Pyrolysis of Xanthium strumarium in a fixed bed reactor: Effects of boron catalysts and pyrolysis parameters on product yields and character

Pyrolysis of Xanthium strumarium has been performed in a fixed-bed tubular reactor with boron minerals (ulexite, colemanite, and borax) and without catalyst at three different temperatures ranging from 350°C to 550°C with heating rate of 50°C/min. The amounts of bio-oil, bio-char, and gas generated, also the compositions of the resulting bio-oils were identified by GC-MS and FT-IR. The influences of pyrolysis parameters, such as temperature and catalyst on product yields were investigated. Temperature and catalyst were found to be the main factors affecting the conversion of Xanthium strumarium into solid, liquid, and gaseous products. The highest liquid yield (27.97%) including water was obtained with 10% colemanite (Ca₂B₆O₁₁.5H₂O) catalyst at 550°C temperature at a heating rate of 50°C/min when 0.224 > D_p > 0.150 mm particle size raw material and 100 cm³/min of sweeping gas flow rate were used.     

Evaluation of influence of two different catalysts on the pyrolysis of laurel (Laurus nobilis L.) extraction residues

Laurel extraction residues with zeolite and alumina catalysts were pyrolyzed in a fixed-bed reactor with a constant heating rate of 10°C min^–1. The final pyrolysis temperature and sweep gas flow rate were kept constant at 500°C and 100 ml min^–1 in all of the experiments, respectively. The influence of catalysts and their ratio (10, 20, 30, 40, and 50% w/w) on the pyrolysis conversion and product yields were investigated in detail. The physicochemical properties of the catalytic bio-oil were determined and compared to those of non-catalytic bio-oil. The catalytic bio-oils were examined using some spectroscopic and chromatographic techniques.     

Experimental study of the pyrolysis of waste bitumen for oil production

This work focuses on bitumen slow pyrolysis. Mass and energy yields of oil, solid and gas were obtained from pyrolysis experiments using a semi-batch reactor in a nitrogen atmosphere, under three non-isothermal conditions (maximum temperature: 450 °C, 500 °C and 550 °C). The effect of temperature on the product yields was discussed. The gas compositions were analysed using gas chromatography (GC) and the heating value of oil and solid residue was also measured. Using a thermo-gravimetric analyser, kinetic parameters were evaluated through Ozawa-Flynn-Wall (OFW) method. Results showed that oil yield is maximum at 500 °C (50%). Moreover, gas yield increased with increasing pyrolysis temperature from 18% to 36%. On the other hand, solid yield showed an opposite trend: it decreased from 39% to 32%. As regard energy yields, they showed a similar trend with the mass ones. H_2, CH₄, C₂H₄, C₂H₆ and C₃H₈ are the main components of the produced gas phase. It has been noticed that the recovery of bitumen to liquid oil through pyrolysis process had a great potential since the oil produced had high calorific value comparable with commercial fuels.     

Potentiality of “orujillo” (olive oil solid waste) to produce hydrogen by means of pyrolysis

The extraction of olive oil generates great amounts of solid waste and wastewater. The objective of this work is to evaluate the potentiality of slow pyrolysis of the solid oil waste, known as “orujillo”, to produce hydrogen rich gases. The effect of temperature and of different treatments of pyrolysis vapors on the yield and composition of the gases has been experimentally studied. “Orujillo” was pyrolyzed at 500 °C and 700 °C, and the pyrolysis vapors produced were directly fed to a second reactor where they were treated at 800 °C in different ways: just thermally, thermally treated through a refractory alumina bed and thermo-catalytically treated through a three layer bed (alumina + SiC mixed with Ni catalyst + alumina). The catalyst used was a commercial prereduced nickel-catalyst which contains 44 wt% Ni over calcium aluminate support (CaO/Al₂O₃). Concerning the effect of temperature, it has been proved that the raise in temperature leads to a decrease in the liquid yields and an increase in the gas yields, as well as to an increase in H₂ and a decrease in CO₂ content of the gases. With respect to the vapors treatments it has been observed that as a general rule any of the treatments reduces liquid and increases gas yields, and concerning gas composition, H₂ content increases, CO slightly increases and CO₂ decreases. These effects are more pronounced when the Ni-catalyst is used. With the Ni-catalyst about 50 wt% gas yield is obtained, with ≈ 50 vol% H₂ both at 500 and at 700 °C.     

