Hydropyrolysis of kraft hardwood and softwood black liquor

The hydropyrolysis of hardwood and softwood derived black liquor was studied to develop material balance data and to investigate the potential yield of phenolic oils that might be obtained as chemical by-products of a kraft pulp mill. Hydropyrolysis reactions on softwood liquors were found to be more efficient in char formation than those on hardwood liquors. The yield of extractible phenolic oils was low, around 20–30 percent of black liquor organics, but the yields of simple phenols determined by gas chromatography were found to be even lower at 1–5 percent on black liquor organics.     

PRODUCTION OF BIOFUEL FROM SOFT SHELL OF PISTACHIO (PISTACIA VERA L.)

Soft shell of pistachio (Pistacia vera L.) pyrolysis experiments were performed in a fixed-bed reactor to produce bio-oil. The effects of temperature, heating rate, and sweep gas (N₂) flow rates on the yields and compositions of products were investigated. Pyrolysis runs were performed using reactor temperatures between 350° and 500°C with heating rates of 15° and 50°C/min. Nitrogen flow rates varied between 50 and 200 cm³/min and mean particle size was 0.8 mm. The maximum bio-oil yield of 33.18% was obtained in a nitrogen atmosphere with nitrogen flow rate of 150 cm³/min and at 450°C pyrolysis temperature with a heating rate of 50°C/min.The elemental analysis and gross heating value of the bio-oil were determined, and then the chemical composition of the bio-oil was investigated using chromatographic and spectroscopic techniques. The chemical characterization has shown that the bio-oil obtained from soft shell of pistachio can be used as a renewable fuel and chemical feedstock.     

Effects of pyrolysis temperature on the chemical composition of refined softwood and hardwood lignins

The current study uses nuclear magnetic resonance, Fourier-transform infrared spectroscopy and Raman spectroscopy to investigate the evolution of refined softwood and hardwood lignins under various pyrolytic exposures. Little chemical change occurred at pyrolysis temperatures of 250 and 300 °C, whereas significant mass loss and chemical change was observed at 400 and 500 °C. These losses were mainly attributed to evolution of methoxyl, hydroxyl, and propyl groups. Mass loss plateaued following pyrolysis at 500 °C, but rearrangements continued to occur at higher temperatures, resulting in char that became increasingly polyaromatic in nature. Following brief pyrolytic exposures at 500 and 600 °C, the refined hardwood and softwood lignins yielded coal-like products. Lignin pyrolyzed at higher temperatures yielded chars with greater order, similar in composition to coke. These coal and coke-like products are called “lignin-based carbon” (LBC). The polyaromatic nature of the LBC after high temperature pyrolysis was perceived as the result of radical formation and recombination, leading to fused aromatic structures, which occurs more readily at higher temperatures.     

Fixed-bed pyrolysis of coal under hydrogen pressure at low heating rates

Fixed-bed hydropyrolysis has been investigated by treating 100 g coal up to 900°C and 10 MPa. The devolatilization rate of Beringen coal (32.8 wt% volatile matter) treated on a fixed bed approximates to that obtained by flash hydropyrolysis. However, the oil yield is smaller because of the slower heating of the coal and the rather longer residence time of the primary volatile matter in the reaction space. The product gas is mainly methane. The oil composition depends on the temperature of pyrolysis. The benzene content of the oil rises with temperature. At constant temperature, the influence of hydrogen partial pressure is important between 0–1 MPa. At higher pressure, the yields and compositions vary only slightly with pressure. It has also been shown that from 580°C pyrolysis under hydrogen yields an additional quantity of water, when compared with pyrolysis under inert atmospheres or under atmospheric pressure. This additional water comes from the hydrogenation reactions of the hydroxyl functions of heavy phenols and xylenols. This implies a hydrogen consumption (from 0.2–0.3 wt% of the coal), varying with the pyrolysis temperature.     

