Pyrolysis Of Manure Research Articles

Suppression of carbon footprint through the CO2-assisted pyrolysis of livestock waste.

Concentrated animal feeding operation facility in modern livestock industry is pointed out as a point site causing environmental pollution due to massive generation of manure. While livestock manure is conventionally treated through biological processes, composting and anaerobic digestion, these practices pose difficulties in achieving efficient carbon utilization. To address this, this study suggests a pyrolytic valorization of livestock manure, with a focus on enhancing syngas production. Hen manure was particularly chosen due to its abundance of calcium carbonate (CaCO3) compared to other mammalian livestock, exhibiting distinctive thermolytic behaviours. The thermolysis of CaCO3 in hen manure releases carbon dioxide (CO2), simultaneously served as a partial oxidant for the carbon monoxide (CO) enhancement. To further evaluate the effectiveness of CO2, hen manure was pyrolyzed under the presence of CO2. The use of CO2 demonstrated a gas-phase interaction with hen manure-derived volatiles, re-allocating the pyrogenic products into CO-rich syngas. To accelerate the reaction kinetics of CO2, catalytic pyrolysis over a supported Ni catalyst was conducted, further enhancing CO-rich syngas. To assess the environmental advantages, the carbon footprints under various pyrolysis conditions were estimated by confirming the energy consumption and CO2 mitigation potential of pyrogenic products. Therefore, this study highlights that the CO2-mediated pyrolysis of hen manure globally generated offers a potential to mitigate 934.67milliontons of CO2 in annual.

Tandem catalytic upgrading of cow manure pyrolysis vapors by Beta zeolite and nitrogen-doped activated carbon dual catalysts prepared from coal gasification fine slag to produce light aromatic hydrocarbons

Tandem catalytic upgrading of cow manure pyrolysis vapors by Beta zeolite and nitrogen-doped activated carbon dual catalysts prepared from coal gasification fine slag to produce light aromatic hydrocarbons

Fast pyrolysis of raw and acid-washed cattle manure in a fluidized bed reactor for the production of bio-oil

Fast pyrolysis of raw and acid-washed cattle manure in a fluidized bed reactor for the production of bio-oil

Aspects of thermal utilization of organic poultry waste

Relevance. Currently, poultry farming, as part of the agro-industrial complex, is showing strong growth, which leads to an increase in the generation of organic waste. Chicken manure is a problematic organic waste from poultry farming in terms of its quantity, environmental hazard and moisture content. On the other hand, chicken manure is a potential renewable source of phosphorus. The use of chicken manure as a technogenic deposit of phosphorus will improve the level of environmental and food security. Aim. Research of influence of parameters of plasma and pyrolysis treatment of chicken manure on waste weight loss and phosphorus content in biochar. Methods. Experimental studies of the treatment of chicken manure with microwave plasma and induction pyrolysis; determination of the mass fraction of moisture during drying and loss of waste mass during disposal by the gravimetric method; determination of phosphorus in biochar using the Denizhe colorimetric method modified by A. Malyugin and S. Khrenova. Results and conclusions. The author has carried out the experimental studies on the treatment of chicken manure with microwave plasma and induction pyrolysis. It was shown that effective ways to reduce the mass of chicken manure and prevent environmental pollution are the treatment of manure with microwave plasma and its induction pyrolysis. It was established that when chicken manure is processed in microwave plasma in an inert environment at temperatures up to 1560°C, the mass of waste is reduced by 92.76% with an exposure duration of 7 minutes. At the same time, the content of P2O5 in biochar is up to 52.2 g/100 g of biochar. Further exposure to plasma leads to vitrification of the waste. As the time of treatment of chicken manure with microwave plasma increases, the loss of waste mass grows exponentially. Induction pyrolysis of chicken manure in an inert environment at a temperature of 1000°C makes it possible to reduce the mass of waste by 92.30%. P2O5 content in biochar grows with increasing pyrolysis temperature and amounts to 12.64 g/100 g of biochar. Biochar obtained by treating chicken manure with microwave plasma and induction pyrolysis can be considered as a source of phosphorus. The results obtained indicate the possibility of utilizing chicken manure using microwave plasma and induction pyrolysis.

