Influence of feedstock properties and pyrolysis conditions on biochar carbon stability as determined by hydrogen pyrolysis

We produced 18 thermosequences of biochar from common feedstocks at ten temperatures from 300 to 900 °C to investigate their influence on carbon stabilization in biochar. Using hydrogen pyrolysis we were able to isolate the stable polycyclic aromatic carbon (SPAC) fraction that is likely to be resistant to mineralization on centennial timescales. SPAC formation was generally <20% of total organic carbon (TOC) at temperatures <450 °C and rises to >80% of TOC at temperatures above 600–700 °C depending on feedstock type. SPAC formation was retarded in feedstocks with high ash contents, and further retarded in those feedstocks when the final hold time at maximum pyrolysis temperature was reduced from one hour to 10 min. Given that aromatization of organic material in many feedstocks is usually completed by ca. 450 °C, the data suggests that a significant pool of aromatic biochar carbon exists in a ‘semi-labile’ form that may not be persistent on centennial timescales. For most feedstocks biochar yield and SPAC content are optimized at pyrolysis temperatures of 500–700 °C.     

Steam gasification of biochars derived from pruned apple branch with various pyrolysis temperatures

In this study, the gas production behavior from the steam gasification of the biochar derived from the pruned apple brunch was investigated using a fixed-bed reactor. The optimal biochar obtained at the pyrolysis temperature of 550 °C was gasified under different operating conditions for the hydrogen rich gas production. The experimental results indicated that high reaction temperature and high water flow rate were both beneficial to the hydrogen gas yield, but excess steam had a negative impact contrarily. Besides, the small size particles (0.5–1.0 mm) showed better performance in the hydrogen gas production at the low water flow rates (0.05–0.20 g/min); while the large size particles (1.0–2.8 mm) showed better performance at the high water flow rates (0.25–0.30 g/min). The suitable operating conditions for the gasification of the biochar were determined as the reaction temperature of 850 °C, water flow rate of 0.25 g/min, and particle size of 1.0–2.8 mm.     

Comparison between hydrogen-rich biogas production from conventional pyrolysis and microwave pyrolysis of sewage sludge: is microwave pyrolysis always better in the whole temperature range?

To investigate the influence of the pyrolysis temperature on biogas production from sewage sludge, conventional pyrolysis and microwave pyrolysis were carried out in the temperature range from 600 °C to 900 °C and all products were analyzed. With the temperature increasing, the product yields for conventional pyrolysis varied significantly, while those for microwave pyrolysis changed quite slightly. In conventional pyrolysis, the yield of H₂ increased from 1.26 mmol/g at 600 °C to 9.07 mmol/g at 900 °C, while it was varied only from 1.84 mmol/g to 3.67 mmol/g in microwave pyrolysis. Under microwave pyrolysis, a high ratio of H/C indicated that more hydrogen atoms converted directly to tar instead of being released into biogas, which was caused by side reactions (such as the hydrogen transfer reaction). More aromatic compounds in the tar during microwave pyrolysis illustrated that the hydrogen transfer reaction was enhanced by microwave at the higher temperatures. It has been found that the sludge microwave pyrolysis had some drawbacks for the hydrogen-rich biogas production, because it could promote some side reactions to suppress the H₂ production, especially the hydrogen transfer reaction.     

Enhancing the aromatic hydrocarbon yield from the catalytic copyrolysis of xylan and LDPE with a dual-catalytic-stage combined CaO/HZSM-5 catalyst

The high concentration of oxygenated compounds in pyrolytic products prohibits the conversion of hemicellulose to important biofuels and chemicals via fast pyrolysis. Herein CaO and HZSM-5 was developed to convert xylan and LDPE to valuable hydrocarbons by thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and elucidate the reaction mechanism were also investigated in detail. The results indicated that xylan/LDPE copyrolysis was more complicated than pyrolysis of the individual components. LDPE hindered the thermal decomposition and aromatic hydrocarbon formation from xylan at temperatures under 350 °C and had a synergistic effect at high temperatures. 50% LDPE was proven to be more beneficial than other percentages for the formation of monocyclic aromatic hydrocarbons. Simultaneously, the addition of CaO/HZSM-5 significantly reduced the reaction Ea and increased the reaction rate. CaO can effectively improve the deoxygenation and aromatization reaction, enhancing the yield and selectivity of aromatics to a certain extent. The maximum yield of hydrocarbons (96.01%), mono-aromatic hydrocarbons (88.53%) and S_BTXE (85.79%) were obtained at a CaO/HZSM-5 ratio of 1:2, a pyrolysis temperature of 450 °C, a catalytic temperature of 550 °C, a catalyst dose of 1:2 and a xylan-to-LDPE ratio of 1:1 via an ex situ process. The system was dominated by toluene, xylene and alkyl benzene. Diels-Alder reactions of furans and hydrocarbon pool mechanism of nonfuranic compounds improved aromatic formation. This study provides a fundamental for recovering energy and chemicals from pyrolysis of hemicellulose.     