The formation of mesophase microstructures during the pyrolysis of selected coker feedstocks

Five coker feedstocks ranging from a gilsonite to a decant oil were pyrolyzed at increasing temperatures. The mesophase microstructures in the pyrolysis residues from successive temperature intervals were examined. Observations by polarized-light microscopy revealed that a common pattern of mesophase precipitation, coalescence, and deformation leads to a series of microconstituents whose structures are dependent primarily on the temperature of precipitation, but whose relative proportions depend on the feedstock. For a heating rate of 5°C/hr, the initial mesophase to precipitate during pyrolysis (at 400°C to 430°C) forms a fine-textured Isotropie microstructure which is frozen-in by hardening soon after coalescence of the spherules. Above 430°C, the freshly precipitated mesophase forms a coarse morphology which is deformable by bubble percolation to produce the fine fibrous microstructures of needle coke. The results indicate that the temperature range of the mesophase transformation is one indication of the quality of a feedstock for production of an isotropic or needle coke.     

Bio-oil from olive oil industry wastes: Pyrolysis of olive residue under different conditions

Olive residues were pyrolysed in a fixed bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 7 °C/min. Final temperature range studied was between 400 and 700 °C and the highest liquid product yield was obtained at 500 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. Liquid products obtained under the most suitable conditions were characterised by elemental analyses, FT-IR and ¹H-NMR. In addition, column chromatography was employed and the yields of the sub-fractions were calculated. Gas chromatography was achieved on n-pentane fractions. The results show that it is possible to obtain liquid products similar to petroleum from olive residue if the pyrolysis conditions are chosen accordingly.     

Bio-oil from olive oil industry wastes: Pyrolysis of olive residue under different conditions

Olive residues were pyrolysed in a fixed bed reactor under different pyrolysis conditions to determine the role of final temperature, sweeping gas flow rate and steam velocity on the product yields and liquid product composition with a heating rate of 7 °C/min. Final temperature range studied was between 400 and 700 °C and the highest liquid product yield was obtained at 500 °C. Liquid product yield increased significantly under nitrogen and steam atmospheres. Liquid products obtained under the most suitable conditions were characterised by elemental analyses, FT-IR and ¹H-NMR. In addition, column chromatography was employed and the yields of the sub-fractions were calculated. Gas chromatography was achieved on n-pentane fractions. The results show that it is possible to obtain liquid products similar to petroleum from olive residue if the pyrolysis conditions are chosen accordingly.     

椰衣微波热解工艺的响应面法优化及液体产物组成分析

利用Box-Behnken试验设计，采用响应面法对椰衣微波热解工艺进行优化，考察了热解温度、氮气流速、升温速率和热解时间对液体产物产率的影响。试验结果表明：回归方程模型拟合较好且显著。各个因素对液体产物的产率影响的主次顺序为热解温度>氮气流速>热解时间>升温速率。最佳热解条件为热解温度550℃、氮气流速80 mL/min、升温速率20℃/min、热解时间25 min，在此条件下液体产物产率为38.28%。对液体产物的性质和组成分析发现：优化条件下得到的液体产物中含水量为14.32%，pH值为3.78，热值为24.61 MJ/kg。通过GC-MS对液体产物进行分析，最佳条件下得到的液体产物中主要含有酚、醛、酸、酮类化合物，分别为84.35%、6.01%、3.37%、2.05%，其中酚类化合物的量最高，包括苯酚（33.51%）、对甲酚（9.71%）、2-甲氧基苯酚（10.99%）和4-乙基-2-甲氧基苯酚（5.57%）。     

Influence of alcohol addition on properties of bio-oil produced from fast pyrolysis of eucalyptus bark in a free-fall reactor

Fast pyrolysis of eucalyptus bark was carried out in a free-fall pyrolysis unit at different temperatures ranging from 400 to 550 °C to produce bio-oil, char and gas. The bio-oil produced at optimum temperature was mixed with alcohols with an aim to improve its properties. The results showed that the maximum bio-oil yield of 64.65 wt% on dry biomass basis could be obtained at the pyrolysis temperature of 500 °C. The addition of a small proportion (2.5–10%) of alcohol into the bio-oil could improve its viscosity, stability and heating value. These effects were further enhanced when increasing the alcohol.     

Investigation and Characterization of Lignin Precipitation in the LignoBoost Process

Lignin of high purity can be separated from black liquor using the LignoBoost process, of which the overall efficiency is largely dependent on the precipitation yield of lignin, which depends on the properties of black liquor and process conditions. In this paper, the influences of process conditions on the precipitation yield of lignin from mixed hardwood/softwood black liquor were investigated. The Klason and standard UV method were used to determine lignin concentration. The chemical and structural properties of lignin were also analyzed. The results showed that the precipitation yield of lignin increased along with a decrease in pH and temperature, or with an increase in the ion strength of black liquor, and the yield was lower when mixed softwood/hardwood black liquor was used. It also showed that at a higher precipitation yield the precipitated lignin had a lower average molecular weight but had higher methoxyl and phenolic hydroxyl content.     