Influence of potassium addition on phosphorus availability and heavy metals immobility of biochar derived from swine manure

Pyrolysis of animal manure at high temperature is necessary to effectively immobilize heavy metals, while the available phosphorus (P) level in biochar is relatively low, rendering it unsuitable for use as fertilizer. In this study, the pretreatment of swine manure with different potassium (K) sources (KOH, K2CO3, CH3COOK and C6H5K3O7) was conducted to produce a biochar with enhanced P availability and heavy metals immobility. The addition of all K compounds lowered the peak temperature of decomposition of cellulose in swine manure. The percentage of ammonium citrate and formic acid extractable P in biochar increased with K addition compared to undoped biochar, with CH3COOK and C6H5K3O7 showing greater effectiveness than KOH and K2CO3, however, water- extractable P did not exhibit significant changes. Additionally, the available and dissolved Si increased due to the doping of K, with KOH and K2CO3 having a stronger effect than CH3COOK and C6H5K3O7. X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed that K addition led to the formation of soluble CaKPO4 and silicate. In addition, the incorporation of K promoted the transformation of labile copper (Cu) and znic (Zn) into the stable fraction while simultaneously reducing their environmental risk. Our study suggest that the co-pyrolysis of swine manure and organic K represents an effective and valuable method for producing biochar with optimized P availability and heavy metals immobility.

Energy potential of plant and animal biomass using in relation to its thermal processing

Relevance. The need for effective utilization of biomass waste generated in significant quantities. Pyrolysis, accompanied by exothermic reactions, is a promising way of biomass processing. Aim. Assessment of the possibility of covering the thermal costs of plant and animal biomass pyrolysis due to heat release during decomposition. Methods. Proximate and ultimate analysis of biomass are determined according to certified methods. Thermal analysis of the studied raw materials was carried out on a Netzsch STA 449 F5 Jupiter synchronous thermal analyzer with an integrated gas analyzer QMS 403 Aeolos; quantitative yield of pyrolysis products was determined according to GOST 3168-93, gas composition was established using the gas analyzer TEST-1 (БОНЭР, Russia). Results and conclusions. According to the results of thermal analysis, it was found that pyrolysis of plant (pine nut shells) and animal (cattle manure) biomass is accompanied by exothermic reactions associated with the organic part decomposition in the temperature range 240–700°C. The value of heat release of exothermic reactions during pine nut shell destruction is 1.39 MJ/kg, a similar value during manure decomposition is 0.31 MJ/kg. This amount of heat allows you to fully cover the thermal costs of pine nut shell pyrolytic processing, the share of covering the thermal costs of manure pyrolysis is ∼30%. An additional source of heat is pyrolysis gaseous products with energy potential equal to 3.28 and 1.58 MJ of thermal energy per 1 kg of processed pine nut shells and manure, respectively.

13. Slow pyrolysis of poultry manure – Performance of the process and fertilising effect of biochar

13. Slow pyrolysis of poultry manure – Performance of the process and fertilising effect of biochar

Involvement of Acid-Leachable Inorganics in Pyrolysis of Pig Manure

Involvement of Acid-Leachable Inorganics in Pyrolysis of Pig Manure

Optimization of Vertical Fixed-Bed Pyrolysis for Enhanced Biochar Production from Diverse Agricultural Residues.

This study examines the pyrolysis of agricultural residues, namely, coconut shells, rice husks, and cattle manure, in a vertical fixed-bed reactor at varying temperatures from 300 to 800 degrees Celsius for biochar production. The research aimed to evaluate the potential of biochar as biofuels, adsorbents, and soil amendments. Proximate, ultimate, and elemental analyses were conducted to determine their composition and caloric values. Several analytical techniques were used in the physical and chemical characterization of the biochar (SEM, FTIR, BET). The results indicated that the highest SBET values were achieved under different conditions for each biochar: 89.58 m2/g for BC-CS-700, 202.39 m2/g for BC-RH-600, and 42.45 m2/g for BC-CD-800. Additionally, all three biochars exhibited the highest caloric values at 600 °C. The results showed that 600 °C is the general optimal temperature to produce biochar from an assortment of biomass materials, considering their use for a variety of purposes. BC-CS-800 had the highest elemental carbon content at 93%, accompanied by a relative decrease in oxygen content. The van Krevelen diagram of biochar products shows that biochars derived from coconut shells and rice husks are suitable for use as fuels. Furthermore, FTIR analysis revealed the presence of oxygen-containing functional groups on the biochar surface, enhancing their pollutant adsorption capabilities. This study provides valuable insights into the scalable and environmentally sustainable production of biochar, emphasizing its role in improving soil quality, increasing energy density, and supporting sustainable agricultural practices.

