One-step synthesis of biochar-supported potassium-iron catalyst for catalytic cracking of biomass pyrolysis tar

In this work, K–Fe bimetallic catalyst supported on porous biomass char was synthesized via a one-step synthesis method by pyrolysis of biomass (peanut shells) after impregnation of a small amount of potassium ferrate (PSC–K₂FeO₄), and was evaluated for the cracking of biomass pyrolysis tar. Control experiments using the pure char (PSC) and char-supported catalysts after impregnation of KOH (PSC–KOH) and FeCl₃ (PSC–FeCl₃) were also performed for comparison. The as-prepared PSC-K₂FeO₄ possessed a porous structure with the dispersion of particles/clusters of Fe metal, K₂CO₃ and KFeO₂ on the char support. Tar cracking experiments showed that the PSC-K₂FeO₄ exhibited excellent catalytic activity on the cracking of biomass pyrolysis tar in the temperature range of 600–800 °C, and the obtained tar conversion efficiencies were obviously higher than that in the control experiments, particularly at relatively lower temperatures (600 and 700 °C). The yields of combustible gas compounds including CO, H₂ and CH₄ increased significantly using PSC-K₂FeO₄ as the catalyst due to the enhanced tar cracking and reforming reactions. The porous structure and the active crystal structures of the spent catalyst were well retained, indicating the potential for efficient and long-term utilization of the catalyst in tar cracking. PSC-K₂FeO₄ exhibited excellent reusability during the five times reuse under the same conditions without regeneration, which showed almost no obvious decrease in the tar conversion efficiency and gas yields.     

Exergy analysis of biomass staged-gasification for hydrogen-rich syngas

Using Aspen Plus simulations, exergy analyses of hydrogen-rich syngas production via biomass staged-gasification are carried out for three configurations, namely, staged-gasification with pyrolysis gas combustion and char gasification (C-1), staged-gasification with pyrolysis gas reforming and char gasification (C-2), and staged-gasification with pyrolysis gas reforming and char combustion (C-3). The results show that, for the gasification and reforming processes, the exergy loss of pyrolysis gas with tar reforming is less than that of char gasification. As for the system, it is conducive to generating hydrogen by making full use of the hydrogen element (H) in biomass instead of the H in water. The benefits of C-1 are that it removes tar and produces higher yield and concentration of hydrogen. However, C-2 is capable of obtaining higher exergy efficiency and lower exergy loss per mole of H₂ production. C-3 theoretically has greater process performances, but it has disadvantages in tar conversion in practical applications. The appropriate gasification temperature (T_G) are in the range of 700–750 °C and the appropriate mass ratio of steam to biomass (S/B) are in the range of 0.6–0.8 for C-1 and C-3; the corresponding parameters for C-2 are in the ranges of 650–700 °C and 0.7–0.8, respectively.     

Yields of pyrolysis products from refuse-derived fuel

Pyrolysis yields and gas characteristics must be studied to control pollution caused by waste-energy recycling and to develop a refuse-derived fuel technology. In this study, refuse-derived fuel pyrolysis experiments were performed in a high-temperature tube furnace. The effects of the final pyrolysis temperature, material mixture ratio, and pyrolysis rate on the yields of pyrolysis products, including gas, tar, and semi-coke, were studied. The volume fractions of the pyrolysis gas components (H₂, CO, CH₄, and CO₂) of the samples were also detected. Results showed that with increased final temperature, the tar and gas yields increased but the semi-coke yield decreased. The volume fractions of the components had the following trends: H₂ increased, CO initially decreased and then increased, CH₄ initially increased and then decreased, and CO₂ decreased. With decreased biomass, the tar yield decreased and then increased, whereas the semi-coke and gas yields increased and then decreased. Compared with slow pyrolysis, fast pyrolysis decreased the tar yield by 9.13%, increased the gas yield by 7.45%, increased the CO and CH₄ volume fractions, and decreased the CO₂ volume fraction.     