Fixed-Bed Pyrolysis of Hazelnut (Corylus Avellana L.) Bagasse: Influence of Pyrolysis Parameters on Product Yields

Fixed-bed slow pyrolysis experiments have been conducted on a sample of hazelnut bagasse to determine particularly the effects of pyrolysis temperature, heating rate, particle size and sweep gas flow rate on the pyrolysis product yields. The temperature of pyrolysis, heating rate, particle size and sweep gas flow rate were varied in the ranges 350–550° C, 10 and 50° C/min, 0.224–1.800 mm and 50–200 cm³/min, respectively. Under the various pyrolysis conditions applied in the experimental studies, the obtained char, liquid, and gas yield values ranged between 26 and 35 wt%, 23 and 34.40 wt%, and 25 and 32 wt%, respectively. The maximum biooil yield of 34.40% was obtained at the final pyrolysis temperature of 500°C, with a heating rate of 10° C/min, particle size range of 0.425–0.600 mm and a sweep gas flow rate of 150 cm³/min.     

Catalytic effects of borax and iron(III) chloride on supercritical liquefaction of Anchusa azurea with methanol and isopropanol

Anchusa azurea is a lignocellulosic gramineous plant, and it has been selected as a renewable feedstock to be used in a liquefaction process to obtain biofuel. Milled Anchusa azurea stalks were converted to liquid products in methanol and isopropanol with (borax or iron(III) chloride) and without catalyst in an autoclave at temperatures of 260, 280, and 300°C. The liquefaction parameter effects such as catalyst, solvents, and temperature were investigated. The highest percentages of liquid yields from methanol and isopropanol conversions were 64.70% (with borax) and 29.20% (with borax) at 300°C in the catalytic runs, respectively. The highest conversion (73.80%) was obtained in methanol with borax catalyst at the same temperature. The obtained liquid products at 300°C were analyzed and characterized by elemental, Fourier transform infrared spectroscopy and gas chromatography–mass spectrometry (GC-MS). Seventy-three different compounds have been identified by GC-MS in the liquid products obtained in methanol at 300°C.     

Tailoring Cu/Al2O3 catalysts for the catalytic pyrolysis of tomato waste

In this study, pyrolysis of tomato waste has been performed in fixed bed tubular reactor at 500 °C, both in absence and presence of Cu/Al₂O₃ catalyst. The influences of heating rate, catalyst preparation method and catalyst loading on bio-oil yields and properties were examined. According to pyrolysis experiments, the highest bio-oil yield was obtained as 30.31% with a heating rate of 100 °C/min, 5% Cu/Al₂O₃ catalyst loading ratio and co-precipitation method. Results showed that the catalysts have strong positive effect on bio-oil yields. Bio-oil quality obtained from fast catalytic pyrolysis was more favorable than that obtained from non-catalytic and slow catalytic pyrolysis.     