Comparative investigation on composting and pyrolysis of swine manure: Heavy metals transformation, nitrogen immobilization and integrated environmental risk assessment

Harmless treatment of livestock manure has been a pressing issue due to its contamination of heavy metals and volatilization of nitrogen(N)-containing components during processing. In this paper, the chemical species transformation, leaching characteristics of Cr, Mn, Zn, Cu and conversion of amine N and inorganic N during composting and pyrolysis of swine manure (400°C, 500°C, 600°C and 700°C) were comparatively investigated, and their integrated environmental risk (η) was assessed. According to the ultimate and proximate analysis, pyrolyzed char exhibited better aromaticity and richer functional groups compared with that of compost; Cr, Mn, Zn, Cu were transformed into more stable residual states (F3+F4), and better inhibition of leaching in simulated landfill experiments was shown than compost. However, deamination and cyclocondensation reactions under higher pyrolysis temperatures resulted in N escaping in the form of NH3 and HCN. Considering various pollution coefficients, the integrated ecological risk was reduced by 59.24 % after 600°C pyrolysis, which is the optimal condition for the minimization of the risk of heavy metal toxicity and N volatilization among all the compost and pyrolysis process.

Comparative analysis of kinetic model-fitting methods and selection priority for horse manure pyrolysis

The diverse origins of biomass wastes provide a constraint on the practical application of pyrolysis, as it leads to uncertain chemical reactions, feedstock conversion, and energy consumption. Various model-fit methods are available to identify the decomposition kinetics, however, limited studies have compared the reliability and accuracy of those kinetic models. This work compared five different kinetic models, two based on model-fit methods (Coats–Redfern (CR), Kennedy-Clark (KC) and three based on the application forms of Criado Master Plots (CMP I, CMP II and CMP III). The mass loss data from the pyrolysis of horse manure (HM) through a thermogravimetric analyser was used as a biomass sample for evaluation. Results demonstrated that all five model-fit methods report different kinetics data. Although the model-fit methods (CR and KC) allow a direct determination of kinetic triplets, the accuracy of data is lower. The CMP-II and CMP-III methods (incorporating model-free data in the model-fit methods) showcase multi-step chemical kinetics and better describe the decomposition behavior of HM due to its multi-compositional properties. To obtain kinetic triplets with enhanced accuracy, it is recommended to incorporate model-free data into the model-fit method. Improved precision of the kinetics data is essential for developing experimental parameters and optimizing the process. Future research should include the selection criteria of model-fit methods shown in this study to improve the accuracy of kinetic data.

Impact of Pyrolyzed and Unpyrolyzed Animal Manures on Soil Properties, Carbon Sequestration, and Clover Productivity in Andisol

The use of organic waste in agricultural soil can enhance crop yields, improve waste management, and boost soil carbon (C) sequestration. However, more field data are required to fully understand the impacts of pyrolyzed and unpyrolyzed animal manures. The objectives of this study were (i) to analyze the impact of two pyrolyzed and unpyrolyzed manures on soil properties, soil C storage, and clover productivity and (ii) to examine the biochar’s movement through the soil profile. Poultry litter (PL), dairy manure (DM), poultry litter biochar (PLBC), and dairy manure biochar (DBC) were applied at rates of 8 t ha−1 in a field experiment with red clover (Trifolium pratense L. var. Quiñequeli) in an Andisol. We monitored changes in soil chemical properties, foliar properties, and crop yield after three clover cuttings. To examine the movement of biochars through the soil profile, we set up a lab experiment where field conditions were simulated. PLBC, DBC, and PL increased soil pH by 0.5 (6.44), 0.28 (6.22), and 0.25 (6.19) units, respectively. Soil available P increased in both pyrolyzed and unpyrolyzed PL treatments (by 8.53 mg P kg−1, on average). Clover yields only increased in treatments with amendments that provided more available P and increased the pH. The addition of DBC increased soil total C (30.3%). Both biochars added to the soil surface exhibited little movement through the soil profile (2 to 4 cm). In this study, the pyrolysis of manures emerged as an option for reducing waste volume from the farming industry. Manure biochars proved useful at low rates for enhancing crop yields (PLBC) and storing C in the soil (DBC).

