Liquid phase equilibrium of phenol extraction from bio-oil produced by biomass pyrolysis using thermodynamic models

Utilization of biomass as a new and renewable energy source is being actively conducted by various parties. One of the technologies for utilizing or converting biomass as an energy source is pyrolysis, to convert biomass into a more valuable product which is bio-oil. Bio-oil is a condensed liquid from the vapor phase of biomass pyrolysis such as coconut shells and coffee shells. Biomass composition consisting of hemicellulose, cellulose, and lignin will oxidize to phenol which is the main content in bio-oil. The total phenolic compounds contained in bio-oil are 47.03%(coconut shell) and 45%(coffee shell). The content of phenol compounds in corrosive bio-oils still quite high, the use of this bio-oil directly will cause various difficulties in the combustion system due to high viscosity, low calorific value, corrosivity, and instability. Phenol compounds have some benefits as one of the compounds for floor cleaners and disinfectants which are contained in bio-oil.The correlation between experimental data and calculations shows that the UNIQUAC Functional-group Activity Coefficients(UNIFAC) equilibrium model can be used to predict the liquid–liquid equilibrium in the phenol extraction process of the coconut shell pyrolysis bio-oil. While the Non-Random Two Liquid(NRTL) equilibrium model can be used to predict liquid–liquid equilibrium in the extraction process of phenol from bio-oil pyrolysis of coffee shells.

Bio-Oil Production from Biomass by Flash Pyrolysis in a Three-Stage Fluidized Bed Reactors System

A novel system of fast pyrolysis and vapour quenching was developed at pilot scale to obtain bio-oil from biomass. The system uses three-stage of interconnected fluidized bed reactors that continuously circulate silica sand from an internal pyrolysis reactor to a second external annular reactor for char burning, which generates most of the heat required by the pyrolysis reactor, and a third sand-preheating reactor that burns non-condensable pyrolysis gas. The hot vapours, after high temperature cleaning, are quenched in a flash cooling system. The process generates up to 62% of bio-oil, 25% of char and 13% of non-condensable gas. The heat requirements for the total system are provided by burning part of the char and non-condensable gases generated in the pyrolysis step and by preheating the fluidizing gas for the pyrolysis reactor.

Production of Bio-Oil from Pyrolysis of Olive Biomass with/without Catalyst

In this study olive biomass was pyrolysis in a 400 cm3 stainless steel reactor. It was externally heated by an electrical furnace in which the temperature is measured by a thermocouple inserted into the bed. The effect of the catalyst ratio to the biomass (5%, 10%, 15%, 20%, 30% and 40%) on the pyrolysis yield was investigated and compared with the uncatalyzed pyrolysis yield product. The bio-oil products yield from the pyrolysis process was found to increase as the catalyst ratio increased. The bio-oil yield from the olive oil-cake, which was 36.1% without the catalyst, reached the maximum value of 39.3% on using activated catalyst at 10% by weight. The gas products yield was found to increase upon using catalyst compared to the non-catalytic pyrolysis. The reduction in the bio-oil yield product was accompanied with a significant reduction in the oxygen content. The pyrolysis oil was examined using chromatographic analysis techniques. The chemical characterization showed that the bio-oil obtained from olive oil cake might be potentially valuable as a fuel and chemical feedstock.

High Quality Bio-Oil Obtained from Catalyzed Pyrolysis of Olive Mill Solid Wastes in a Bi-Functional Reactor

Olive Mill Solid Wastes (OMSW) released in nature without any treatment is a major environmental problem in the Mediterranean region. In this work, the catalyzed pyrolysis of OMSW has been investigated. A catalyst based on SBA-15 mesoporous silica doped with chromium ferrite nanoparticles was prepared by the double solvent technique (DS). The prepared catalyst was characterized by scanning electron microscopy (SEM), Wide and Small Angle X-ray Scattering (WAXS, SAXS), Energy Dispersive X-ray (EDX) and FT-IR spectroscopies. Reverse spinel chromium ferrite nanoparticles were located inside the SBA-15 pores as confirmed by SEM images. The obtained catalyst was tested for pyrolysis reactions of OMSW. Several parameters were studied to optimize the conditions of the pyrolysis reaction in order to increase the bio-oil conversion yield. The GC-MS results demonstrated that the quality of the obtained bio-oil was improved by decreasing the quantity of phenolic and oxygenated components as well as the size of the obtained molecules. The produced bio-oil from pyrolysis of OMSW is identical to that obtained from the pyrolysis of commercial cellulose under the same conditions. A 37% conversion yield of bio-oil was obtained for the best conditions.

