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.     

The effect of clay catalyst on the chemical composition of bio-oil obtained by co-pyrolysis of cellulose and polyethylene

Cellulose/polyethylene (CPE) mixture 3:1, w/w with and without three clay catalysts (K10 – montmorillonite K10, KSF – montmorillonite KSF, B – Bentonite) addition were subjected to pyrolysis at temperatures 400, 450 and 500 °C with heating rate of 100 °C/s to produce bio-oil with high yield. The pyrolytic oil yield was in the range of 41.3–79.5 wt% depending on the temperature, the type and the amount of catalyst. The non-catalytic fast pyrolysis at 500 °C gives the highest yield of bio-oil (79.5 wt%). The higher temperature of catalytic pyrolysis of cellulose/polyethylene mixture the higher yield of bio-oil is. Contrarily, increasing amount of montmorillonite results in significant, almost linear decrease in bio-oil yield followed by a significant increase of gas yield. The addition of clay catalysts to CPE mixture has a various influence on the distribution of bio-oil components. The addition of montmorillonite K10 to cellulose/polyethylene mixture promotes the deepest conversion of polyethylene and cellulose. Additionally, more saturated than unsaturated hydrocarbons are present in resultant bio-oils. The proportion of liquid hydrocarbons is the highest when a montmorillonite K10 is acting as a catalyst.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

Recycling nickel from spent catalyst of Phu My fertilizer plant as a precursor for exhaust gas treatment catalysts preparation

In this study, a very promising way of treating and recycling spent nickel catalysts of fertilizer plants in Vietnam was proposed. Firstly, nickel was recovered from spent catalyst using HNO₃—leaching process. Results show that nickel recovery of over 90% with a purity of over 90% can be achieved with HNO₃ 2.1–2.5 M at 100?°C in 75 min. The residue after leaching is not considered as a hazardous waste according to the Vietnamese regulations. Then, the leachate solution was used as a precursor to prepare a model catalyst for exhaust gas (CO, HC, NO_x) treatment. In comparison with the catalyst prepared from the commercial nickel nitrate solution, the catalyst synthesized from recovered nickel exhibits similar properties and activities. The influence of Ni loading of Ni/alumina catalyst as well as the modification of active phase by some metals addition (Mn, Ba, Ce) was also investigated. It is feasible to modify active phase by transition metals such as Mn, Ba, and Ce for complete oxidation of CO and HC at 270?°C and a reduction of NO_x below 350?°C at high volumetric flow condition (GHSV?=?110.000 h^?1).     

The Role of Catalyst Properties on Methanol Oxidation over V2O5–TiO2 Using Ozone

Oxidation of methanol over V₂O₅ catalysts supported on anatase TiO₂ that were prepared using sol-gel formation and impregnation procedures were investigated. The effects of incorporating Mg in sol-gel to influence the properties of the catalyst were also studied. The process provides an alternative low temperature reaction pathway for reducing emissions of hazardous air pollutant (HAPs) such as methanol and total reduced sulfur compounds (TRS) from pulp and paper mills. The bulk and surface composition of the catalysts were determined by XRD and SEM-EDAX, respectively. The X-ray diffraction patterns of the vanadia–titania catalysts showed mainly the anatase phase of TiO₂. Temperature programmed desorption of methanol from the different catalyst showed that the α and β peaks differ significantly with V content and addition of Mg. The combination of gas phase and surface reactions on the V/TiO₂ catalysts reduced the amount of ozone required for high degradation of methanol to mainly CO _x with small quantities of methyl formate. In the absence of ozone the catalysts showed very low activity. It is hypothesized that the ozone is directly influencing the V⁴⁺ and V⁵⁺ redox cycle of the catalyst. Oxidation of methanol is influenced by the operation variables and catalyst properties. The results of this study revealed that the V content has significant influence on the catalyst activity, and the optimum vanadia loading of about 6 wt%. Higher turnover frequencies were observed over sol-gel catalysts than with catalysts prepared by the impregnation method.     

压裂返排液的处理及回用

制备了沸石负载纳米TiO_2催化剂和蒙脱土负载纳米零价铁吸附剂,结合传统处理技术,构建了"絮凝—预氧化(Fenton氧化)—沸石负载纳米TiO_2催化臭氧氧化—蒙脱土载负纳米零价铁吸附"组合工艺,处理压裂返排液,考察了影响COD去除效果的因素。实验结果表明:在催化剂投加量1.0 g/L、臭氧通入时间5 min、吸附剂投加量5.0 g/L、吸附时间4 h的最佳条件下,COD从原水的4 032.60 mg/L降至37.03 mg/L,处理后出水各项指标均达到GB 8978—1996《污水综合排放标准》中的一级标准;80℃下,出水回用配制的压裂液黏度为4.4 mPa·s,高于自来水配制和压裂返排液配制的压裂液,耐温性有一定提升。     

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.     