Pyrolysis and co-pyrolysis of cattle manure, rape straw, and their blend: Physicochemical characterization, kinetic triplets, reaction mechanism, and thermodynamic analysis

Cattle manure (CM) and rape straw (RS) are typical agricultural wastes. In present study, pyrolysis and co-pyrolysis of CM, RS, and their blend (MM) were studied by thermogravimetric experiments at different heating rates (10, 20, and 30 °C/min). The kinetic analysis was carried out using three iso-conversional methods, Friedman (FR), Kissinger-Akahira-Sunose (KAS), and Flynn-Wall-Ozawa (FWO). The average apparent activation energies (Eα) values calculated by FR, KAS, and FWO methods were 181.82 kJ/mol, 176.09 kJ/mol, and 196.50 kJ/mol for CM, 221.55 kJ/mol, 204.91 kJ/mol, and 215.08 kJ/mol for RS, and 314.35 kJ/mol, 294.08 kJ/mol, and 304.33 kJ/mol for MM. The overall pyrolysis processes of CM, RS, and MM followed the diffusional and order of reaction models by the master-plots method. Thermodynamic parameters indicated the non-spontaneous and endothermic characteristics of the CM, RS, and MM pyrolysis. The kinetic and thermodynamic analysis will provide critical information for the safe and efficient design of pyrolysis reactors with CM, RS, and MM as feedstocks.

Developing a sorptive material of cadmium from pyrolysis of hen manure

A large amount of manure is generated from concentrated animal feeding operations (CAFOs), leading to serious environmental issues and hazardous risks from pathogens, such as methicillin-resistant Staphylococcus aureus. Therefore, developing an effective method for manure disposal is essential. Thus, in this study, we suggest the use of CO2 in pyrolysis of hen manure (HM) as an effective method to convert the carbon in HM into syngas (especially carbon monoxide (CO)). HM was used and tested as the model compound. From the results of thermo-gravimetric analysis, the decarboxylation of CaCO3 in HM in the presence of N2 was realized at temperatures ranging from 638 to 754 °C. The Boudouard reaction was observed at ≥ 664 °C in the presence of CO2. Despite the lack of occurrence of the Boudouard reaction, more CO formation was observed in the presence of CO2 at ≥ 460 °C. This was deemed as a homogeneous reaction induced by CO2. Considering the high Ca content of HM, HM biochar in N2 and CO2 were used as adsorbent for removal of Cadmium (Cd), which is toxic heavy metal. The adsorption capacities of HM_N2 and HM_CO2 were 302.4 and 95.7 mg g−1, respectively. The superior performance of HM_N2 is mainly attributed to the presence of Ca(OH)2, which provides favorable (alkaline) conditions for precipitation and ion exchange. Our results indicate the environmental benefits from using CO2. Specifically, CO2 (representative greenhouse gas) converted into fuel. Given this, pyrolysis of HM in the presence of CO2 was achieved at ≤ 640 °C, and the atmospheric condition should be switched from CO2 to N2 at ≥ 640 °C to ensure the decarboxylation of CaCO3.

Migration of phosphorus in pig manure during pyrolysis process and slow-release mechanism of biochar in hydroponic application

Pyrolysis is an effective method for treating of livestock and poultry manure developed in recent years. It can completely decompose pathogens and antibiotics, stabilize heavy metals, and enrich phosphorus (P) in biochar. To elucidate the P migration mechanism under different pig manure pyrolysis temperatures, sequential fractionation, solution 31P nuclear magnetic resonance, X-ray photoelectron spectroscopy, X-ray diffraction, and K-edge X-ray absorption near-edge structure techniques were used to analyze the P species in pig manure biochar (PMB). The results indicated that most of the organic P in the pig manure was converted to inorganic P during pyrolysis. Moreover, the transformation to different P groups pathways was clarified. The phase transition from amorphous to crystalline calcium phosphate was promoted when the temperature was above 600 °C. The content of P extracted by hydrochloric acid, which was the long-term available P for plant uptake, increased significantly. PMB pyrolyzed at 600 °C can be used as a highly effective substitute for P source. It provides the necessary P species (e.g. water-soluble P.) and metal elements for the growth of water spinach plants, and which are slow-release comparing with the Hogland nutrient solution.