Characterization of bio-oil and its sub-fractions from pyrolysis of Scenedesmus dimorphus

In the present study, microalgae Scenedesmus dimorphus was reported for pyrolysis in a fixed-bed reactor to determine the effects of temperature on products yield and the chemical compositions of the liquid and solid products. Experiments were carried out at a temperature range of 300–600 °C with heating rate of 40 °C/min and nitrogen flow rate of 100 ml/min. The yield of bio-oil was found to be maximum (39.6%) at the temperature of 500 °C and was further fractionated into n-hexane, toluene, ethyl acetate and methanol sub-fractions by using liquid column chromatography. Various characteristics of bio-oil and its sub-fractions were determined by ¹H NMR, FTIR and GC–MS. The biochar produced as a co-product can be a potential soil amendment with multiple benefits including soil fertility and C-sequestration. The present investigation suggests the suitability of Scenedesmus dimorphus as a potential feedstock for exploitation of energy and biomaterials through pyrolytic conversion.     

Effect of temperature on the fast pyrolysis of organic-acid leached pinewood; the potential of low temperature pyrolysis

In this paper, we have evaluated the potential of organic acid (mixture of acetic, formic and propionic acid) leaching of biomass and subsequent fast pyrolysis to increase the organic oil, sugars and phenols yield by varying the fluidized bed temperature between 360 °C and 580 °C (360 °C, 430 °C, 480 °C, 530 °C, and 580 °C). The pyrolysis of acid leached pinewood resulted in more organic oil and less water and residue compared to untreated pinewood over the whole temperature range. Below 500 °C the difference was most profound; for acid leached pinewood at 360 °C the organic oil was already 650 g kg⁻¹ pine with a sugar yield of 230 g kg⁻¹ pine. At this low pyrolysis temperature no bed agglomeration was observed for acid leached pine whereas at the higher temperatures tested agglomerates were found, which were identified to be clusters of fluidization sand glued together by sticky pyrolysis products (melt). Low reactor temperatures also favored the production of monomeric phenols, though their absolute yields remained low for both untreated and leached pine (maximum: 23 g kg⁻¹ pine, 80 g kg⁻¹ lignin). GPC, GC/MS and UV-fluorescence spectroscopy showed that acid leaching did not influence significantly the yield and molecular size of the aromatic fraction in the produced pyrolysis oils. Back impregnation of the removed AAEMs into leached biomass revealed that the effects of the applied acid leaching, both with respect to the product yields and bed agglomeration, can be mainly assigned to the removal of AAEMs.     

Effect of sawdust addition and composting of feedstock on renewable energy and biochar production from pyrolysis of anaerobically digested pig manure

Pyrolysis experiments were conducted on the separated solid fraction of anaerobically digested pig manure (SADPM). The aim of these experiments was to investigate the influence of (1) sawdust addition and (2) composting the feedstock, on the products of pyrolysis and on the net energy yield from the pyrolysis process. Mixtures of SADPM and sawdust were made to give the following treatments; manure only, 4:1(w/w) and 3:2(w/w). These mixtures were pyrolized at 600 °C both before and after aerobic composting. The yields of the biochar, bio-liquid and gas were influenced by the addition of sawdust to the SADPM and by composting of the feedstock. With the addition of sawdust, biochar and gas higher heating values (HHV) increased, while bio-liquid HHV decreased. More than 70% of the original energy in the feedstock remained in the biochar, bio-liquid and gas after pyrolysis, increasing as the proportion of sawdust increased. The HHV of the biochar decreased, while the HHV of the bio-liquid increased, after the feedstocks were composted. The energy balance showed that increasing the rate of sawdust addition to SADPM resulted in an increased net energy yield. The addition of a composting stage increased the net energy yield for the manure only feedstock only. However, with increasing sawdust addition, composting of the feedstock reduced the net energy yield.     