The influence of pyrolysis conditions on yield and microporosity of lignocellulosic chars

Chars were prepared from lignocellulosic precursors (plant tissues) by pyrolysis under argon at varying heating rates to final temperatures of 500–900°C. Char yield was found to depend on precursor composition, heating rate below 500°C, and the final temperature attained. Char microporosity, determined by adsorption of CO₂ at 298 K, was found to be relatively independent of the precursor composition and pyrolysis heating rate. The basic microstructure defining the micropore system appeared to be formed by 500°C, although access to the pore volume was restricted at such low temperatures by mass that would be volatilized at higher temperatures.     

The role of carbon biotemplate density in mechanical properties of biomorphic SiC

Biomorphic SiC was prepared from four types of Mediterranean wood as carbon precursor. Carbon biotemplates were obtained by pyrolysis and carbonization up to 1400 °C and they were infiltrated with liquid silicon in two different directions. A linear correlation between bending strength and bioSiC density for different types of softwood and hardwood has been found. Mechanical properties were modelled according to the MSA (minimum solid area) approach. Fairly good correlation was found when biomorphic SiC is treated as porous solid. Moreover, the fabrication of bioSiC from carbon biotemplates heat-treated up to 2500 °C has been additionally studied. An improvement up to 56% in flexural strength has been reached by densification of bioC at such high temperature.     

Value-added products from waste: Slow pyrolysis of used polyethylene-lined paper coffee cup waste

The objectives of this study were to examine how to recycle cup waste efficiently and effectively and to determine if cup waste can be converted into liquid, solid, and gas value-added products by slow pyrolysis. The characteristics and potential utilizations of the pyrolysis products were investigated. The study included the effects of temperature, heating rate, and different feedstocks. The yield of pyrolysis oil derived from cup waste increased from 42% at 400°C to 47% at 600°C, while the yield of char decreased from 26% at 400°C to approximately 20% at 600°C. Acetic acid and levoglucosan were identified as the main components of the pyrolysis oil. The char obtained at 500°C was physically activated at 900°C for 3 h with CO₂. The adsorption capacity of the activated char was investigated with model compounds, such as methyl orange, methylene blue, ibuprofen, and acetaminophen. The results showed that the adsorption capacity of the activated char was similar to that of commercial activated carbon produced from peat. The higher heating value of the produced gas stream calculated at 400°C was 19.59 MJ/Nm³. Also, conventional slow pyrolysis (CSP) and microwave-assisted pyrolysis (MAP) technologies were compared to determine the differences in terms of products yields, composition and characteristics of the pyrolysis oil, and their potential applications. The CSP yields higher liquid products than MAP. Also, the pyrolysis oil obtained from the CSP had significantly more levoglucosan and acetic acid compared to that of the MAP.     

Pyrolysis and hydropyrolysis of Louisiana lignite

Pyrolysis and hydropyrolysis kinetics of five samples of Louisiana lignite have been studied in an atmospheric pressure TG system as a function of heating rate and atmosphere. Final pyrolysis temperature was always 800 °C. The total volatile yield (dry basis) was 33.5–43.8wt%. For all lignites the volatile yield in hydrogen was greater than that obtained in nitrogen at similar conditions. However, variation in heating rate produced an opposite result in the two atmospheres with volatile yield increasing with heating rate in nitrogen but decreasing in hydrogen. Results have been analysed using the distributed activation energy pyrolysis model and parameters compared to similar studies using North Dakota and Montana lignites.     

