy recovery has become increasingly important because energy recovery and climate change are emerging issues. Various types of catalysts, such as dolomite, steel slag and calcium oxide, were tested for tar reduction during the sewage sludge gasification process. For the experiments on sewage sludge gasification reactions and tar reduction using the catalysts, a fixed bed of laboratory-scale experimental apparatus was set up. The reactor was made of quartz glass using an electric muffle furnace. The sewage sludge samples used had moisture contents less than 6%. The experimental conditions were as follows: sample weight was 20 g and reaction time was 10 min, gasification reaction temperature was from 600 to 800°C, and the equivalence ratio was 0.2. The quantity of catalysts was 2–6 g, and temperatures of catalyst layers were 500–700°C. As the reaction temperature increased up to 800°C, the yields of gaseous products and liquid products increased, whereas char and tar products decreased, showing effects on gas product compositions. These results were considered to be due to the increase of the water-gas reaction and Boudouard reaction. In the case of experiments with catalysts, dolomite (4 g), steel slag (6 g) and calcium oxide (6 g) were used. When the temperature of catalysts increased, the weight of the tar produced decreased with different cracking performances by different catalysts. Reforming reactions were considered to occur on the surface of dolomite, steel slag and calcium oxide, causing cracking of the hydrocarbon structure, which eventually showed reduced tar generation.     

Gasification of refuse derived fuel in a fixed bed reactor for syngas production

Steam gasification of two different refuse derived fuels (RDFs), differing slightly in composition as well as thermal stability, was carried out in a fixed-bed reactor at atmospheric pressure. The proximate and ultimate analyses reveal that carbon and hydrogen are the major components in RDFs. The thermal analysis indicates the presence of cellulose and plastic based materials in RDFs. H2 and CO are found to be the major products, along with CO2 and hydrocarbons resulting from gasification of RDFs. The effect of gasification temperature on H2 and CO selectivities was studied, and the optimum temperature for better H2 and CO selectivity was determined to be 725 degrees C. The calorific value of product gas produced at lower gasification temperature is significantly higher than that of gas produced at higher process temperature. Also, the composition of RDF plays an important role in distribution of products gas. The RDF with more C and H content is found to produce more amounts of CO and H2 under similar experimental conditions. The steam/waste ratio showed a notable effect on the selectivity of syngas as well as calorific value of the resulting product gas. The flow rate of carrier gas did not show any significant effect on products yield or their distribution.     

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

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.     

Synthesis of zeolite from waste fly ash for adsorption of CO2

Zeolitic sorbents for CO₂ adsorption were prepared from waste coal fly ash (FA) through hydrothermal treatment at various ratios of NaOH/FA and NaAlO₂/FA, including an initial alkali fusion step. The fusion step decomposed the fly ash into very small amorphous particulate zeolite forms. The fly ash was converted to Na-P1 type with a NaOH/FA ratio of 0.5 and Na-A type with a NaAlO₂/FA ratio of 0.53. The product properties were affected by the reaction temperature: Na-P1 and Na-A types were formed at 100°C. Temperatures above 140°C led to the formation of more sodalite because of the redissolving and recrystallization of zeolite crystals. Alkali metal and alkaline earth metal cations were impregnated in the synthesized Na-P1 and Na-A zeolite through an ion-exchange method. The completed zeolitic sorbents were applied to the adsorption of low-level CO₂. As a result of the experiments, calcium ions were found to be the best for CO₂ adsorption owing to their electrostatic behavior and acid-base interaction.     

Biomass waste gasification - can be the two stage process suitable for tar reduction and power generation?

A pilot scale gasification unit with novel co-current, updraft arrangement in the first stage and counter-current downdraft in the second stage was developed and exploited for studying effects of two stage gasification in comparison with one stage gasification of biomass (wood pellets) on fuel gas composition and attainable gas purity. Significant producer gas parameters (gas composition, heating value, content of tar compounds, content of inorganic gas impurities) were compared for the two stage and the one stage method of the gasification arrangement with only the upward moving bed (co-current updraft). The main novel features of the gasifier conception include grate-less reactor, upward moving bed of biomass particles (e.g. pellets) by means of a screw elevator with changeable rotational speed and gradual expanding diameter of the cylindrical reactor in the part above the upper end of the screw. The gasifier concept and arrangement are considered convenient for thermal power range 100-350 kW_th. The second stage of the gasifier served mainly for tar compounds destruction/reforming by increased temperature (around 950 °C) and for gasification reaction of the fuel gas with char. The second stage used additional combustion of the fuel gas by preheated secondary air for attaining higher temperature and faster gasification of the remaining char from the first stage. The measurements of gas composition and tar compound contents confirmed superiority of the two stage gasification system, drastic decrease of aromatic compounds with two and higher number of benzene rings by 1-2 orders. On the other hand the two stage gasification (with overall ER = 0.71) led to substantial reduction of gas heating value (LHV = 3.15 MJ/Nm³), elevation of gas volume and increase of nitrogen content in fuel gas. The increased temperature (>950 °C) at the entrance to the char bed caused also substantial decrease of ammonia content in fuel gas. The char with higher content of ash leaving the second stage presented only few mass% of the inlet biomass stream.     

Steam gasification of waste tyre: Influence of process temperature on yield and product composition

An experimental survey of waste tyre gasification with steam as oxidizing agent has been conducted in a continuous bench scale reactor, with the aim of studying the influence of the process temperature on the yield and the composition of the products; the tests have been performed at three different temperatures, in the range of 850–1000 °C, holding all the other operational parameters (pressure, carrier gas flow, solid residence time). The experimental results show that the process seems promising in view of obtaining a good quality syngas, indicating that a higher temperature results in a higher syngas production (86 wt%) and a lower char yield, due to an enhancement of the solid–gas phase reactions with the temperature. Higher temperatures clearly result in higher hydrogen concentrations: the hydrogen content rapidly increases, attaining values higher than 65% v/v, while methane and ethylene gradually decrease over the range of the temperatures; carbon monoxide and dioxide instead, after an initial increase, show a nearly constant concentration at 1000 °C. Furthermore, in regards to the elemental composition of the synthesis gas, as the temperature increases, the carbon content continuously decreases, while the oxygen content increases; the hydrogen, being the main component of the gas fraction and having a small atomic weight, is responsible for the progressive reduction of the gas density at higher temperature.     

Catalytic gasification of tars from a dumping site

The work deals with catalytic gasification, pyrolysis and non-catalytic gasification of tar from an industrial dumping site. All experiments were carried out in a vertical stainless steel gasification reactor at 800 °C. Crushed calcined dolomite was used as the gasification catalyst. Parameters such as addition of water and air, and the influence of the catalyst in regard to the composition of the process gas were investigated. The catalytic gasification experiment in the steady state produced process gas with the composition: 56 % of H₂, 9 % of CO, 11 % of CH₄ and 12 % of CO₂ (mol.%). Concentration of the C₂ fraction was lower than 1 mol.%. Volume flow of air was later changed from 120 to 230 ml min^?1 reducing the amount of hydrogen to 51 mol.% and that of methane to 10 mol.%. Process gas created in a non-catalytic gasification process contained 26–30 mol.% of methane, 13–15 mol.% of carbon monoxide and 15–17 mol.% of the C₂ fraction and lower amounts of hydrogen (20 mol.%) and carbon dioxide (2–3 mol.%). The highest apparent conversion of tar was reached in the catalytic gasification processes. A higher rate of catalyst deactivation can be observed when water or air is not added.