Performance of active nickel loaded lignite char catalyst on conversion of coffee residue into rich-synthesis gas by gasification

Performance of nickel-loaded lignite char catalyst on conversion of coffee residue into synthesis gas by catalytic steam gasification was carried out at low reaction temperatures ranging from 500 °C to 650 °C in the two-stage quartz fixed bed reactor. The effects of steam pressures (30, 36 and 50 kPa corresponding to S/B = 2.23, 2.92 5.16, respectively) and catalyst to biomass ratios (C/B ratio = 0, 1, 3) were considered. Nickel-loaded lignite char was prepared as a catalyst with a low nickel loading amount of 12.9 wt%. The gas yields in the catalytic steam gasification process strongly depended on the reaction temperature and C/B ratio. The total gas yields obtained in catalytic steam gasification was higher than that of catalytic pyrolysis, steam gasification and non-catalytic pyrolysis with steam absence by factors of 3.0, 3.8 and 7.7, respectively. To produce the high synthesis gas, it could be taken at 600 °C with total gas yields of 67.13 and 127.18 mmol/g biomass-d.a.f. for C/B ratios of 1.0 and 3.0, respectively. However, the maximum H₂/CO ratio was 3.57 at a reaction temperature of 600 °C, S/B of 2.23 and C/B of 1.0. Considering the conversion of coffee residue by catalytic steam gasification using the nickel-loaded lignite char catalyst, it is possible to covert the coffee residue volatiles into rich synthesis gas.     

Energy Applications of Biomass: Pyrolysis of Apricot Stone

Apricot stone (Prunus armeniaca L.) was pyrolyzed in a directly heated fixed-bed reactor under nitrogen atmosphere. Effects of sweeping gas flow rates and pyrolysis temperature on the pyrolysis of the biomass were also studied. Pyrolysis runs were performed using reactor temperatures between 400°C and 700°C with heating rate of about 300°C min^?1. As the pyrolysis temperature was increased, the percentage mass of char decreased while gas product increased. The product yields were significantly influenced by the process conditions. The bio-oil obtained at 550°C, at which the liquid product yield was maximum, was analyzed. It was characterized by Fourier transform infrared spectroscopy (FT-IR). In addition, the solid and liquid products were analyzed to determine their elemental composition and calorific value. Chemical fractionation of bio-oil showed that only low quantities of hydrocarbons were present, while oxygenated and polar fractions dominated.     

Promotion of bio oil,H2 gas from the pyrolysis of rice husk assisted with nano silver catalyst and utilization of bio oil blend in CI engine

This paper reports on the pyrolytic distillation of rice husk with catalyst and its influence on both condensable and non-condensable volatiles. The catalyst used for pyrolysis was nano sized silver particles obtained through chemical reduction method. The structural features of the nano silver particles were explored through X-ray diffraction (XRD) and Field Emission Scanning Electron Microscope (FESEM) with Energy-dispersive-X-ray spectroscope (EDX), and the size of the nano particles was confirmed as 90 nm. After intimately mixing the rice husk (30 g) with the catalyst, the pyrolysis at various temperatures (400 °C, 450 °C, 500 °C, 550 °C) was performed. The products obtained during catalytic pyrolysis like gaseous fuel, bio oil, and bio char were separately collected and characterized through Gas Chromatography-Mass Spectrometer (GC-MS) and Inductively Coupled Plasma – Optical Emission Spectrometer (ICP-OES). About 50% of the solid biomass was converted into more useful liquid and gaseous fuel. It was noticed that during catalytic pyrolysis, the quantity of H₂ obtained was more (19.12%) in contrast to thermal pyrolysis and could be attributable to the influence of silver nano particles towards the enhancement in hydrogen gas production. The liquid hydrocarbon obtained during the catalytic distillation was blended with diesel in the ratio 20:80 in the compression ignition (CI) engine. The quality of the blended bio oil was assessed from brake thermal efficiency (BTE), brake specific fuel consumption (BSFC) and emission of nitrogen oxides (NO_X), carbon monoxide (CO) and unburnt hydrocarbon (UHC). At full load, the diesel fuel emitted 1780 ppm of NO_x while the diesel blended with bio oil emitted only 1510 ppm which was 15.17% less than the diesel oil which proved its eco-friendly nature. In future, the bio oil obtained from catalytic pyrolysis can be used as a blend for diesel oil, since it reduces NO_x emission and replaces 20% of diesel oil.     