Co-hydrothermal gasification of microbial sludge and algae Kappaphycus alvarezii for bio-hydrogen production: Study on aqueous phase reforming

In this study, wastewater obtained from a sewage treatment plant was treated successively by using microbial consortium and macroalgae Kappaphycus alvarezii to generate microbial sludge and algal biomass. The production of green fuel was carried out via co-gasification of microbial sludge and macroalgae Kappaphycus alvarezii for a duration of 60 min, feedstock to solvent ratio (5 to 20 g of feedstock in 200 mL), sludge to algae ratio (ranging from 1:1 to 3:1) and temperature (300–400 °C) respectively. Maximum bio-hydrogen yield was 36.1% and methane yield was 38.4% at a temperature of 360 °C at a feedstock to solvent ratio of 15:200 g/mL and sludge to algae ratio of 2:1 individually. The liquid by product of co-gasification process was later subjected to photocatalytic reforming, resulted in an enhanced hydrogen composition of 61.25%.     

A comparative study on the quality of bioproducts derived from catalytic pyrolysis of green microalgae Spirulina (Arthrospira) plantensis over transition metals supported on HMS-ZSM5 composite

This study investigated three different types of catalysts: Ni/HMS-ZSM5, Fe/HMS-ZSM5, and Ce/HMS-ZSM5 in the thermochemical decomposition of green microalgae Spirulina (Arthrospira) plantensis. First, non-catalytic pyrolysis tests were conducted in a temperature ranges of 400–700 °C in a dual-bed pyrolysis reactor. The optimum temperature for maximized liquid yield was determined as 500 °C. Then, the influence of acid washing on bio-products upgrading was studied at the optimum temperature. Compared to the product yields from the pyrolysis of raw spirulina, a higher bio-oil yield (from 34.488 to 37.778 %wt.) and a lower bio-char yield (from 37 to 35 %wt.) were observed for pretreated spirulina, indicating that pretreatment promoted the formation of bio-oil, while it inhibited the formation of biochar from biomass pyrolysis. Finally, catalytic pyrolysis experiments of pretreated-spirulina resulted that Fe as an active phase in catalyst exhibited excellent catalytic activity, toward producing hydrocarbons and the highest hydrogen yield (3.81 mmol/gr spirulina).     

Optimization of the operating conditions for steam reforming of slow pyrolysis oil over an activated biochar-supported Ni–Co catalyst

Highly performing activated biochar-based catalysts were produced for steam reforming of slow pyrolysis oil. The raw biochar obtained from the slow pyrolysis step was physically activated with CO₂ at 700 °C and 1.0 MPa and then employed as support. Preliminary tests on steam reforming of acetic acid at 600 °C showed that using activated biochar-supported catalysts containing 10 wt % Ni and 7 wt % Co led to a conversion above 90% with a relatively slow deactivation rate. When a representative organic model compounds mixture was used as feed, relatively fast deactivation of the catalyst was observed, probably due to the adsorption of heavy organic compounds, which could subsequently react to form not easily desorbable reaction intermediates. However, the dual Ni–Co catalysts exhibited a good performance during the steam reforming of a real slow pyrolysis oil at 750 °C, showing long stability and a constant carbon conversion of 65%.     

Characterization of the physicochemical and structural evolution of biomass particles during combined pyrolysis and CO2 gasification

The combination of pyrolysis and CO₂ gasification was studied to synergistically improve the syngas yield and biochar quality. The subsequent 60-min CO₂ gasification at 800 °C after pyrolysis increased the syngas yield from 23.4% to 40.7% while decreasing the yields of biochar and bio-oil from 27.3% to 17.1% and from 49.3% to 42.2%, respectively. The BET area of the biochar obtained by the subsequent 60-min CO₂ gasification at 800 °C was 384.5 m²/g, compared to 6.8 m²/g for the biochar obtained by the 60-min pyrolysis at 800 °C, and 1.4 m²/g for the raw biomass. The biochar obtained above 500 °C was virtually amorphous.     