Influence of calcium promoter on catalytic pyrolysis characteristics of iron-loaded brown coal in a fixed bed reactor

The Fe–Ca catalysts in catalytic pyrolysis of brown coals were studied to investigate the catalytic activity of the Fe–Ca in a fixed-bed reactor. Experimental results showed the maximum yields of the light aromatic hydrocarbons (LAHs) were 5.90 wt% (0.88 wt% of benzene, toluene and xylene ‘BTX’, 4.10 wt% of phenol and cresol ‘PC’ and 0.92 wt% of naphthalene) when the 1.5% Ca was added into 5% Fe-loaded brown coal. The yields of water and gas significantly reduced, the tar yield gradually increased with increasing heating rate. The characterization results indicated that when calcium promoter was impregnated with iron, Ca₂Fe₂O₅, CaO, Fe₂O₃ and α-Fe were formed on the surface of the coal char, Ca₂Fe₂O₅ and α-Fe decomposed polyaromatic tar, CaO and Fe₂O₃ accelerated water gas shift reaction to enhance the H₂ yield, the Fe₂O₃ and Ca₂Fe₂O₅ could be reduced to α-Fe by volatiles (C, CO and H₂) under high temperature catalytic pyrolysis. The synergistic effects between iron and calcium improved brown coal pyrolysis and the volatiles such as free radical fragments were further pyrolyzed, indicating that Fe–Ca catalysts inhibited α-Fe deactivation by tar and carbon deposition, thus promoting brown coal pyrolysis and formation of CO_x, H₂ and LAHs.     

基于三组分的生物质快速热解实验研究

在管式炉内对纤维素、半纤维素和木质素进行热解实验研究,考察热解温度对于热解产物(焦炭、焦油和不凝性气体)分布的影响。实验结果表明:随温度的升高,三组分热解产生的焦炭产量不断降低,气体产量不断增加,焦油产量先升后降,存在一最佳反应温度。不凝气体组分随温度变化有不同的变化趋势,焦油的组分也不同。选取稻秸和玉米秸秆为原料,按照这两种生物质中三组分含量的不同将纤维素、半纤维素和木质素的产物进行叠加,并与稻秸和玉米秆的热解实验结果作对比,分析三组分含量对于热解产物的影响。结果表明:按照三组分叠加的方法来考察生物质的热解在一定程度上是可行的,产物产量的总体趋势一致,在产量上稍有差异。     

Synergistic effects during co-pyrolysis of biomass and plastic: Gas,tar, soot,char products and thermogravimetric study

Synergistic effects of biomass and plastic co-pyrolysis on gas, tar, soot and char production and pyrolysis kinetics were studied using a fixed-bed reactor and a thermogravimetric analyzer, respectively. These pyrolysis products' yields and compositions were measured during the individual pyrolysis of biomass and plastic at 800–1100 °C, and synergistic effects were explored under non-sooty (900 °C) and sooty (1100 °C) conditions. Results shows that the soot starts to form from tar at 900–1000 °C for both biomass and plastic and that the soot from plastic pyrolysis is of greater yield and size than the biomass pyrolysis. Under non-sooty conditions, the synergistic effect of co-pyrolysis results in higher char yields but lower tar yields, while under sooty conditions co-pyrolysis inhibits the gas and soot formation, resulting in higher tar yields and different soot morphologies. The synergistic effect observed by the thermogravimetric analysis agrees with that in a fixed-bed reactor.     

Pyrolysis characteristics and Cr speciation of chrome-tanned leather shavings: influence of pyrolysis temperature

Chrome-tanned leather shavings (CTLS) are a type of solid waste generated from the leather industry. In this study, the pyrolysis experiment of CTLS was conducted in a high-temperature tubular furnace reactor at different temperatures. The results showed that the pyrolysis temperature highly affected the product yields. The tar generated from the CTLS pyrolysis presented a wide distribution of pyrolytic compounds, and nitrogenated derivatives were the major group. The scanning electronic microscopy (SEM) investigation showed that a continuous structure of irregular but rather uniformly distributed interconnected pores of the chars. Cr was found to exist in the char as its reduced state (Cr³⁺). This study provided basic data for the determination of pyrolysis temperatures of CTLS targeting different products.     