Production of liquid bio-fuel from catalytic de-oxygenation:Pyrolysis of beech wood and flax shives

This study presents a detailed analysis of the catalytic de-oxygenation of the liquid and gaseous pyrolytic products of two biomasses (beech wood and flax shives) using different catalysts (commercial HZSM-5 and H-Y,and lab-synthesised Fe-HZSM-5,Fe-H-Y,Pt/Al2O3 and CoMo/Al2O3). The experiments were all conducted in a semi-batch reactor under the same operating conditions for all feed materials. BET specific surface area,BJH pore size distribution and FT-IR technologies have been used to characterise the catalysts,while gas chromatography-mass spectrometry (GC-MS),flame ionisation detection (GC-FID) and thermal conductivity detection (GC-TCD) were used to examine the liquid and gaseous pyrolytic products. It was firstly seen that at higher catalyst-to-biomass ratios of 4∶1,de-oxygenation efficiency did not experience any further significant improvement. FeHZSM-5 was deemed to be the most efficient of the catalysts utilised as it helped reach the lowest oxygen contents in the bio-oils samples and the second best was HZSM-5. It was also found that HZSM-5 and H-Y tended to privilege the decarbonylation route(production of CO),whilst their iron-modified counterparts favoured the decarboxylation one (production of CO2) for both biomasses studied. It was then seen that the major bio-oil components (carboxylic acids) underwent almost complete conversion under catalytic treatment to produce mostly unoxygenated aromatic compounds,phenols and gases like CO and CO2. Finally,phenols were seen to be the family most significantly formed from the actions of all catalysts.

纤维素生物质与废塑料共催化热解制取富烃液体燃料的研究进展

生物质能是国际公认的零碳可再生能源,其高效利用成为缓解能源与环境危机的关键,并对中国实现“碳达峰”和“碳中和”的目标具有重要意义。纤维素生物质与废塑料的共催化热解技术,不仅能制备高附加值的富烃液体燃料,还可达到“以废治废”的目的,进而实现生物质与废塑料的高效资源化利用。本工作从生物质与废塑料高值化利用的角度出发,对生物质和废塑料共催化热解制备富烃液体燃料的研究现状进行了综述,介绍了纤维素生物质和废塑料的基础化学特性差异,论述了废塑料种类、催化剂种类、物料和催化剂比例、催化热解温度等因素对生物质和废塑料共催化热解生物油产率和品质的影响,阐述了生物质和废塑料单独催化热解过程中的化学反应机理,并揭示了共催化热解过程中的协同反应机理,展望了该领域未来的发展方向,为生物质与废塑料的高附加值利用提供参考与思路。

灰分中碱和碱土金属对生物质快速热解生物油组分的影响

生物质灰分中的碱和碱土金属(AAEMs)对快速热解生物油的产率和组分分布具有显著影响。本研究选取玉米秸秆为原料,研究梯级脱灰预处理(蒸馏水、醋酸铵和盐酸)对AAEMs的选择性脱除及其生物油组分的影响,研究了碱和碱土金属类别(K、Ca、Na和Mg)、盐质量分数(0.5%、2.5%、5%)和不同钾盐的酸根(SO_(4)^(2-)、NO_(3)^(-)、CO_(3)^(2-)、HCO_(3)^(-)、AC^(-)、PO_(4)^(3-))对生物油组分的影响。结果表明,在梯级脱灰预处理过程中,随着脱灰溶液酸性程度加深,AAEMs的脱除率逐渐上升,根据AAEMs在梯级脱灰过程中的选择性脱除规律,可将其在生物质中的赋存形态分为水溶性(K)、离子交换性(Ca和Mg)和酸溶性(Na)等形态。经过碱和碱土金属盐浸渍后,AAEMs将起到催化剂的作用,促进热解中间产物左旋葡聚糖的二次降解,导致其相对含量显著降低,形成更多的呋喃和酮类等轻质含氧化合物,导致2,3-二氢苯并呋喃、酮类和长链烷烃等组分的含量显著增加。不同钾盐酸根离子对脱水糖的二次裂解反应及木质素芳基醚键和酚羟基的裂解反应具有较大的影响,根据酸根的酸性强弱,对脱水糖裂解反应的影响大小顺序为HCO_(3)^(-)>CO_(3)^(2-)>AC^(-)>PO_(4)^(3-)>Cl^(-)>NO_(3)^(-)>SO_(4)^(2-),而对木质素芳基醚键和酚羟基的裂解反应影响大小顺序为CO_(3)^(2)->Cl^(-)>HCO_(3)^(-)PO_(4)^(3-)≈AC^(-)>SO_(4)^(2-)≈NO_(3)^(-).