Effect of pyrolysis temperature on physicochemical characteristics and toxic elements for grub manure-derived biochar.

While traditional solutions for disposing of animal manure are limited by their time-consuming nature and inefficiency, the pyrolysis of animal manure into biochar is considered a promising disposal option, offering high-value benefits. However, there are few research studies on the physicochemical properties and potential utilization pathway of grub manure-derived biochar (GB) prepared at different temperatures. In this study, grub manure (GM) was pyrolyzed at 450, 600 and 750 °C, and the effect of pyrolysis temperature on the characteristics and applications of GB was illustrated. The results showed that increasing pyrolysis temperature promoted the formation of an aromatic structure, enhanced the stability, and improved the surface pore structure of GB. The relationship between pyrolysis temperature and C/N-containing functional groups in GB was quantitatively analyzed. In the process of pyrolysis of GM to GB, carbonates first decomposed, and then, C[double bond, length as m-dash]O broke into C-O and finally condensed to form an aromatic ring structure at elevated pyrolysis temperature. Although GM was rich in organic matter and total N/P/K, the potentially toxic elements (PTEs) (Ni, Cu, Cd, Pb, Zn and As) in GM presented potential risk. The hazard of PTEs in GB was significantly decreased after GM was pyrolyzed. Overall, pyrolysis provided an opportunity for the sustainable management of GM, and GB is a multi-purpose and high-value product that could be applied in soil improvement, environmental remediation, and climate change mitigation for achieving sustainable development.

A new neodymium complex on renewable magnetic biochar nanoparticles as an environmentally friendly, recyclable and efficient nanocatalyst in the homoselective synthesis of tetrazoles.

Inexpensive, stable, selective, and recyclable nanocatalysts, waste regeneration, and utilization of safe and available solvents are of interest and important factors in laboratory science and industrial applications of green chemistry. Therefore, herein, biochar nanoparticles (BNPs) were synthesized through chicken manure pyrolysis as a novel method for waste recycling. Then, in order to improve their recyclability, the obtained BNPs were magnetized using magnetic nickel nanoparticles. Then, the surface of the biochar magnetic nanoparticles (BMNPs) was modified by (3-chloropropyl)trimethoxysilane (3-CPTMS) and further a novel neodymium Schiff-base complex was immobilized on the surface of the modified BMNPs, denoted as Nd-Schiff-base@BMNPs. The obtained supported neodymium complex was used as a practical, selective, biocompatible, commercial, and reusable heterogeneous nanocatalyst. The biochar support of this nanocatalyst was formed from pyrolysis of chicken manure; therefore, it is cheap, economically viable, green and also compatible with the principles of green chemistry. Nd-Schiff-base@BMNPs acts selectively in organic reactions and also it can easily be recovered using an external magnet and reused, which is compatible with the principles of green chemistry. This nanocatalyst was characterized by wavelength-dispersive X-ray spectroscopy (WDX), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), inductively coupled plasma (ICP), and N2 adsorption-desorption (BET method) techniques. In the next step, the catalytic utilization of Nd-Schiff-base@BMNPs was investigated in the homoselective synthesis of 5-substituted 1H-tetrazole compounds from [3 + 2] cycloaddition of sodium azide (NaN3) and organo-nitriles in PEG-400 as a green solvent. Utilizing PEG-400 as a solvent offers various advantages, e.g. cheap, readily available, and environmentally friendly solvent as well as rapid separation and high purity of products. Therefore, this work is fully compatible with the principles of green chemistry.