生物质炭催化裂解焦油的实验研究

通过实验方法研究了生物质炭对生物质热解焦油的催化特性。通过分析焦油裂解率在催化剂及其重量、蒸汽加入量和加入方式、氮气流量等条件下的变化可知:在蒸汽条件下,生物质炭对焦油有显著的催化裂解效果,最高焦油转化率可达96.1%。通过对实验条件下裂解产物、裂解气体积分数的分析可知,生物质炭和蒸汽可以促进热解产物里面的可凝结相转化为不可凝结的气体,并且导致气体组分体积分数的变化。裂解气中氢气产量增加较快,最高可达裂解气体积的50.2%。     

Products properties from fast pyrolysis of enzymatic/mild acidolysis lignin

The conversion of enzymatic/mild acidolysis lignin (EMAL) isolated from moso bamboo to aromatic chemicals by fast pyrolysis were investigated under nitrogen atmosphere and atmospheric pressure. The experiment of EMAL pyrolyzing was set on a tubular reactor furnace at the temperature levels of 400, 500, 600, 700, 800 and 900 °C, and the products derived from EMAL pyrolyzing were classified into three-phase of gas, condensed liquid (tar), and solid (char). The chemical structure and surface morphology of solid product were characterized by fourier transforms infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the ingredients of gas product and liquid (tar) were analyzed with gas chromatography (GC) and gas chromatography/mass spectrometer (GC/MS). The analysis results indicated that the yield of char decreased rapidly from 43% to 28% with an increase of temperature, and the yield of gas product increased gradually from 6% to 26%, and the yield of tar attained a maximum at 700 °C. SEM showed that char took on lots of vesicles that resulted from the gas release from EMAL pyrolyzing. The ingredients of gas product were comprised of H₂, CO, CO₂ and light hydrocarbons (CH₄, C₂H₄ and C₂H₆), and the amount of H₂, CO were high. Besides a huge amount of phenols, the tar contained aromatic hydrocarbons, chain hydrocarbons, monoaromatic aromatic hydrocarbons and some ketones, and the carbon number of chemical compounds were C₆–C₁₀.     

The influence of temperature and heating rate on the slow pyrolysis of biomass

The slow pyrolysis of biomass in the form of pine wood was investigated in a static batch reactor at pyrolysis temperatures from 300 to 720°C and heating rates from 5 to 80 K min⁻¹. The compositions and properties of the derived gases, pyrolytic oils and solid char were determined in relation to pyrolysis temperatures and heating rates. In addition, the wood and the major components of the wood—cellulose, hemicellulose and lignin—were pyrolysed in a thermogravimetric analyser (TGA) under the same experimental conditions as in the static batch reactor. The static batch reactor results showed that as the pyrolysis temperature was increased, the percentage mass of solid char decreased, while gas and oil products increased. There was a small effect of heating rate on product yield. The lower temperature regime of decomposition of wood showed that mainly H₂O, CO₂ and CO were evolved and at the higher temperature regime, the main decomposition products were oil, H₂O, H₂, hydrocarbon gases and lower concentrations of CO and CO₂. Fourier transformation infra-red spectroscopy and elemental analysis of the oils showed they were highly oxygenated. The TGA results for wood showed two main regimes of weight loss, the lower temperature regime could be correlated with the decomposition of hemicellulose and the initial stages of cellulose decomposition whilst the upper temperature regime correlated mainly with the later stages of cellulose decomposition. Lignin thermal decomposition occurred throughout the temperature range of pyrolysis.     

Inhibition of steam gasification of biomass char by hydrogen and tar

The influence of hydrogen and tar on the reaction rate of woody biomass char in steam gasification was investigated by varying the concentrations in a rapid-heating thermobalance reactor. It was observed that the steam gasification of biomass char can be separated into two periods. Compared with the first period, in the second period (in which the relative mass of remaining char is smaller than 0.4) the gasification rate is increased. These effects are probably due to inherent potassium catalyst. Higher hydrogen partial pressure greatly inhibits the gasification of biomass char in the first and second periods. By calculating the first-order rate constants of char gasification in the first and second periods, we found that the hydrogen inhibition on biomass char gasification is caused by the reverse oxygen exchange reaction in the first period. In the second period, dissociative hydrogen adsorption on the char is the major inhibition reaction. The influence of levoglucosan, a major tar component derived from cellulose, was also examined. We found that not only hydrogen but also vapor-phase levoglucosan and its pyrolysates inhibited the steam gasification of woody biomass char. By mixing levoglucosan with woody biomass sample, the pyrolysis of char proceeds slightly more rapidly than with woody biomass alone, and gas evolution rates of H₂ and CO₂ are larger in steam gasification.     