FLASH PYROLYSIS OF BIOMASS PARTICLES IN FLUIDIZED BED FOR BIO-OIL PRODUCTION

Biomass utilization could relieve the pressure caused by conventional energy shortage and environmental pollution. Advantage should be taken of the abundant biomass in China as clean energy source to substitute for traditional fossil fuels. At present, flash pyrolysis appears to be an efficient method to produce high yields of liquids that could either be directly used as fuel or converted to other valuable chemicals. Experiments were carried out of pyrolyzing biomass particles in a hot dense fluidized bed of sand to obtain high-quality bio-oil. Among four kinds of biomass species adopted in our experiment, Padauk Wood had the best characteristics in producing bio-oil. GC-MS analysis showed bio-oil to be a complex mixture consisting of many compounds. Furthermore, an integrated model was proposed to reveal how temperature influences biomass pyrolysis. Computation indicated that biomass particles underwent rapid heating before pyrolysis.

On-line catalytic upgrading of biomass fast pyrolysis products

Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was employed to achieve fast pyrolysis of biomass and on-line analysis of the pyrolysis vapors. Four biomass materials (poplar wood, fir wood, cotton straw and rice husk) were pyrolyzed to reveal the difference among their products. Moreover, catalytic cracking of the pyrolysis vapors from cotton straw was performed by using five catalysts, including two microporous zeolites (HZSM-5 and HY) and three mesoporous catalysts (ZrO2&TiO2, SBA-15 and Al/SBA-15). The results showed that the distribution of the pyrolytic products from the four materials differed a little from each other, while catalytic cracking could significantly alter the pyrolytic products. Those important primary pyrolytic products such as levoglucosan, hydroxyacetaldehyde and 1-hydroxy-2-propanone were decreased greatly after catalysis. The two microporous zeolites were ef-fective to generate high yields of hydrocarbons, while the three mesoporous materials favored the formation of furan, furfural and other furan compounds, as well as acetic acid.

Semi-Interpenetrating Novolac-Epoxy Thermoset Polymer Networks Derived from Plant Biomass

Bio-based phenol-formaldehyde polymer (BioNovolac) was developed by reacting molar excess of bio-oil/phenolwith formaldehyde in acidic medium. Glycidyl 3,5-diglycidoxybenzoate (GDGB), was prepared by directglycidylation of α-resorcylic acid (RA), a naturally occurring phenolic monomer. GDGB was crosslinked in thepresence of BioNovolac by anionic polymerization. Fourier transform infrared spectroscopy (FTIR) confirmedthe formation of semi-interpenetrating polymer networks. The glass transition temperature and moduli of biobasedcrosslinked systems were observed to increase with increasing GDGB content. Active chain density andmass retention measured by dynamic mechanical analysis (DMA) and Soxhlet extraction, respectively, indicated ahigh crosslink density of the cured networks. Scanning electron microscopy (SEM) images depicted thehomogeneity of the bulk phase. The preparation of bio-based epoxy-novolac thermoset network resulted inreduced consumption of petroleum-based chemicals.

Upgrading of biomass fast pyrolysis oil over a moving bed of coal char

Fast pyrolysis of sawdust(SD)and upgrading of the derived bio-oil*(water-free basis)over Shenmu bituminous coal char(SMC)were conducted in an integrated free fall pyrolyzer and moving bed upgrading reactor.The water soluble and heavy bio-oil*(THF soluble)yields decrease and the content of light bio-oil*(CH_(2)Cl_(2) soluble)increases significantly compared that without SMC despite the decrease of light bio-oil*yield.Chemical analyses of the light bio-oil*were performed using GC-MS and ^(1)H NMR techniques.The results show that during volatiles-char interaction,the SMC plays important roles in deoxygenation and denitrogenation.The role of SMC in the upgrading process was explored by BET,FT-IR and XRD characterization.The porous structure provides reaction active sites for the bio-oil upgrading.After volatiles-char interaction,the specific surface area of SMC decreases significantly and the carbon crystallite size increases.With increasing the char updating rate from 1 g/min to 4 g/min,the relatively fresh SMC surface leads to the increased active sites,the conversion of heavy bio-oil*is slightly promoted and the removal effects of heteroatoms(O,N)compounds in the light bio-oil*are enhanced.The changes in SMC specific surface area and microcrystalline size are weakened accordingly.