Development of a catalytic cracking process for converting waste plastics to petrochemicals

The catalytic degradation of polyolefin using H-gallosilicates was examined using a bench-scale reactor (0.8kg/h) with semicontinuous feeding and the following plastics: (1) low-density polyethylene (LDPE) pellets; (2) linear low-density polyethylene (L-LDPE) pellets; (3) high-density polyethylene (HDPE) pellets; (4) polypropylene (PP) pellets; (5) polyolefin obtained from pulverized industrial waste plastics. The yields of liquid compounds from these materials, which were aromatics in most cases, ranged from 55wt% to 68wt%. With an increase in the ratio of total reactant to catalyst, the liquid yield remained the same. Yields of benzene, toluene, and xylenes (BTXs) decreased rapidly to below 50wt% at a ratio of more than 30. Differences in this ratio for BTXs were always small and were independent of the material. Only about half of the gas product was propane with a fresh catalyst. When the experiments were repeated, propylene, isobutane, and isobutene were found to increase.     

Pyrolysis of aseptic packages (tetrapak) in a laboratory screw type reactor and secondary thermal/catalytic tar decomposition

Pyrolysis of aseptic packages (tetrapak cartons) in a laboratory apparatus using a flow screw type reactor and a secondary catalytic reactor for tar cracking was studied. The pyrolysis experiments were realized at temperatures ranging from 650 °C to 850 °C aimed at maximizing of the amount of the gas product and reducing its tar content. Distribution of tetrapak into the product yields at different conditions was obtained. The presence of H₂, CO, CH₄, CO₂ and light hydrocarbons, HCx, in the gas product was observed. The Aluminum foil was easily separated from the solid product. The rest part of char was characterized by proximate and elemental analysis and calorimetric measurements. The total organic carbon in the tar product was estimated by elemental analysis of tars. Two types of catalysts (dolomite and red clay marked AFRC) were used for catalytic thermal tar decomposition. Three series of experiments (without catalyst in a secondary cracking reactor, with dolomite and with AFRC) at temperatures of 650, 700, 750, 800 and 850 °C were carried out. Both types of catalysts have significantly affected the content of tars and other components in pyrolytic gases. The effect of catalyst on the tetrapack distribution into the product yield on the composition of gas and on the total organic carbon in the tar product is presented in this work.     

复合载体对选择性催化还原催化剂低温脱硝性能的影响

采用浆液浸涂法在堇青石蜂窝陶瓷载体上涂覆Al2O_3-TiO_2-ZSM-5分子筛复合载体,并通过浸渍法负载活性组分Mn-Fe-Ce,制备了M/ATZ-CC选择性催化还原催化剂。考察了催化剂的低温脱硝活性和抗水性能,表征了催化剂的物性参数和氨-程序升温脱附性能。实验结果表明,M/ATZ-CC催化剂具有优异的脱硝活性和抗水性能,在反应温度为160℃、水蒸气加入量为10%(φ)、NO体积分数为0.1%、n(NH_3)∶n(NO)=1、O_2体积分数为3.0%、体积空速为3 000~10 000 h~(-1)的条件下,NO去除率在80%以上。表征结果显示,该催化剂的比表面积、孔径、弱酸酸量、中强酸酸量和总酸量得到了显著提高。     

Effect of Metal Oxide Catalysts on Degradation of Waste Polystyrene in Hydrogen at Elevated Temperature and Pressure in Benzene Solution

Degradation of waste polystyrene is carried out in presence of hydrogen using several metal oxide catalysts at elevated temperature and pressure for recycling. Benzene is used as a solvent for degradation. Initial hydrogen pressure in the autoclave is kept at 7.0 kg/cm² (g) and polystyrene degradation is carried out at 240 °C. After degradation, degraded polystyrene residue is separated and analyzed by Fourier transform infra red (FTIR) spectroscopy whereas filtrate is analyzed by gas chromatography (GC) for finding the degradation mechanism of polystyrene. Degradation rate is enhanced in presence of hydrogen and time dependent weight average molecular weight of degraded polystyrene is determined using viscosity method. Degradation rate constants for the different catalysts are calculated based on the proposed degradation mechanism. Alkali metal oxide catalyst shows higher reactivity towards polystyrene degradation as compare to the transition metal oxide catalyst i.e., degradation rate constant decreases with the increase in electro negativity of metal element of the catalyst. Though manganese (IV) oxide is a transition metal catalyst, but shows higher reactivity due to its reduction towards stable manganese (II) oxide under degradation environment. Finally, degradation rate constant of polystyrene is correlated with the catalyst activity i.e., electro negativity of metal element in the catalyst.     

NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝性能

采用浸渍法制备了不同NiO和CuO质量分数的NiO-CuO/ZSM-5催化剂，并以CH4为还原剂研究了NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝活性。XRD分析结果表明，NiO质量分数为4%、CuO质量分数为6%的催化剂4%NiO-6%CuO/ZSM-5中的ZSM-5结构完好，CuO和NiO高度分散在ZSM-5骨架中，表明具有较好的催化活性。4%NiO-6%CuO/ZSM-5的脱硫脱硝起活温度均较低，无氧条件下最高NO转化率和SO2转化率分别为94.7%和95.9%，O2体积分数为1.0%时的NO转化率和SO2转化率分别为97.7%和89.0%。     

Hydroreforming over Ni/H-beta of the thermal cracking products of LDPE, HDPE and PP for fuel production

The thermal cracking at 400?°C of pure polyolefins—low density polyethylene (LDPE), high density polyethylene (HDPE) and polypropylene (PP) and a standard polyolefin mixture (46?% LDPE?+?27?% HDPE?+?28?% PP)—was studied together with the catalytic hydroreforming of the obtained oils over Ni/h-beta at 310?°C under 20?bar of hydrogen. The oils obtained after the thermal cracking of PP contain the highest amount of gasoline (58?%), while those coming from HDPE the lowest (39?%). The bromine index of the oils was very high, ranging from 54.1 (LDPE) to 83.8 (PP), indicating a high olefinic content of the oils. Additionally, the thermal cracking of the mixture indicates the occurrence of a synergestic effect among plastics, with transfer of methyl groups from PP to polyethylenes. Ni/h-beta (Si/Al?=?25; Ni content?=?6.2?wt%) catalyst was used in the hydroreforming since it contains a bimodal pore size distribution (0.6/3.1?nm), which improves accessibility of the oil molecules to the catalytic sites. After the hydroreforming and regardless of the plastics used, the share of lighter products (gasoline and gases) increases, reaching a remarkable 68?% of gasolines with the oils coming from PP. Regardless of the starting feed, the amount of useful fuels (gasoline?+?light diesel) was within 80–85?%. Additionally, the oils were successfully hydrogenated since the bromine indexes dropped below 7, indicating that more than 90?% of the starting olefins were saturated. The usage of catalysts increased the amount of aromatics in the obtained oils within 13–20?%, depending on the starting plastic. Likewise, the isoparaffin content of the gasolines was within 35–40?%, except for PP, where it was enhanced to 62?%. However, the research octane number (RON) of the gasolines from LDPE and PP and the cetane indexes of the diesel from all the plastics were promising for their application as fuels.     

Effects of fly ash addition on physical properties of porous clay-fly ash composites via polymeric replica technique

The porous composites of clay and fly ash have the potential to be used in many fields, such as catalyst support and gas adsorbents. In this study, various ratios of fly ash (1–2) with different percentage of suspension (50–70 wt%) were applied to produce porous clay-fly ash composites via polymeric replica technique. Fabrication process starts by mixing clay and fly ash in distilled water to form slurry. The process is followed by fully immersing polymer sponge in slurry. The excess slurry is then removed through squeezing. Finally, the sponge coated with slurry is sintered at 500 and 1250 °C for 1 h. It is found that the compressive strength of porous composites improves significantly (0.178–1.28 MPa) when the amount of clay-fly ash suspension mixture (50–70 wt%) increases. The compressive strength of porous composites is mainly attributed to the mullite, quartz and amorphous phase formations. These results are supported by X-ray diffraction analysis. On the other hand, increase in the amount of suspension reduces the apparent density (from 2.44 to 2.32 g/cm³) and porosity (from 97 to 85 %). The reduction in apparent density is believed to be caused by the presence of high fly ash content in porous composites. The melted fly ash cenospheres have closed the internal pores and increased density of samples. Higher suspension level not only reduces porosity, but also increases close pores of the porous composites. The results are justified through the observation from the structures of porous clay-fly ash composites.     

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.     

Optimization of two-step catalyzed biodiesel production from soybean waste cooking oil

An acid–base-catalyst-based two-step biodiesel production experiment from soybean waste cooking oil was carried out to identify which parameter is the most influential among the experimental parameters by using the Taguchi method. Heterogeneous catalysts were used to avoid a water-consuming homogeneous catalyst removal process. Ferric sulfate and calcium oxide were used as acid and base catalysts, respectively, for the heterogeneous reaction. Reaction time and methanol-to-triglyceride mole ratio were significant factors. The optimum parameters for step 1 (acid esterification) were 4 h of reaction time, 4 wt. % of ferric sulfate amount, a 16:1 methanol to triglyceride mole ratio, and 400 rpm of mixing speed, respectively. For the transesterification step, the most influential factor was reaction time, and CaO amount was significant as well. On the other hand, the mole ratio of methanol and oil was relatively less significant. Optimum parameters were 3 h of reaction time, 2 wt. % of CaO, and a 12:1 methanol to triglyceride mole ratio with mixing speed at 400 rpm in this experimental range. Under the optimum conditions, waste cooking oil with 5.27 mg KOH/g of acid value was converted into crude biodiesel by a two-step process with fatty acid methyl ester content reaching 89.8 % without any further post-purification.     