Multifaceted analysis of products from the intermediate co-pyrolysis of biomass with Tetra Pak waste

This study investigates the co-pyrolysis of two types of biomass (pine bark and wheat straw) with Tetra Pak waste (TPW). The experiments were performed using a fixed-bed reactor equipped with an innovative system, where a sample was rapidly heated to 600 °C before being rapidly cooled. The multifaceted analysis included the determination of the i) physical and chemical properties of the feedstocks and chars, ii) aqueous phase, tars, and waxes, iii) char ignition and burnout temperature, iv) chemical composition of gas, and v) distribution of carbon and hydrogen in the obtained products. The results showed that the addition of TPW to the both types of biomass significantly reduced the char mass and aqueous phase, decreased the carbon, hydrogen, and nitrogen contents of the char, and increased the wax and tar yields retained in the water cooler. Different organic compounds such as alkenes, aromatic hydrocarbons, and acids were found in tars and waxes. The chemical composition of the released gases was detected in situ (by a flue-gas analyser) and ex-situ (using gas chromatography). Changes in the concentrations of H₂, CH₄, CO, CO₂, and C2–C4 were observed. The addition of Tetra Pak to the two types of biomass had an evident and positive effect on the hydrogen content of the pyrolysis gas.     

Experimental investigation of pyrolysis process of woody biomass mixture

This paper describes an experimental investigation of pyrolysis of woody biomass mixture. The mixture consists of oak, beech, fir, cherry, walnut and linden wood chips with equal mass fractions. During the experiment, the sample mass inside the reactor was 10 g with a particle diameter of 5-10 mm. The sample in the reactor was heated in the temperature range of 24-650℃. Average sample heating rates in the reactor were 21, 30 and 54 ℃/min. The sample mass before, during and after pyrolysis was determined using a digital scale. Experimental results of the sample mass change indicate that the highest yield of pyrolytic gas was achieved at the temperature slightly above 650℃ and ranged from 77 to 85%, while char yield ranged from 15 to 23%. Heating rate has sig- nificant influence on the pyrolytic gas and char yields. It was determined that higher pyrolysis temperatures and heating rates induce higher yields of pyrolytic gas, while the char mass reduces. Condensation of pyrolytic gas at the end of the pyrolysis process at 650℃ produced 2.4-2.72 g of liquid phase. The results obtained represent a starting basis for determining material and heat balance of pyrolysis process as well as woody biomass pyrolysis equipment.     

Steam gasification of Miscanthus X Giganteus with olivine as catalyst production of syngas and analysis of tars (IR, NMR and GC/MS)

Steam gasification of Miscanthus X Giganteus (MXG) at high heating rate in a fluidised bed reactor with the use of olivine as catalyst was investigated. The effects of temperature (815-880 °C) on the yields and the compositions of syngas and tars were determined. The experimental results show that the gas yields and the content of H₂ increase with the temperature, while the yields of tar, char and the content of CO, CO₂ and CH₄ in the product gas decrease. Noteworthy is that about 1.1 m³ of dry gas (at ambient conditions) per kg of dry ash free biomass were obtained with about 46% of H₂ and 24% of CO by volume at 880 °C.The tars composition was determined by FTIR, NMR and GC/MS. The identification of different compounds shows mainly the presence of simple molecules. This may be facilitating the possibility of complete tar reforming process (hot gas cleaning), to improvement of the syngas yield and the decrease of the formation of pollutants.     