Non-catalytic and catalytic pyrolysis of Ulva prolifera macroalgae for production of quality bio-oil

Pyrolysis of Ulva prolifera macroalgae (UM), an aquatic biomass, was carried out in a fixed-bed reactor in the presence of three zeolites based catalysts (ZSM-5, Y-Zeolite and Mordenite) with the different catalyst to biomass ratio. A comparison between non-catalytic and catalytic behavior of ZSM-5, Y-Zeolite and Mordenite catalyst in the conversion of UM showed that is affected by properties of zeolites. Bio-oil yield was increased in the presence of Y-Zeolite while decreased with ZSM-5 and Mordenite catalyst. Maximum bio-oil yield for non-catalytic pyrolysis was (38.5 wt%) and with Y-Zeolite catalyst (41.3 wt%) was obtained at 400 °C respectively. All catalyst showed a higher gas yield. The higher gas yield might be attributed to that catalytic pyrolysis did the secondary cracking of pyrolytic volatiles and promoted the larger small molecules. The chemical components and functional groups present in the pyrolytic bio-oils are identified by GC–MS, FT-IR, ¹H-NMR and elemental analysis techniques. Phenol observed very less percentage in the case of non-catalytic pyrolysis bio-oil (9.9%), whereas catalytic pyrolysis bio-oil showed a higher percentage (16.1%). The higher amount of oxygen present in raw biomass reduced significantly when used catalyst due to the oxygen reacts with carbon and produce (CO and CO₂) and water.     

Catalytic pyrolysis of biomass: Effects of pyrolysis temperature,sweeping gas flow rate and MgO catalyst

Cotton seed, as a biomass source, is pyrolysed in a tubular fixed-bed reactor under various sweeping gas (N₂) flow rates at different pyrolysis temperatures. In the non-catalytic work, the maximum bio-oil yield was attained as 48.30% at 550 °C with a sweeping gas flow rate of 200 mL min⁻¹. At the optimum conditions, catalytic pyrolysis of biomass samples was performed with various amounts of MgO catalyst (5, 10, 15, and 20 wt.% of raw material). Catalyst addition decreased the quantity of bio-oil yet increased the quality of bio-oil in terms of calorific value, hydrocarbon distribution and removal of oxygenated groups. It was observed that increasing the amount of catalyst used, decreased the oil yields while increased the gas and char yields. Bio-oils obtained at the optimum conditions were separated into aliphatic, aromatic and polar sub-fractions. After the application of column chromatography, bio-oils were subjected into elemental, FT-IR and ¹H NMR analyses. Aliphatic sub-fractions of bio-oils were analyzed by GC–MS. It was deduced that the fuel obtained via catalytic pyrolysis mainly consisted of lower weight hydrocarbons in the diesel range. Finally, obtained results were compared with petroleum fractions and evaluated as a potential source for liquid fuels.     

Energy production from the pyrolysis of waste biomasses

Pyrolysis of waste biomasses was carried out at the temperatures of 450 and 500°C by heating at 5°C min^?1. Products were collected from emitted gases in a nitrogen purge stream; condensable liquids in the gases were collected by condensation. Gaseous, condensed liquid products and residual solids were collected and analyzed. Condensates were extracted with ether to recover the bio oils (BOs). The maximum liquid yield was obtained from the pyrolysis of soybean oil cake (SBOC) at 500°C with a yield of 60% ca. The BO was higher in the case of SBOC than that of sunflower oil cake (SFOC) at the temperatures of 450 and 500°C. With increasing temperature, bio char yield from the pyrolysis of SFOC decreased, while the liquid yield increased. The increase in temperature did not significantly affect the product distribution for the pyrolysis of SBOC. The compositions of BOs were similar for both SBOC and SFOC. Phenols, phenol derivatives including guaiacols and alkyl‐benzenes were the most common and predominant in BOs from both the pyrolysis of SBOC and SFOC. Carbon dioxide was the major gas product for both SBOC and SFOC. Copyright © 2008 John Wiley & Sons, Ltd.     