Bio-oil production from pyrolysis of oil palm biomass and the upgrading technologies:A review

Oil palm biomass(OPB)represents major portion of the lignocellulosic waste in Malaysia that can be converted into bio-oil.This review aims to provide important insights in OPB-derived bio-oil production by first discussing the chemical compositions of different OPB and their effects to the bio-oil yield and quality obtained from pyrolysis process,followed by discussing the addition of plastics and catalysts into the pyrolysis for bio-oil upgrading,and lastly summarizing the existing technoeconomic and environmental studies and the potential use of process integration and intensification in this topic.Polypropene(PP),low density polyethylene(LDPE),and high density polyethylene(HDPE)have been commonly used in co-pyrolysis of OPB,which can effectively increase the heating value of bio-oil up to 80%that of diesel.Likewise,acidic,basic,and neutral catalysts have been applied to increase the amount of hydrocarbon and phenol in the bio-oil,further improving the heating value to be comparable to diesel.The bio-oil production from OPB is currently still limited to demonstration scale despite the favorable environmental compatibility and technoeconomic feasibility shown by studies focused on empty fruit bunch(EFB).Several promising advanced pyrolysis processes that integrate other processes such as anaerobic digestion,hydrogen production process,and heat and power generation units as well as the advanced reactor designs are also overviewed here as future innovation of the bio-oil production from OPB,which may play more significant role as the technology matures.

Sustainable Biofuel Production from Brown and Green Macroalgae through the Pyrolysis

The escalating demand for energy coupled with environmental concerns necessitates exploring sustainable alternatives to fossil fuels.The study explores the viability of using large ocean-based seaweeds as a source of thirdgeneration biomass,specifically focusing on their conversion to biofuel via the process of pyrolysis.Sargassum plagiophyllum and Ulva lactuca represent prevalent forms of macroalgae,posing significant discharge challenges for coastal regions globally.However,the exploration of their potential for bio-oil generation via pyrolysis remains limited.This study investigates the pyrolysis process of S.plagiophyllum and U.lactuca for biofuel production,aiming to provide valuable insights into their utilization and optimization.Pyrolysis experiments were conducted within temperature ranges of 400°C to 600°C and durations of 10 to 50 min using a batch reactor.The chemical analysis of the synthesized bio-oil indicated it contains critical compounds such as organic acid derivatives,furans,nitrogenous aromatics,and aliphatic hydrocarbons.The effectiveness of converting the initial biomass into bio-oil is significantly influenced by the pace at which the biomass undergoes decomposition,underscoring the importance of comprehending the kinetic aspects of this conversion.By applying the Arrhenius formula,we calculated the activation energies and frequency factors,with the findings for S.plagiophyllum being 15.27 kJ/mol and 0.477 s^(-1),and for U.lactuca,the values were 43.17 kJ/mol and 0.351 s^(-1),correspondingly.These findings underscore the potential of brown and green macroalgae as sustainable sources for biofuel production via pyrolysis,offering insights for further optimization and valorization efforts in the quest for renewable energy solutions.

Correlation between solubility parameters and recovery of phenolic compounds from fast pyrolysis bio-oil by diesel extraction

Fast pyrolysis bio-oils(fpBO)were extracted with two alternative commercial transportation fuels,hydrocarbon diesel and bio-diesel.The extraction of fpBO with commercial diesel fuel provided a yield of 4.3 wt%,but the yield increased significantly to 26.6 wt%when bio-diesel was the extractant.The molecular weight of fpBO before and after extraction were consistent with the loss of a more soluble,low molecular weight fraction from the crude fpBO.The relative energy difference(RED),based on the Hansen solubility parameter(HSP),is used to examine the extraction efficiency of specific compounds in the two different‘solvents’.Differences in the RED values could be used to rationalize differences in the partitioning of common fpBO phenolics.