Olive residues (cuttings and kernels) rapid pyrolysis product yields and kinetics

A study of pyrolysis of olive residues (cuttings and kernels) at a temperature range from 300 to 600°C, has been carried out. The experiments were performed in a captive sample reactor at atmospheric pressure under helium. The yields of the derived gases, pyrolytic liquids and char were determined in relation to pyrolysis temperature, at heating rates of about 200°C/s.As the pyrolysis temperature was increased the percentage mass of char decreased whilst gas and oil products increased. The oil products increased to a maximum value of ∼30 wt% of dry biomass at about 450–550°C. The major gaseous products are CO and CO₂.A simple first order kinetic model has been applied to the evolution of total losses and gases. Kinetic parameters have been estimated and compared with other reported similar data.     

Hydrogen production by biomass gasification in a fluidized-bed reactor promoted by an Fe/CaO catalyst

Biomass gasification for hydrogen production was performed in a continuous-feeding fluidized-bed with the use of Fe/CaO catalysts. The relationship between catalyst properties and biomass gasification efficiencies was studied. The findings indicated that only CaO was involved in the enhancement of char gasification, resulting in an increased hydrogen production. However, CaO was also easily deactivated by biomass tar. The characterization results indicated that when CaO was impregnated with Fe, Ca₂Fe₂O₅ formed on the surface of the support. Ca₂Fe₂O₅ decomposed polyaromatic tar but was not effective in char gasification. The synergistic effects between Fe and CaO that effectively enhanced biomass gasification mainly involved combustion and pyrolysis, and the biomass gasification products, i.e., char and tar, were further gasified, indicating that tailor-made Fe/CaO catalysts prevented CaO deactivation by tar, thus promoting biomass gasification and hydrogen production.     

Utilization of pyrolytic oil and hydrogen enriched syngas from single feedstock (delonix regia) through pyrolysis process and its influence on performance and emission characteristics in CI engine

The main objective of the present investigation is to conduct the performance, combustion and emission analysis of CI engine operated using hydrogen enriched syngas (pyrolytic gas) and biodiesel (pyrolytic oil) as dual fuel mode condition. Both the pyrolytic oil and syngas is obtained from single feedstock delonix regia fruit pod through pyrolysis process and then pyrolytic oil is converted into biodiesel through esterification. Initially biomass is subjected to thermal degradation at various pyrolysis temperature ranges like 350–600 °C. During the pyrolysis process syngas, pyrolytic oil and char are produced. The syngas is directly used in the CI engine and pyrolytic oil is converted into biodiesel and then used in the CI engine. The pyrolytic oil and syngas is subjected to FTIR and GC/TCD analysis respectively. The syngas analysis confirms the presence of various gases like H₂, CH₄, CO₂, CO and C₂H₄ in different proportions. The various proportions of the syngas is mainly depending upon the reactor temperature and moisture content in the biomass. The syngas composition varies with increase in the temperature and at 400 °C, higher amount of hydrogen is present and its composition are H₂ 28.2%, CO is 21.9%, CH₄ is 39.1% and other gases in smaller amounts. The biodiesel of B20 and syngas of 8lpm produced from the same feedstock are considered as test sample fuels in the CI engine under dual fuel mode operation to study the performance and emission characteristics. The study reveals that BTE has slight increase than diesel of 1.5% at maximum load. On the another hand emission like CO, HC and smoke are reduced by 15%,25% and 32% respectively at full load condition, whereas NO_x emission is increased at all loads in the range of 10–15%. Therefore B20+syngas of 8lpm can be used as an alternative fuel in CI engine without any modification and major products from pyrolysis process with waste biomass is fully used as fuel in the CI engine.     

Reduction of primary tar vapor from biomass by hot char particles in fixed bed gasification