Valorization of cattle manure via a thermo-chemical process

World population growth and improvements in income levels have led to an increase in the global consumption of animal-sourced proteins. However, the massive production of animal manure has resulted in significant environmental burdens, such as increasing greenhouse gas emissions, eutrophication, and water and soil contamination. As such, this study proposed a sustainable and rapid disposal platform for animal manure as a precautionary approach to attenuate the environmental burdens caused by manure. A pyrolysis process was used to convert cattle manure into value-added products with the aim of achieving both rapid volume reduction and sustainable conversion. CO2 was fed into the process to increase the green/sustainable benefits and the results were compared with pyrolysis with the addition of N2 (inert gas). Pyrolysis oil was the major product of cattle manure pyrolysis. However, because of its complicated composition, pyrolysis oil cannot be considered a beneficial product. Thus, pyrolysis oil was converted into value-added syngas (H2/CO). Under pyrolysis with an introduction of CO2, the homogeneous reaction converted the volatile compounds and CO2 into CO at ≥ 510 ˚C. However, the reaction rate leading the CO2 reactivity was insufficient. To improve CO2 reactivity, supported Ni catalyst was introduced for catalytic pyrolysis. The concentration of CO from CO2-induced pyrolysis jumped 3.5 times (42.0 wt%) when the supported Ni catalyst was loaded in comparison with catalyst free pyrolysis setup. The increase in CO generation led to a decrease in the pyrolysis oil content (benzene analogs and polycyclic aromatic hydrocarbons) because the carbon was mostly reallocated to CO. The results of this study offer a strategic means of valorizing manure into syngas by tailoring the carbon length of the pyrogenic products.

Aromatics production from relay catalytic pyrolysis of cow manure using Ru/C and ZSM-5 dual catalysts synthesized from coal gasification fine slag

Resource utilization of solid waste can aid in gradual substitution of fossil fuels while achieving waste recycling. In this study, residual carbon and ash slag from the coal gasification fine slag were separated by froth flotation, and then was used to prepare Ru/C and ZSM-5 dual catalysts with carbon-rich and ash-rich components as raw materials, respectively. The performance of two catalysts for catalytic upgrading of volatiles from pyrolysis of cow manure (CM) to produce light aromatic hydrocarbons was systematically investigated. The direct pyrolysis products of CM mainly included alcohols, ketones, ethers, and other oxygen-containing compounds. When ZSM-5 was used as the catalyst, the yield of monocyclic aromatic hydrocarbons (MAHs) increased significantly due to the better catalytic cracking and aromatization abilities of ZSM-5 catalyst. However, the yield of phenols in the pyrolysis products improved when Ru/C was used as the catalyst due to the cleavage effect of Ru/C on the C–O bond. When Ru/C and ZSM-5 were used as dual catalysts in relay catalytic pyrolysis of volatiles, the increase in MAHs yield in the pyrolysis product was higher than the total increase obtained under Ru/C and ZSM-5 single catalysis. The possible pathways for the generation of MAHs from CM under Ru/C and ZSM-5 relay catalytic pyrolysis were revealed by the pyrolysis experiment performed on model compounds.

Properties of Poultry-Manure-Derived Biochar for Peat Substitution in Growing Media.

Peat is considered a contentious input in horticulture. Therefore, there is a search for suitable alternatives with similar properties that can be used for partial or complete peat substitution in growing media. Poultry-manure-derived biochar (PMB) is considered such an alternative. This study aimed at determining the properties of PMBs obtained through pyrolysis at selected temperatures and assessing their potentials to substitute peat in growing media based on the selected properties. The scope included the laboratory-scale pyrolysis of poultry manure at the temperatures of 425-725 °C; the determination of selected physico-chemical and physical properties of the obtained biochars, including the contaminants; and the assessment of the potentials of produced biochars to be used as peat substitutes. PMBs contained less than 36% of total organic carbon (TOC). The contents of P and K were about 2.03-3.91% and 2.74-5.13%, respectively. PMBs did not retain N. They can be safely used as the concentrations of heavy metals, polycyclic aromatic hydrocarbons (PAHs), polychlorinatd biphenyls (PCBs), dioxins, and furans are within the permissible values (except for Cr). Due to high pH (9.24-12.35), they can have a liming effect. High water holding capacity (WHC) in the range of 158-232% w/w could allow for the maintenance of moisture in the growing media. PMBs obtained at 525 °C, 625 °C, and 725 °C showed required stability (H/Corg < 0.7).