Comparison of pyrolysis and hydrothermal liquefaction of Chlamydomonas reinhardtii. Growth studies on the recovered hydrothermal aqueous phase

The production of bio-oil by pyrolysis with a high heating rate (500 K s⁻¹) and hydrothermal liquefaction (HTL) of Chlamydomonas reinhardtii was compared. HTL led to bio-oil yield decreasing from 67% mass fraction at 220 °C to 59% mass fraction at 310 °C whereas the bio-oil yield increased from 53% mass fraction at 400 °C to 60% mass fraction at 550 °C for pyrolysis. Energy ratios (energy produced in the form of bio-oil divided by the energy content of the initial microalgae) between 66% at 220 °C and 90% at 310 °C in HTL were obtained whereas it was in the range 73–83% at 400–550 °C for pyrolysis. The Higher Heating Value of the HTL bio-oil was increasing with the temperature while it was constant for pyrolysis. Microalgae cultivation in aqueous phase produced by HTL was also investigated and showed promising results.     

Non-isothermal pyrolysis of the mixtures of waste automobile lubricating oil and polystyrene in a stirred batch reactor

Kinetic tests on pyrolysis of the mixture of waste automobile lubricating oil (WALO) and polystyrene (PS) were carried out with a thermogravimetric analysis (TGA) technique at a heating rate of 0.5 °C/min, 1.0 °C/min and 2.0 °C/min in a stirred batch reactor. WALO and PS were mainly decomposed 400–455 °C and 370–410 °C, respectively. The mixture of WALO and PS, however, was decomposed between 355 °C and 470 °C, and decomposition proceeded in two broad steps. The apparent activation energies for the pyrolysis of WALO/PS mixture were in the range of 176 kJ mol⁻¹–369 kJ mol⁻¹ at various conversions of 1–100%. The effect of heating rate on the product distribution was studied. The carbon number distribution of the produced oil shifted slightly to light hydrocarbons with a decrease in heating rate. The selectivity of hydrocarbons corresponding to the styrene monomer was high for the pyrolysis of the WALO/PS mixture.     

The production of hydrogen gas from modified water hyacinth (Eichhornia Crassipes) biomass through pyrolysis process

In this study, the generation of hydrogen from synthesis gas through the pyrolysis of modified Water Hyacinth (Eichhornia Crassipes) biomass was investigated. The modified Water Hyacinth feedstocks were prepared by immersing its dried samples into Iron Chlorides (III) solution under different concentrations (0.5, 1, 1.5, and 2 M). After a 60 min pyrolysis at 540 °C, each created biochar sample also generates a different volume of synthesis gas depending on the properties of the feedstock that were applied to the system. In that manner, it is clear that the value of ferric chloride concentration plays an important role in the generating of synthesis gas. The study indicates that the increase of ferric chloride concentration may also raise the production of synthesis gas, and the amount of hydrogen as well. The result indicates that the 2WH sample (with 2 M of ferric chloride catalyst) exhibited the highest conversion for Water Hyacinth pyrolysis volatiles, with 280 mL of total gas production (42% of hydrogen included, 23% of carbon dioxide, 22% of carbon monoxide and 7% of methane). Therefore, the main objective of the work is achieved by revealing the influence of the metal catalyst over the production of gases via the pyrolysis. On the other hand, the fact that the Water Hyacinth can be utilized effectively also contributes greatly to the matter of environmental betterment.     

Steam reforming of simulated pre-reformed naphtha in a PdAu membrane reactor

Process intensification in a membrane reactor is an efficient and compact way to produce hydrogen. A methane-rich gas mixture that simulated the composition of pre-reformed naphtha (PRN; with a steam-to-carbon ratio of 2.7) was reformed at temperatures of 550 °C–625 °C and pressures up to 40 barg. The reactor contained commercial steam reforming catalyst and a 14.8 cm long, 2.6 μm thick Pd-1.8Au (wt. %) membrane on a porous alumina support. Methane conversions approaching 90% were obtained in the membrane reactor at a gas-hourly space velocity of 676 h^?1, compared to ≤30% conversion at the same conditions in conventional reactor mode (CM) without withdrawing hydrogen through the membrane. The results were compared to steam methane reforming (SMR) in the membrane reactor at similar conditions. The nitrogen leak through the membrane increased slowly during the testing, because of both pinhole formation and some leakage through the end seals.     

Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (E_a) for 5–80% conversions was 213 kJ mol⁻¹, and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C.     