This study investigated the reduction of primary tar vapor from biomass pyrolysis over a bed of hot char particles, focusing on the effect of different operating conditions and char properties. The char samples were prepared from wood, paddy straw, palm kernel shell, and activated carbon. The primary tar was produced from fir wood by pyrolysis at 500 °C and passed through a reactor filled with char particles with different lengths and temperatures.The tar cracking reactions became active above 700 °C, and the presence of hot char particles promoted more tar reduction compared with thermal cracking alone. The mass yield of the primary tar was reduced from 24.8% by pyrolysis to 13.7% by thermal cracking at 800 °C, and further to 7.7% by hot char particles in a reactor volume of 1.48 cm³/g_wood. In terms of carbon yield, these values correspond to 32.1%, 19.9% and 11.8%, respectively. The tar with smaller molecular weights was quickly decomposed to gases, whereas the heavy tar was resistant to cracking, even when the reactor volume was increased to 6.90 cm³/g_wood. The tar cracking behaviors were similar for four char types despite differences in microscopic surface areas, pore-size distributions, and inorganic contents. The results suggest that creating a tar-cracking zone using char particles situated between the pyrolysis and gasification zones could be helpful in converting the primary tar vapor in a downdraft fixed-bed gasifier, but the degree of conversion is not high enough to eliminate tar issues completely.     

Numerical simulation on biomass-pyrolysis and thermal cracking of condensable volatile component

We studied the physical and chemical properties of the condensable volatiles of biomass pyrolysis products. We redefine the liquid product and divide the condensable volatiles into two categories, biomass oil and tar, the latter of which comes from the secondary pyrolysis or cracking reaction of the former. We further establish a kinetic model of biomass pyrolysis and secondary cracking. The chemical reaction kinetics equation and heat transfer equation are coupled to simulate the biomass pyrolysis process. For biomass solid particles, the model not only considers the initial reaction of biomass and secondary cleavage reaction of condensable gas, but also introduces a reaction mode in which biomass oil is converted into tar. When the pyrolysis temperature is below 500 °C, the pyrolysis products are essentially biomass oil. However, when the pyrolysis temperature exceeds 500 °C, the biomass oil gradually converts into tar. The model also considers characteristics of the reaction medium (porosity, intrinsic permeability, thermal conductivity) and the unsteady gas phase process based on Darcy's law of velocity and pressure, heat convection, diffusion, and radiation transfer. We analyze the relationships among the internal temperature of the particles, particle size and position, mass fraction of the reactants and products, the gas mixture, the production share of tar and biomass oil, and the relationship between gas pressure and time. The results show that the effects of the secondary cracking reaction and internal convective flow in the biomass pyrolysis process are coupled because the flow field in the porous medium determines the volatile residence time and thus species that affect the secondary cracking reaction. The rate of volatile formation in the initial and secondary cracking reactions affects the pressure gradient and gas diffusion. Additionally, the endothermic effect influences the temperature field of the pyrolysis reaction but has no apparent effect on small particles whose chemical reaction is the control mechanism. For large particles, heat transfer inside the particles is the diffusion control mechanism and the chemical reaction on the particle surface is the speed control mechanism. Two peaks are observed in the pyrolysis gas mass proportion curve, which result from the consumption of biomass oil and tar as they flow toward hot surfaces. The first peak is the decomposition of biomass oil into non-condensable volatile matter and tar, and the second peak is the further cracking of tar into gas and coke at high temperature.     

Pyrolysis of sugarcane bagasse pretreated with sulfuric acid

Pyrolysis is a promising technique for the recovery of useful gas, tar, and solid products from biomass waste. However, the low tar yields obtained from lignocellulosic biomass are a significant drawback. To enhance tar yields, sugarcane bagasse, which is the most abundant agricultural waste in Fiji, was pretreated at ambient temperature and atmospheric pressure using various sulfuric acid (H₂SO₄) concentrations. Here, the ether bonds of cellulose, hemicellulose, and lignin were partially hydrolyzed. The pretreated samples were then pyrolyzed at 500 °C, and it was confirmed that H₂SO₄-pretreatment disrupted the bagasse cell structure, with the thermogravimetry and differential thermogravimetry results confirming that decomposition occurred at lower temperatures after pretreatment. In addition, tar yields were significantly enhanced from 5.6 wt% to 13.4 wt% for the untreated and 3 M H₂SO₄-pretreated samples respectively. The main components detected in this tar product were levoglucosan, andcellulose-and hemicellulose-derived products, whose proportions were increased following pretreatment. Thus, our work demonstrates that dilute acid pretreatment enhances tar production from sugarcane bagasse due to the production of shorter chain components via the partial hydrolysis of ether bonds.