蔗渣碱木素的热裂解特性

利用热重分析法研究了蔗渣碱木素的热解特性,并利用TG-FTIR和Py-GCMS对碱木素的热解产物种类及分布规律进行了分析。结果表明,木素热解呈现宽温度区域,可分为4个阶段,主要裂解温度范围为200～500℃,在400℃左右失重率最大,残余物得率较高。TG-FTIR分析显示了木素热解过程中气体产物的释放规律,300～500℃为主要热解挥发阶段,大部分气体产物在400℃左右产率达到最大。Py-GCMS分析表明,木素的热解产物大致可分为杂环、苯类芳香族、酚类芳香族、酯和酸等化合物,在主要热分解阶段,随着热解温度的升高,苯类和酚类芳香族化合物的含量增多,600℃时酚类物质的含量最高。     

Characterization of products from slow pyrolysis of palm kernel cake and cassava pulp residue

Slow pyrolysis studies of palm kernel cake (PKC) and cassava pulp residue (CPR) were conducted in a fixed-bed reactor. Maximum liquid yield (54.3 wt%) was obtained from PKC pyrolysis at 700 °C, heating rate of 20 °C/min, N₂ gas flow rate of 200 cm³/min and particle size of 2.03 mm. Fuel properties of bi-oils were in following ranges: density, 1.01–1.16 g/cm³; pH, 2.8–5.6; flash point, 74–110 °C and heating value, 15 MJ/kg for CPR oil and 40 MJ/kg for PKC oil. PKC oil gave main contents of n-C₈–C₁₈ carboxylic acids, phenols, and esters, whereas CPR oil gave the highest amount of methanol soluble fraction consisting of polar and non-volatile compounds. On gas compositions, CPR pyrolysis gave the highest yield of syngas produced, while PKC pyrolysis offered the highest content of CO₂. Pyrolysis chars possessed high calorific values in range from 29–35 MJ/kg with PKC char showing a characteristic of reasonably high porosity material.     

Biofuel production using slow pyrolysis of the straw and stalk of the rapeseed plant

Amongst the renewable alternative energy sources, biomass has a large potential for commercial usage. Pyrolysis is the most important among the thermal conversion processes of biomass. In this study, slow pyrolysis of the straw and stalk of the rapeseed plant was investigated within a tubular reactor under the conditions of static atmosphere, varying temperatures of 350°, 450°, 550° and 650°C and at heating rates of 10°C min⁻¹ and 30°C min⁻¹. The maximum liquid yield was observed to be evolving at 650°C pyrolysis temperature and at a heating rate of 30°C min⁻¹. The various characteristics of pyrolytic oil obtained under these conditions were identified. Following the chemical characterization, the pyrolytic oil originated from the straw and stalk of the rapeseed plant is presented as a biofuel candidate.     

Mathematical modelling of lignin pyrolysis

Seven lignins from different sources were pyrolysed (i) isothermally in vacuum over the temperature range 300–1300 °C and (ii) at a constant heating rate of 30 °C min^?1 and a pressure of 0.1 MPa over the temperature range 150–900 °C. The mass fraction of each product—char, tar and gas species—and the elemental composition of the char and the tar were determined for the flash pyrolysis experiments. The evolution rates of the gas species and the tar versus the dynamic temperature of pyrolysis were determined for the constant heating rate pyrolysis experiments. Although the amount of each product species varied from lignin to lignin, the evolution rates were insensitive to the lignin source and the extraction process. To model the data, modifications were made to a recently developed model of coal pyrolysis. The model proved to be successful in simulating both the data from vacuum flash pyrolysis and constant heating rate pyrolysis of Iotech lignin.     

Pyrolytic characteristics of Jatropha seedshell cake in thermobalance and fluidized bed reactors

Pyrolytic kinetic parameters of Jatropha seedshell cake (JSC) were determined based on reaction mechanism approach under isothermal condition in a thermobalance reactor. Avrami-Erofeev reaction model represents the pyrolysis conversion of JSC waste well with activation energy of 36.4 kJ mol^?1 and frequency factor of 9.18 s^?1. The effects of reaction temperature, gas flow rate and feedstock particle size on the products distribution have been determined in a bubbling fluidized bed reactor. Pyrolytic bio-oil yield increases up to 42 wt% at 500 °C with the mean particle size of 1.7 mm and gas flow rate higher than 3U _mf , where the maximum heating value of bio-oil was obtained. The pyrolytic bio-oil is characterized by more oxygen, lower HHVs, less sulfur and more nitrogen than petroleum fuel oils. The pyrolytic oil showed plateaus around 360 °C in distribution of components’ boiling point due to high yields of fatty acid and glycerides.