Characterization of bio-oils from the fast pyrolysis of white oak and sweetgum

Conversion of lignocellulosic biomass into bio-oil through fast pyrolysis process is considered one of the promising routes to supplement conventional fossil oil. Future bio-refineries require production large amounts of bio-oil from several biomass types. Characterization of the produced bio-oils is important to determine their suitability as bio-refinery feedstock. In this study, bio-oils were produced from white oak and sweetgum woods in an auger reactor at 450°C. The yields of char, liquid, and gas were calculated. The physical characterization of bio-oils was performed based on the investigation of different properties, such as pH, density, viscosity, water content, acid value, and molecular weight distribution of bio-oil components. The chemical compositions of the bio-oils were also investigated by gas chromatography/mass spectrometry and Fourier transform infra-red analyses. The physicochemical properties of the produced bio-oils were comparable to those obtained from similar woody biomass and the oils were suitable for fuel production.     

Comparison of catalytic and noncatalytic pyrolysis and product yields of some waste biomass species

The products obtained by fast pyrolysis of biomass can be used as an energy source or chemical raw material. In this study, samples of hazelnut shells, tea bush, and hazelnut knot selected as waste biomass were from the cities of Trabzon and Rize in the Eastern Black Sea Region. Firstly, the waste biomass samples were granulated into four different particle sizes by milling and sieving operations. Fast pyrolysis of the samples with specific mixing rates was carried out in a fixed bed reactor. Additionally, 2 wt% vanadium (V) oxide (V₂O₅) was used as catalyst to maximize the yield of pyrolysis liquid products. The influence of temperature, heating rate, and particle size on fast pyrolysis yields under both catalytic and noncatalytic conditions were investigated and compared. While the amount of liquid product increased with the addition of catalyst, the amount of solid products decreased. It has been found that the temperature and heating rate parameters are very effective in liquid product yield. In all experiments, the maximum liquid yield was acquired at the same heating rate of 450°C min^?1 and the temperature of 450°C with particle size of 0.5 to 1.0 mm. The maximum pyrolysis liquid (bio‐oil) was obtained with catalytic pyrolysis, and this value was 60.58 wt%.     

Integrated process of coal pyrolysis and CO2 reforming of methane with and without using dielectric barrier discharge plasma

The integrated processes of Shenmu subbituminous coal pyrolysis and CO₂ reforming of methane over catalyst (Ni/SiO₂) with and without using dielectric barrier discharge plasma (ICCP and ICCC) were carried out to check the effectiveness of the integrated process on improving the tar yield of coal pyrolysis. The effects of the pyrolysis temperature and time on product yields were investigated. The results indicate that both the ICCC and ICCP have an effect on increasing the tar yield compared with coal pyrolysis under N₂ or H₂. The tar yield increases with the increase of pyrolysis temperature and time in the ICCC, while relatively lower pyrolysis temperature and shorter pyrolysis time is preferable in the ICCP. The highest tar yield is 24.8 wt% at 600°C for 22 min in the ICCC and that is 23.7 wt% at 500°C for 7 min in the ICCP.     

Study of Mo-based sepiolite catalyst on depolymerization of lignin under supercritical ethanol

A unique Mo/SEP catalyst using low-cost and available sepiolite as support was prepared by wet impregnation method. All catalyst performances of the Mo/SEP catalysts were studied in process of lignin catalytic depolymerization (LCD) under supercritical ethanol with nitrogen pressure, and the effects of reaction temperatures and reaction time on LCD process were also investigated. X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy techniques were used to characterize the structural characteristics of the fresh and spent catalysts, and gas chromatography-mass spectrometry (GC-MS) was employed to analyze the compositions of the obtained liquid product. The results indicated that Mo/SEP catalyst had unique performance for LCD, and the highest soluble fraction yield of petroleum ether of 47.6% and yield of liquid product of 63.5% were obtained with constantly reacting for 4 hours at 290°C and 6.5 MPa N₂. In addition, relevant characterizations demonstrated that the reaction temperature could cause the phase transfer of catalyst and change of Mo⁶⁺ to Mo⁵⁺ species. The conversion degree of Mo⁶⁺ to Mo⁵⁺ was the major reason responding for the catalytic performance of Mo/SEP catalyst during LCD process.     