Manufacturing gaseous products by pyrolysis of microalgal biomass

Algal biomass is considered as an alternative raw material for biofuel production. The search for new types of raw materials including high-energy types of microalgae remains relevant, since the share of motor fuels in the world energy balance remains consistently high (about 35%) with the oil price characterized by high volatility. The authors have considered the advantages of microalgae as raw materials for fuel production. Biochemical and thermochemical conversion are proposed as technologies for their processing. The paper presents the results of the study on the pyrolysis of the biomass of the blue-green microalgae/cyanobacterium Arthrospira platensis rsemsu 1/02-P clonal culture from the collection of the Research Laboratory of Renewable Energy Sources of the Lomonosov Moscow State University. The experimental investigation on the pyrolysis process of microalgal biomass has been carried out with the experimental setup made at the Institute of High Temperatures RAS in pure nitrogen 6.0 to create an oxygen-free medium with a linear heating rate of 10°С/min from room temperature to 1,000°С. The entire pyrolysis process has proceeded in the endothermic region. The specific values for solid residue, pyrolysis liquid and gaseous products have been experimentally determined. The following products have been manufactured by pyrolysis of microalgal biomass weighing 15 g: 1) char with a solid residue mass of 2.68 g, or 17.7% of MAB initial mass (while 9.3% of MAB initial mass has remained in the reactor); 2) pyrolysis liquid with a mass of 3.3 g, or 21.9% of initial mass; 3) noncondensable pyrolysis gases, 1.15 L. The specific volumetric gas yield (amount of gas released from 1 kg of RM) has amounted to 0.076 nm³/kg.In the paper, the analysis of the composition and specific volumetric yield of non-condensable pyrolysis gases produced in the pyrolysis process depending on temperature has been carried out. It is shown that the proportion of high-calorific components of the gas mixture (hydrogen, methane and carbon monoxide) increases with the temperature increase. The heating value assessment for the mixture of these gases has been performed as well.     

Artisanal and controlled pyrolysis-based biochars differ in biochemical composition,thermal recalcitrance,and biodegradability in soil

Biochar composition and stability is under intense research. Yet the question remains to what extent the current state-of-the-art applies to artisanally charred biomass in tropical regions. We compared kiln and drum based biochars with their counterpart controlled (at 400 °C) slow pyrolysis biochars from coconut shells, rice husks and Palmyra nutshell for their biochemical composition, thermal stability and biodegradability in soil. Thermal behavior of individual organic constituents was quantified by pyrolysis-field ionization mass spectroscopy (Py-FIMS). Comparison of the mass spectra demonstrated higher abundances of either phenols, lignin and carbohydrate monomers or of lipids in the artisanally produced biochars. Hence, relatively more untransformed plant matter was preserved by artisanal charring and also the thermal stability of carbohydrates, alkylaromatics and N-containing compounds was lower for all three feedstocks. This indicates lower prevailing temperatures compared to controlled pyrolysis biochar, at least in parts of the biomass charring in the kilns or drum. Nine-weeks biochar derived C mineralization upon soil incorporation revealed a relatively lower biological stability of the controlled pyrolysis biochars. The proportion of detected ion intensity from thermolabile lower mass signals (<400 °C, m/z < 250) was negatively correlated to the net-biochar derived C mineralization. We hypothesize this fraction to be composite and act both as a C-substrate and at the same time to hold unidentified substances inhibiting microbial activity. Compared to controlled pyrolysis biochar, traditionally charred biomass, i.e. the ‘biochar’ most likely to be actually applied to soil in developing countries, has a heterogeneous thermal and biochemical composition and unpredictable biological stability.     

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.     

Pretreated mesocarp fibre biochars as carbon fuel for direct carbon fuel cells

This work focuses on the effect of acid and alkali pretreatment of palm mesocarp fibre (PMF) on its fuel performance in a direct carbon fuel cell (DCFC). PMF is pretreated with acid and alkali in the range of 0.1 M–4 M and followed by pyrolysis to produce biochar fuel. Performance is evaluated in the DCFC at 750 °C, 800 °C, and 850 °C. This work reveals that 2.0 M HCl treated PMF biochar gives the lowest ash value (0.1 wt%) and the highest O/C ratio among all tested biochars. The acid pretreatment contributes to enhanced electrochemical reactivity of the PMF biochar, which gives a peak power density output of 11.8 mW cm^?2 at 850 °C in the DCFC. This obtained peak power density is higher than the power density of untreated biochar, recorded at a value of 0.70 mW cm^?2. The results indicate that reduced ash, the existence of oxygen functional groups, and porous fibrous structure have increased the electro-oxidation active sites of the pretreated biochar fuel in DCFC.