Preparation of biochar catalyst with saccharide and lignocellulose residues of corncob degradation for corncob hydrolysis into furfural

This paper presented a novel process for production of furfural by hydrothermal degradation of corncob over biochar catalyst, in which it was prepared with the recycling degradation solution and lignocellulosic solid residues. The biochar catalyst was papered by lignocellulose residues and concentrated saccharide solution, and then impregnated in 0.5 mol/L sulphuric acid at room temperature for 24 h assisted by the ultrasonic vibration. In the system of recycling, 8.8 % lignocellulose residues and 100 % concentrated saccharide solution from corncob hydrolysis have been recycled. Hydrolysis of corncob was carried out at 180 °C for duration of 170 min over the biochar catalyst. The experimental results have shown that the furfural yield of up to 37.75 % and overall corncob conversion rate of 62.00 % could be achieved under optimum operating conditions for the catalysts preparation and the corncob hydrolysis. It is believed that the acid density of 4.27 mmol/g of biochar catalyst makes the SO₃H groups cleave β-1,4 glycosidic linkages effectively and hydrolyze the cellulose and hemicellulose to water-soluble sugars, as well as to facilitate dehydration of xylose to give the product of furfural.     

前驱体溶液pH对核壳型Cr/CeO2催化剂低温选择性催化氧化脱硝性能的影响

采用一步水热法合成了具有核壳结构的铬铈复合氧化物（Cr/CeO₂）,并将其用于选择性催化氧化（SCO）烟气脱硝,考察了前驱体溶液pH对催化剂低温催化活性的影响。实验结果表明,当前驱体溶液pH为2时制得的催化剂（CrCe2）具有较高的低温SCO活性,其在200 ℃下的NO转化率高达59%。XRD,SEM,BET,UV-Vis,TPD等表征结果显示：核壳结构的生成促进了Cr物种的高分散性,同时Cr的掺杂增大了催化剂的比表面积,从而提高了活性位点的总量;在该系列催化剂中,CrCe2催化剂具有最高的表面六价铬和化学吸附氧的占比,因此呈现出最高的低温SCO活性。     

Catalytic degradation of PP with an Fe/activated carbon catalyst

We investigated the function of Fe and activated carbon (AC) as a catalyst by comparing Fe/AC with Fe/SiO₂ or AC, and also the effect of H₂ as a reaction gas on the product distribution in the catalytic degradation of polypropylene. Supported Fe promotes H₂ consumption to decompose solid residues, and AC support degrades heavy oil to produce light oil. As a result, using Fe/AC as a catalyst gives the maximum yield of the liquid product. For the reaction conditions, with a high reaction temperature or a long reaction time, the product distribution is more influenced by the thermal degradation than by the catalytic degradation. For the amount of Fe to load, 5wt% is the optimum condition in our reaction system. We demonstrated the mechanism of the degradation of polyolefins with hydrogen-capping catalysts.     

Effect of Gamma Radiation on the Properties of Crosslinked Chitosan Nano-composite Film

Chitosan nano-composite film crosslinked by citric acid and with glycerol as plasticizer and MgO as antibacterial agent was prepared by casting method. MgO nanoparticles were synthesized via calcination method in furnace at 500 °C for 4 h and characterized by X-ray diffraction and transmission electron microscope. The chitosan nano-composite film with composition chitosan/citric/glycerol/magnesium oxide (1 wt%:1 wt%:75 vol%:10 wt%) has high mechanical properties than other films. The effects of different irradiation doses on the mechanical, thermal and antibacterial activity were investigated. The tensile strength enhanced by increasing irradiation dose up to 10 kGy and the elongation negligible changed as irradiation dose increased. The thermal stability slightly increased up to dose 2.5 kGy then decreased with dose increment. The antimicrobial activity film was studied against white mulberry-borne bacterial pathogens either Gram positive or Gram negative bacteria and has positive impact of gamma irradiation on the antimicrobial activity. The use of the selected chitosan nano-composite film which irradiated by dose of 2.5 kGy and has magnesium oxide of average particle size 54.3 nm as new packaging materials found to improve storage quality and shelf-life of mulberry fruit.