杨木湿法烘焙预处理耦合金属改性多级孔分子筛催化热解制取轻质芳烃

轻质芳烃是化工领域重要的基础有机原料,生物质催化热解的技术路线可制取生物基的轻质芳烃化学品。首先,采用湿法烘焙预处理,对杨木进行协同脱氧和脱灰改性提质;其次,采用NaOH脱硅预处理和负载活性金属(Zn、Ga和Fe),对微孔HZSM-5进行修饰改性,构建金属改性多级孔HZSM-5催化剂,并将其用于湿法烘焙杨木催化热解,研究烘焙温度、催化剂改性、催化剂与原料质量比和热解温度等参数对轻质芳烃产率的影响。结果表明,随着湿法烘焙温度的升高,杨木的脱氧率和碱/碱土金属脱除率逐渐增加,其中,O、K、Mg、Ca和Na的最大脱除率分别为47.96%、90.99%、86.65%、66.09%和36.29%。与HZSM-5相比,采用NaOH脱硅后的多级孔HZSM-5(Hie-H)及金属改性的多级孔HZSM-5(Ga/Hie-H、Zn/Hie-H和Fe/Hie-H),均促进了轻质芳烃的形成,其中,Zn/Hie-H对杨木湿法烘焙后固体产物催化热解制取轻质芳烃产率最高;在湿法烘焙温度为220℃,Zn/Hie-H与烘焙杨木质量比为3∶1,热解温度为850℃时,轻质芳烃的产率达到最大值,为7.83×107p.a./mg。

温和条件下ZnCl_(2)原位催化松木粉快速热裂解制生物油及生物炭应用

生物质快速热裂解是生物质转化利用的有效途径,但常因是非催化过程,裂解温度高导致生物油成分复杂难控。本实验以ZnCl_(2)为催化剂,研究了木质素、纤维素、玉米芯和松木粉的热解过程,旨在探索原位催化对快速热裂解的强化作用。本实验通过热重曲线拟合,获得了热裂解的活化能;通过快速热裂解实验,研究了催化作用下热解油组成变化。结果表明,ZnCl_(2)催化可显著降低生物质裂解温度,简化生物油组成。在350℃快速热裂解松木粉获得了47%生物油产率,主要成分是纤维素和半纤维素的衍生物。ZnCl_(2)可显著降低纤维素裂解的活化能(由304.78 kJ/mol降低至112.46 kJ/mol),而对木质素的裂解影响不大。裂解后的碳渣在600℃二次碳化可获得性能良好的活性炭,苯酚吸附容量可达165 mg/g。

Multi-parametric optimization of the catalytic pyrolysis of pig hair into bio-oil

The low yield and poor fuel properties of bio-oil have made the pyrolysis production process uneconomic and also limited bio-oil usage.Proper manipulation of key pyrolysis variables is paramount in order to produce high-quality bio-oil that requires less upgrading.In this research,the pyrolysis of pig hair was carried out in a fixed-bed reactor using a calcium oxide catalyst derived from calcination of turtle shells.In the pyrolysis process,the influence of three variables-temperature,heating rate and catalyst weight-on two responses-bio-oil yield and its higher heating value(HHV)-were investigated using Response Surface Methodology.A second-order regression-model equation was obtained for each response.The optimum yield of the bio-oil and its HHV were obtained as 51.03%and 21.87 mJ/kg,respectively,at 545oC,45.17oC/min and 2.504 g of pyrolysis temperature,heating rate and catalyst weight,respectively.The high R2 values of 0.9859 and 0.9527,respectively,obtained for the bio-oil yield and its HHV models using analysis of variance revealed that the models can adequately predict the bio-oil yield and its HHV from the pyrolysis process.

生物质快速裂解液体产物的分析

应用萃取及柱层析的分离方法将生物质快速裂解油分离成 4种组分 :烷烃、芳烃、极性组分和难挥发性组分 ;并应用气相色谱、气相色谱 -质谱、核磁共振等现代分析测试技术 ,对水相和油相中各分离组分分别分析和鉴定 。

生物质快速热解制备液体燃料

本文回顾了生物质快速热解液化技术的国内外研究现状,重点叙述了初级生物油的化学组成和燃料性质,指出生物油是一种复杂的含氧有机混合物,具有水分含量高、氧含量高、热值低、酸含量高、安定性差和化石燃油不互溶等独特的性质;针对这些性质,介绍了几种常用的生物油精制提炼方法,包括催化裂解、催化加氢、高温热解气过滤、添加助剂、催化酯化、柴油乳化以及制备富氢合成气与费托合成,并分析了各种精制技术发展的关键问题。

流化床生物质快速热裂解试验及生物油分析

在自行研制的一套进料量为5kg/h流化床上,选用高铝矾土为流化床床料,选择450℃、475℃、500℃和525℃四个反应温度对玉米秸秆粉的快速热裂解规律进行了研究,主要考察了不同反应温度对热裂解产物收集率的影响。在热解温度为500℃左右时,生物油收集率具有相对高的数值:37.5%。所得到生物油有两个分层,利用气相色谱-质谱联用仪对各自成分进行了定性分析。