Conversion of waste tires to liquid products via sodium carbonate catalytic pyrolysis

This study deals with the pyrolysis of waste tires supplied from the transport industry. The base material of tire is latex, which is derived from natural rubber trees. Nowadays rubber (Hevea brasiliensis) is a fast-growing tropical tree crop, which is being cultivated for latex and ultimately for tire production. Waste tires can be recycled for energy and valuable materials in many ways; however tire burning is the most common practice for heat generation. In recent years, the catalytic conversion of waste tires through pyrolysis into liquid, solid, and gas products was investigated. Liquids product was produced from the catalytic pyrolysis of waste tire at high temperature (up to 600°C) using sodium carbonate (Na₂CO₃) as a catalyst. Thermo-physical characteristics of the produced liquid samples showed that up to 85% of the produced oil can be used in internal combustion engines. Gasoline and diesel fuel contents in the liquid products are 45% and 40%, respectively. The gas chromatographic (GC) analysis of the volatile fraction of pyrolysis products showed styrene (28.1%) and butadiene (10.7%) as dominant compounds. The gaseous phase includes C₁–C₄ hydrocarbons (4.8%) and the liquid phase includes C₅–C₈ hydrocarbons (6.5%) of the total products.     

Enhanced activity of NiZrBEA catalyst for upgrading of biomass pyrolysis vapors to H2-rich gas

The main objective of these studies was development of competitive catalyst for the upgrading of biomass pyrolysis vapors to H₂-rich gas. The performed experiments were devoted to determination of the effect of incorporation of zirconium into the structure of BEA zeolite on the performance of NiBEA in the mentioned process. Moreover, the most important parameters responsible for the increased activity of NiZrBEA catalyst in comparison to nickel supported on parent zeolite have been identified. The activity of synthesized catalysts was tested in two step fixed bed quartz reactor. Firstly, cellulose or pine were heated to the 500 °C in order to decompose lignocellulosic feedstock. Then, formed pyrolysis vapors were directed through catalyst bed (700 °C) where their upgrading took place. The obtained results revealed that an introduction of zirconium in the structure of BEA zeolite allowed for the increase in the efficiency of Ni catalyst in the formation of H₂-rich gas. It was related to the increase in pore volume of the synthesized materials, formation of smaller nickel oxide crystallites and creation of the catalysts with moderate acidity.     

Effect of CO2 atmosphere on biomass pyrolysis and in-line catalytic reforming

To enhance the conversion efficiency of biomass CO₂ gasification and decrease tar, the experimental study of biomass pyrolysis and in-line catalytic CO₂ reforming (BPy-ILCCR) were investigated in a two-stage reactor. The prepared K-Ni/Al catalyst exhibits superior catalytic activity for gas products in BPy-ILCCR. Results show that both CO₂ concentration and temperature promote the rise of the gas production, but the increase slows down when CO₂ concentration is more than 40 vol%. At 700°C, the gas yield and X_c can reach 0.83 g/g-bio and 92.4%, respectively (40 vol% CO₂, 3 g catalyst). The comparative study indicates that steam is slightly better for reducing liquid product under the same concentration of CO₂ and H₂O, and the X_c at 80 vol% CO₂ can reach 93.9%, close to the value obtained at 40 vol% H₂O. Moreover, there exist similar quantities of coke deposition on the catalyst under the CO₂ and H₂O atmosphere.